The purpose of this study is to check out the involvement of entropy in Mpemba effect. Provided that preheating of the water the cooling duration is reduced, we theoretically show that water gains more entropy when warmed and re-cooled to the original temperature.

Materials design for processing and application requires fundamental understanding of their properties based interatomic interaction. The use of the novel concept of total bond order density (TBOD) as a single quantum mechanical metric to characterize the internal cohesion of a crystal and correlate with the calculated physical properties is particularly appealing. This requires detailed first-principles calculation of the electronic structure, interatomic bonding and related properties. In this article, we use this new concept and apply it to chalcogenide crystals based on data obtained from 25 crystals: Ag₂S, Ag₂Se, Ag₂Te, As₂S₃, As₂Se₃, As₂Te₃, As₄Se₄, Cu₂S, Cu₂Se, Cu₂Te, Cu₄GeS₄, Cu₂SnS₃, Cu₂SnSe₃, GeS₂, GeSe₂, Ge₄Se₉, Sb₂S₃, Sb₂Se₃, Sb₂Te₃, SnS, SnSe, CdSe, CdTe, ZnSe, and ZnTe. Together with the calculated optical and mechanical properties, we demonstrate the efficacy of using this novel approach for materials design that could facilitate the exploration and development of new chalcogenide crystals and glasses. Moreover, the TBOD and its partial components (PBOD) could be the key descriptors in machine learning protocol for broader scale design when a large database is available.

The structural performance of reinforced concrete relies heavily on the bond between reinforcement and concrete. In nonlinear finite element analyses, bond is either modelled by merged, also called perfect bond, or coincident with slip, also called bond-slip, approaches. Here, the performance of these two approaches for the modelling of failure of reinforced concrete was investigated using a damage-plasticity constitutive model in LS-DYNA. Firstly, the influence of element size on the response of tension-stiffening analyses with the two modelling approaches was investigated. Then, the results of the two approaches were compared for plain and fibre reinforced tension stiffening and a drop weight impact test. It was shown that only the coincident with slip approach provided mesh insensitive results. However, both approaches were capable of reproducing the overall response of the experiments in the form of load and displacements satisfactorily for the meshes used.

The aim of this study was to using a lignin based resin (LB) to improve the performance of the soy flour based adhesive. Soy flour (SF), polyamidoamine-epichlorohydrin (PAE), LB was used to develop a plywood adhesive. The solid content and viscosity of the adhesive, functional groups, thermo-stability, and crystallinity of the cured adhesive were characterized and the performance of the resultant adhesive was evaluated by fabricating three-ply plywood. Results showed using LB and PAE mixture to modify SF adhesive improves dry and wet bond strength by 66.3 and 184.2%. PAE contributed more for the wet bond strength improvement and the LB contributed more for the dry bond strength. The improvement was attributed to: 1) LB/PAE reacted with the functions of the soy protein and form a cross-linking network; 2) Polycondensation reaction between LB molecules further improved crosslinking density of the adhesive and formed a interpenetration structure with crosslinked protein; 3)The easy penetration of LB on wood surface and formed more interlock with wood. The denser structure created by LB and PAE mixture improved the thermal stability and decreased the crystallinity of cured adhesive. The usage of the LB and PAE mixture increased solid content by 35.5%, meanwhile, makes its viscosity acceptable for the industrial application.

Interfaces between layers in 3D-printed elements produced by extrusion-based material deposition were investigated on both macro- and micro-scales. On the macro-scale, compression and bend tests were performed on two 3D-printable cement-based compositions (3PCs), namely C1 and C2. The influences of binder composition and time interval between layers on layer-interface strength were critically analyzed. In the context of additive manufacturing, the optimized composition C2, containing pozzolanic additives, exhibited mechanical performance superior to that of the mixture with Portland cement as the sole binder. In particular, Mixture C2 showed a less pronounced decrease in interface tensile strength. Even for time intervals between depositions of two layers as long as 1 day the loss in corresponding flexural strength was below 25%, as compared with C2 specimens tested in the perpendicular direction. In contrast, the decrease in flexural strength measured for C1 specimens amounted to over 90% for the same set of parameters. Higher porosity at the interfaces of the printed concrete layers was identified as the cause for the lower interface strengths of C1. Microscopic observations supported the findings of the macroscopic investigations. While a pronounced recovery (“self-healing”) of the porous, discontinuous interlayers was observed with increasing age for Mixture C2, in case of C1 the filling products grown in the porous interlayer were found to be non-strengthening.

Theoretical approaches to calculate pKa values for Brønsted acids is a challenging task that, most of the time, involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, by considering the electrostatic potential on acidic hydrogen atoms in a similar fashion that a σ–hole is defined, we calculated the maximum surface potential, V_S,max, and used it as a descriptor to correlate it with experimental acidity constants. These values were calculated using the CPCM implicit solvent model (water) with six different methods: five density functionals and the Møller–Plesset second order perturbation theory. Six different basis sets were combined with each method in order to benchmark a total of thirty-six levels of theory. Overall, 1080 calculations were performed and found to correlate with experimental data. The ωB97X-D/6-31+G(d,p) level of theory stands as the best one for consistently reproduce the reported pKa values.

A series of MgAl-layered double hydroxide (MgAl-HT), the calcined form at 500^oC (MgAlO_x) and the re-hydrated one at 25^oC (MgAl-HT-RH) were synthesized. Physicochemical properties of the catalysts were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM). Surface area of the as-synthesized, calcined and re-hydrated catalysts was determined by N₂ physisorption at -196^oC. CO₂-teperature programmed desorption (CO₂-TPD) was applied to determine the basic sites of catalysts. The catalytic test reaction was carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. The Henry products (1-15) were obtained in a very good yield using MgAl-HT-RH catalyst either by conventional method at 90^oC in liquid phase, or under microwave irradiation method. The mesoporous structure and basic nature of re-hydrated solid catalyst were responsible for their superior catalytic efficiency. The robust nature was determined by using the same catalyst for five times, where the product % yield was almost unchanged significantly.

Geometallurgy has become an important toll to predict the process behavior of the ores, and to decrease the production risks cause by variability of geological settings. In this paper geometallurgical index for grinding properties of the ore has investigated. In a comprehensive research at Sarcheshmeh porphyry copper mine, geological features, what were supposed to affect the main process responses including product’s grade-recovery, and plant’s throughput, were subjected to investigate as the possible geometallurgical indexes. The rock breakage variability, in terms of a ball mill grinding circuit and its effects on the plant throughput and energy consumption are presented. Ninety samples were collected based on geological features including lithology, hydrothermal alteration, and geological structures. The samples were characterized using XRD, XRF, and electron and optical microscopy. A simulated test method for Bond ball mill work index (BWI) was used to perform the comminution test. The results showed BWI values vary from 5.67 kWh/t to 20.21 kWh/t. Examination of the possible correlations between BWI and the geological features showed that the key geological feature related to comminution variability is lithology. In addition, the hydrothermal alteration would be an effective parameter in the period that the plant is fed with a single lithology

Prereactive complexes in noncovalent organocatalysis are sensitive to the relative chirality of the binding partners and to hydrogen bond isomerism. Both effects are present when a transiently chiral alcohol docks on a chiral α-hydroxy ester, turning such 1:1 complexes into elementary, non-reactive model systems for chirality induction in the gas phase. With the help of linear infrared and Raman spectroscopy in supersonic jet expansions, conformational preferences are investigated for benzyl alcohol in combination with methyl lactate, also exploring p-chlorination of the alcohol and the achiral homolog methyl glycolate to identify potential London dispersion and chirality effects on the energy sequence. Three of the four combinations prefer barrierless complexation via the hydroxy group of the ester (association). In contrast, the lightest complex shows predominantly insertion into the intramolecular hydrogen bond, like the analogous lactate and glycolate complexes of methanol. The experimental findings are rationalized with computations and a uniform helicality induction in the alcohol by the lactate is predicted, independent on insertion into or association with the internal lactate hydrogen bond. p-Chlorination of benzyl alcohol has a stabilizing effect on association, because the insertion motif prevents a close contact between the chlorine and the hydroxy ester. After simple anharmonicity and substitution corrections, the B3LYP-D3 approach offers a fairly systematic description of the known spectroscopic data on alcohol complexes with α-hydroxy esters.

In this paper we investigate the optimal investment strategy for a defined contribution (DC) pension plan during the decumulation phrase which is risk-averse and pays close attention to inflation risk. The plan aims to maximize the expected constant relative risk aversion (CRRA) utility from the terminal wealth by investing the wealth in a financial market consisting of an inflation-indexed bond, an ordinary zero coupon bond and a risk-free asset. We derive the optimal investment strategy in closed-form using the dynamic programming approach by solving the corresponding Hamilton-Jacobi-Bellman (HJB) equation. Our theoretical and numerical results reveal that under some rational assumptions, an inflation-indexed bond do has significant advantage to hedge inflation risk.

Quasicrystals are a class of ordered solids made of typical metallic atoms but they do not exhibit the physical properties usually signaling the presence of metallic bonding and their electrical and thermal transport properties resemble a more semiconductor-like than metallic character. In this paper I first review a number of experimental results and numerical simulations suggesting that the origin of the unusual properties of these compounds can be traced back to two main features. For one thing, we have the formation of covalent bonds among certain atoms grouped into clusters at a local scale. Thus, the nature of chemical bonding among certain constituent atoms should play a significant role in the onset of non-metallic physical properties of quasicrystals bearing transition-metal elements. On the other hand, the self-similar symmetry of the underlying structure gives rise to the presence of an extended chemical bonding network due to a hierarchical nesting of clusters. This novel structural design leads to the existence of quite diverse wave functions, whose transmission characteristics range from extended to almost localized ones. Finally, the potential of quasicrystals as thermoelectric materials is discussed on the basis of their specific transport properties.

It is always a difficult task to assign the peaks recorded from vibrational spectrum. Herein we explored a new pathway of density functional theory (DFT) simulation to present three kinds of spectra of ice XIV and can be referenced as inelastic neutron scattering (INS), IR, and Raman experimental spectrum. The INS spectrum is proportional to phonon density of states (PDOS) while the photon scattering signals reflect the normal vibration frequencies near the Brillouin zone (BZ) center. Based on good agreements with experimental data, we identified the relative frequency and made scientific assignments by normal vibration modes analysis. The debating two hydrogen bond (H-bond) peaks among ice phases from INS have been discussed and the dynamic process of H-bond vibrations were found to be classified into two basic modes. we deduce that two H-bond modes are a general rule among ice family and more works are ongoing to investigate this subject.

Animal-assisted interventions (AAI) use human-animal interactions to positive effect in various contexts including cancer care. This systematic literature review is the first part of a two-part paper series focusing on the research methods and quantitative results of AAI studies in oncology. We find methodological consistency in the use of canines as therapy animals, in the types of high-risk patients excluded from studies, and in the infection precautions taken with therapy animals throughout cancer wards. The investigated patient endpoints are not significantly affected by AAI, with the exceptions of improvements in oxygen consumption, quality of life, depression, mood, and satisfaction with therapy. The AAI field in oncology has progressed significantly since its inception and has great potential to positively impact future patient outcomes. To advance the field, AAI research in oncology should consistently improve the methodological design of studies, report data more completely, and focus on the therapy animal’s well-being.

Flaviviruses replicate in membranous factories associated with the endoplasmic reticulum (ER). Significant levels of flavivirus polyprotein integration contribute to ER stress and the host cell may exhibit an Unfolded Protein Response (UPR) to this protein accumulation, stimulating appropriate cellular responses such as adaptation, autophagy or cell death. These different stress responses support other antiviral strategies initiated by infected cells and can help to overcome viral infection. In epithelial A549 cells, a model currently used to study the flavivirus infection cycle and the host cell responses, all three pathways leading to UPR are activated during infection by Dengue virus (DENV), Yellow Fever virus (YFV) or West Nile virus (WNV). In the present study, we investigated the capacity of ZIKA virus (ZIKV) to induce ER stress in A549 cells. We observed that the cells respond to ZIKV infection by implementing an UPR through activation of the IRE1 and PERK pathway without activation of the ATF6 branch. By modulating the ER stress response, we found that UPR inducers significantly inhibit ZIKV replication. Interestingly, our findings provide evidence that ZIKV could manipulate the UPR to escape this host cell defence system. Since incomplete UPR could lead to unresolved and persistent ER stress, we found that ZIKV infection was associated with an abnormal accumulation of viral envelope proteins, which were aggregated with non-native disulfide bridges. As the presence of these “amyloid like” protein polymers may be cytopathic, our observations provide new insights into specific neuropathologies associated with ZIKA virus infections.

This article aims to solve the problem of robust supervision of a reverse osmosis desalination system (RO-DS) with two models, external model and bond graph model. The structure of an industrial system from the point of view of the external model operates according to several modes of operation (degraded and normal). For this external model, we cannot locate the faults since we are talking about a global operation of the system. The possible solution for the development of research was to use the multidisciplinary model called bond graph. This model by its graphic nature and using a unified language makes it possible to model the industrial system element by element from where it helps the user not only to detect the faults but also to locate them when they appear in the system. The results suggest that the use of the bond graph model for alarm 02 is a reverse osmosis error (RO1); these phenomena are readable on the bond graph model and can be quantified by equations. The equation of the model of this reverse osmosis (RO1) is found in the residual equations (r5, r6 and r7), so that these residues will be sensitive to this rupture. The possible solution during research development was to use the bond graph model to supplement information with physical knowledge and to locate faults. This article also describes the operating safety (by minimizing false alarms and non-detections as well as delays in fault detection) of the desalination system by using the bond graph model described in Linear Fractional Transformation (LFT) form for enable it to manage the robust supervision of a desalination system. An approach based on (LFT-BG) is developed to monitor tank leakage (Cu) and reverse osmosis (RO1 and RO2) faults or valve level (V1 and V2) closures and membrane clogging reverse osmosis (Rm1 and Rm2) that can occur in the reverse osmosis desalination system (RO-DS).

Increased traffic in combination with growing environmental impacts, have led to accelerated degradation of the built infrastructure. In reinforced concrete structures, the corrosion of steel reinforcement is the predominant cause of deterioration. Thus, over the last years the use of glass fiber reinforced polymer (GFRP) composites as internal reinforcement bars (rebars) for concrete structures was evaluated, and has been proved to be a viable alternative to traditional steel reinforcement mainly due to its tensile strength and non-corrosive nature. However, thus far, the GFRP rebar market is diverse and manufacturers around the world produce GFRP rebar types with different surface enhancement to improve the bond to concrete characteristics. In this study, the bond performance of three dissimilar GFRP rebar types (sand coated, helically grooved and with surface lugs) was evaluated over time in seawater environments, with a focus on the bond strength. Accordingly, specimens were expose to seawater in circulating chambers, at three different temperatures (23 °C, 40 °C and 60 °C) for multiple time periods (60 and 120 days). To evaluate the bond performance, pullout tests were conducted according to ASTM D7913 [1]. The results showed that the bond strength varies with surface enhancement features. However, the bond strength didn’t vary significantly with exposure time and temperature for all three evaluated rebar types.

Amorphous solid dispersions are considered a promising formulation strategy for the oral delivery of poorly soluble drugs. The limiting factor for the applicability of this approach is the physical (in)stability of the amorphous phase in solid samples. Minimizing the risk of reduced shelf life for a new drug by establishing a suitable excipient/polymer-type from first principles would be desirable to accelerate formulation development. Here we perform Molecular Dynamics simulations to determine properties of blends of eight different polymer-small molecule drug combinations for which stability data is available from a consistent set of literature data. We calculate thermodynamic factors (mixing energies) as well as mobilities (diffusion rates and roto-vibrational fluctuations). We find that either of the two factors, mobility and energetics, can determine the relative stability of the amorphous form for a given drug. Which factor is rate limiting depends on physico-chemical properties of the drug and the excipients/polymers. The methods outlined here can be readily employed for an in-silico pre-screening of different excipients for a given drug to establish a qualitative ranking of the expected relative stabilities, thereby accelerating and streamlining formulation development.

Chlorotoxin (CTX) is a 36–amino acid peptide with 8 Cys residues that forms four Cys-Cys bonds. It has high affinity for the glioma-specific chloride channel and matrix metalloprotease-2. Structural and binding properties of CTX analogs with various Cys residue substitutions with L-a-aminobutyric acid (Abu) have been previously reported. Using 4.2 ìs molecular dynamics, we compared the conformational and essential space sampling of CTX and analogs [Abu/Ser^2,19]CTX, [Abu/Ser^5,28]CTX, [Abu/Ser^16,33]CTX, [Abu/Ser^20,35]CTX, and [Abu/Ser^{2,5,16,19,20,28,33,35}]CTX. The native and substituted peptides maintained a high degree of a-helix propensity from residues 8 through 21, with the exception of [Ser^5,28]CTX and [Abu^16,33]CTX. In agreement with previous circular dichroism spectropolarimetry results, the C-terminal b-sheet content varied less from residues 25 through 29 and 32 through 36 and was well conserved in all analogs, except: [Abu^16,33]CTX, [Ser^20,35]CTX, [Abu^{2,5,16,19,20,28,33,35}]CTX, and [Ser^{2,5,16,19,20,28,33,35}]CTX. The Cys¹⁶-Cys³³ and Cys²⁰-Cys³⁵ Cys-Cys bonds appear to be required to maintain the ab-motif of CTX. Their selective substitution with Ser^16,33 however, may mitigate the destabilizing effect of Cys¹⁶-Cys³³ substitution by the formation of an inter residue H-bond from OgH of Ser¹⁶ to OgH of Ser³³ bridged by a water molecule. All peptides shared considerable sampled conformational space, which explains the retained receptor binding of the nonnative analogs.

High-level quantum-chemical computations (G4MP2) are carried out in the study of complexes featuring tetrel bonding between the carbon atom in the carbenoid CB11H11 - obtained by hydride removal in the C-H bond of the known closo-monocarbadodecaborate anion CB11H12() and acting as Lewis acid (LA) - and Lewis bases (LB) of different type; the electron donor groups in the tetrel bond feature carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur and chlorine atomic centers in neutral molecules as well as anions H(-), OH(-) and F(-). The empty radial 2pr vacant orbital on the carbon center in CB11H11 , which corresponds to the LUMO, acts as a Lewis acid or electron attractor, as shown by the molecular electrostatic potential (MEP) and electron localization funcion (ELF). The thermochemistry and topological analysis of the complexes {CB11H11:LB} are comprehensively analyzed, and classified according to sharing or closed-shell interactions. ELF analysis shows that the tetrel C···X bond ranges from very polarised bonds, as in H11B11C:F() to very weak interactions as in H11B11C···FH and H11B11C···O=C=O.

Three ternary mixtures composed by choline chloride (ChCl), ethylene glycol (EG) and a second hydrogen bond donor (HBD) as ethanol (A), 2-propanol (B), and glycerol (C) were studied in terms of composition related to the band gap energy (BGE). A Design of Experiments (DoE) approach, and in particular a Simple Lattice three-components design, was employed for determining the variation of the BGE upon the composition of each system. UV-VIS analysis and subsequent Tauc plot methodology provided the data requested from the DoE and multivariate statistical analysis revealed a drop of the BGE in correspondence to specific binary compositions for systems A and B. In particular, a BGE of 3.85 eV was registered for the mixtures ChCl/EtOH (1:1), and ChCl/2-propanol (1:1), which represents one of the lowest values ever observed for these systems.

The one-to-one structural correspondence between any conjugated hydrocarbon CnHm and the borane BnHm+n is extended here, with the B3LYP/cc-pVDZ model, to pure conjugated carbon systems with the example of buckminsterfullerene C60 with the corresponding icosahedral isoelectronic system closo-borane B60H60, and the fluorine substituted systems B60F30H30 and B60F60 , all with icosahedral Ih symmetry. All systems correspond to energy minima in the potential energy hypersurface, except for B60(F30)in(H30)out . Selected electronic structure methods are used to characterize all systems: molecular electrostatic potentials (MEP), atomic charges, bond orders, and topological properties of the electron density within quantum theory of atoms-in-molecules (QTAIM) and electron-localization function (ELF) theory. In the particular case of B60H60 we use the recently developed Hückeloid model to characterize this system. The stability of the energy minimum icosahedral structure B60F60 could have an origin in F···F attractive interactions of the inner fluorine atoms of the cage.

Carbon fiber reinforced polymer (CFRP) has been used widely in strengthening of steel structures. Steel/CFRP systems subjected to elevated temperatures is realistic in a summer climate event in many countries where the temperature in steel may approach 50 °C or even higher, which will lead to the degradation of the bond performance between CFRP and steel. Therefore, predicting the bond behavior of the CFRP/steel system under elevated temperature is critical. This paper investigated the mechanical performance of CFRP/steel adhesively-bonded double strap joints at elevated temperatures. Thirty CFRP-steel double strap joints were tested to failure under temperatures between 10 °C and 90 °C. It was found that the joint failure mode changed from adherend failure to debonding failure as the temperature approached T_g. In addition, the ultimate load and joint stiffness decreased significantly at temperatures near to and greater than T_g. Based on the experimental results, a model is proposed to predict the bond stress of the CFRP/steel at different temperatures.

The consequences of manipulations in structure and amino acid composition of native cyclolinopeptide A (CLA) from linen seeds and its linear precursor on their biological activities and mechanisms of action are reviewed. The modifications included truncation of the peptide chain, replacement of amino acid residues with proteinogenic or non-proteinogenic ones, modifications of peptide bond, and others. The studies revealed changes in the immunosuppressive potency of these analogs investigated in a number of in vitro and in vivo experimental models, predominantly in rodents, as well as differences in their postulated mechanism of action. The modified peptides were compared with cyclosporine A and parent CLA. Some of the synthesized and investigated peptides show potential therapeutic usefulness.

MP2/aug-cc-pVTZ calculations were carried out for the ZFH₃-B complexes (Z = C, Si, Ge, Sn and Pb; B = C₂H₂, C₂H₄, C₆H₆ and C₅H₅^-; relativistic effects were taken into account for Ge, Sn and Pb elements). These calculations are supported by other approaches; the decomposition of the energy of interaction, Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) method. The results show that tetrel bonds with π-electrons as Lewis bases are classified as Z…C links between single centers (C is an atom of the π-electron system) or as Z…π interactions where F-Z bond is directed to the mid-point (or nearly so) of the CC bond of the Lewis base. The analogues systems with Z…C/π interactions were found in the Cambridge Structural Database (CSD). It was found that the strength of interaction increases with the increase of the atomic number of the tetrel element and that for heavier tetrel elements the ZFH₃ tetrahedral structure is more deformed towards the structure with the planar ZH₃ fragment. The results of calculations show that the tetrel bond is sometimes accompanied by the Z-H…C hydrogen bond or even sometimes the ZFH₃-B complexes are linked only by the hydrogen bond interaction.

Atoms in Molecules (AIM), Natural Bond Orbital (NBO), and normal coordinate analysis have been carried out at the global minimum structures of TH₅⁺ (T = C/Si/Ge). All these analyses lead to a consistent structure for these three protonated TH₄ molecules. The CH₅⁺ has a structure with three short and two long C-H covalent bonds and no H-H bond. Hence, the popular characterization of protonated methane as a weakly bound CH₃⁺ and H₂ is inconsistent with these results. However, SiH₅⁺ and GeH₅⁺ are both indeed a complex formed between TH₃⁺ and H₂ stabilized by a tetrel bond, with the H₂ being the tetrel bond acceptor. The three-center-two-electron bond (3c-2e) in CH₅⁺ has an open structure, which can be characterized as a V-type 3c-2e bond and that found in SiH₅⁺ and GeH₅⁺ is a T-type 3c-2e bond. This difference could be understood based on the typical C-H, Si-H, Ge-H and H-H bond energies. Moreover, this structural difference observed in TH₅⁺ can explain the trend in proton affinity of TH₄. Carbon is selective in forming a ‘tetrel bond’ and when it does, it might be worthwhile to highlight it as a ‘carbon bond’.

The development of a stationary phase material for high performance liquid chromatography based on a surface of silica hydride as opposed to silanols on ordinary silica is discussed including synthetic approaches, characterization and applications. There are several synthetic approaches available to create a silica hydride surface. Modification of the Si-H moiety on the silica surface can be accomplished through use of a hydrosilation reaction. Both the intermediate silica hydride and the material modified with an organic moiety can be characterized by a number of spectroscopic as well as a variety of other methods. Further insights into the retention mechanism are provide through chromatographic measurements. The ultimate utility of any chromatographic stationary phase material is determined by its success for solving challenging analytical problems. A broad range of applications are reviewed to illustrate the versatility and usefulness of silica hydride-based stationary phases.

This work demonstrates that a plasmid can function as an efficient biocatalyst in mediating the nitroaldol (Henry) reaction at high temperatures in ultrapure water. Compared with ssDNA, the plasmid displayed a remarkable catalytic efficiency (97% yield within 20 min). Aromatic aldehydes which bear strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane, which afforded the corresponding β-nitroalcohols in good yields within 2 h (up to 98%). By contrast, aliphatic and aromatic aldehydes with electron-donating groups did not react. Moreover, the yield significantly dropped when the size of the carbanion increased, and the yield was only 10% when nitropropane was used as the donor.

In this paper, we study a generalised CIR process with externally-exciting and self-exciting jumps, and focus on the distributional properties and applications of this process and its aggregated process. The first and second moments of this jump-diffusion process are used to calculate the insurance premium based on mean-variance principle. The Laplace transform of the aggregated process is derived, and this leads to an application for pricing default-free bonds which could capture the impacts of both exogenous and endogenous shocks. Illustrative numerical examples and comparisons with other models are also provided.

We investigated the effect of helium atmospheric-pressure plasma (PL) and deep-ultraviolet (UV) light treatments on the adhesive properties of fiber-reinforced poly(ether-ether-ketone)polymer (PEEK). PEEK disks reinforced with carbon (CPEEK) or glass (GPEEK) fibers were polished, modified with PL and UV for 60 s, and the surface energy was calculated by measuring the contact angles. The disk surfaces were analyzed by X-ray photoemission spectroscopy. Shear bond strength testing was performed using a universal testing machine, and the fracture surfaces were observed by electron probe microanalyzer. Data were analyzed with one and two-way ANOVA and Tukey’s post-hoc test (p < 0.05). The surface energies were increased by the modifications, which created OH functional groups on the surfaces. The bond strengths of CPEEK were increased by PL and those of GPEEK were increased by PL and UV, owing to chemical bonding at the interface.

In this study, the influence of graphene oxide nanoparticles on the bond-slip behavior of fiber and fly ash based geopolymer paste was examined. Geopolymer paste incorporating graphene oxide nanoparticles solution was cast in half briquetted specimens and embedded with a fiber. Three types of fibers were used: steel, polypropylene, and basalt. The pullout test was performed at two distinct speeds: 1 mm/second and 3 mm/second. Results showed that the addition of graphene oxide increased the compressive strength of geopolymer by about 7%. The bond-slip responses of fibers embedded in geopolymer mixed with graphene oxide exhibited higher peak stress and toughness as compared to those embedded in normal geopolymer. Each fiber type also showed different mode of failure. Both steel and polypropylene fibers showed full bond-slip responses due to their high ductility. Basalt fiber, on the other hand, because of its brittleness, failed by fiber fracture mode which showed no-slip in pull out responses. Both bond strength and toughness were found to be rate sensitive. The sensitivity was higher in graphene oxide/geopolymer than in conventional geopolymer.

A facile solid-phase synthetic method for incorporating the imidazoline ring motif, a surrogate for a trans peptide bond, into bioactive peptides is reported. The example described is the synthesis of an imidazoline peptidomimetic analog of an insect pyrokinin neuropeptide via a cyclization reaction of an iminium salt generated from the preceding amino acid and 2,4-diaminopropanoic acid (Dap).

Animal-assisted interventions (AAI) are a unique class of complementary medical treatments that can improve a patient’s quality of life, both physically and psychologically. Part I of this two-paper systematic literature review series focused on the study methods and quantitative results of researchers in this field. We continue this in-depth review here in Part II by discussing the common theories associated with AAI in the context of cancer. Of all the factors at work in human-animal interactions, researchers explicitly cite compatible animal personality, physical touch, physical movement, distraction/entertainment, and increased human interaction as the mechanisms responsible for the positive clinical outcomes observed in AAI. In various combinations, these mechanisms group under broader theoretical frameworks that attempt to fully explain the AAI context as it relates to cancer care. The social support hypothesis and the conception of a human-animal bond are the most referenced overarching frameworks. The cognitive activation theory of stress, the science of unitary human beings, and the self-object hypothesis are also referenced. We briefly consider other relevant theories commonly noted in the human-animal interactions literature that have the potential to clarify aspects of cancer-related AAI. We also discuss the neurobiological transduction mechanisms needed to connect theoretical frameworks and their mechanisms directly to the observed clinical outcomes. To advance the field, researchers should consider overarching theories with testable hypotheses when designing studies, and use consistent terminology when reporting results. This review lays a foundation for progress towards a unified theoretical framework and for effective treatment of the whole cancer patient.

In the study of materials and macromolecules by first-principle methods, the bond order is a useful tool to represent molecules, bulk materials and interfaces in terms of simple chemical concepts. Despite the availability of several methods to compute the bond order, most applications have been limited to small systems because a high spatial resolution of the wave function and an all-electron representation of the electron density are typically required. Both limitations are critical for large-scale atomistic calculations, even within approximate density-functional theory (DFT) approaches. In this work we describe our methodology to quickly compute delocalization indices for all atomic pairs, while keeping the same representation of the wave function used in most compute-intensive DFT calculations on high-performance computing equipments. We describe our implementation into a post-processing tool, designed to work with Quantum ESPRESSO, a popular open-source DFT package. In this way we recover a description in terms of covalent bonds from a representation of wave function containing no explicit information about atomic types and positions.

β-cyclodextrin-based star polymers have attracted much interest because of their unique structures and potential biomedical and biological applications. Herein, we synthesized well-defined folic acid (FA)-conjugated and disulfide bond-linked star polymer ((FA-Dex-SS)-βCD-(PCL)14) acted as theranostic nanoparticles for tumor-targeted magnetic resonance imaging (MRI) and chemotherapy. Theranostic nanoparticles were obtained by loading doxorubicin (DOX) and superparamagnetic iron oxide particles (SPIO) were loaded into the star polymer nanoparticles to obtain ((FA-Dex-SS)-βCD-(PCL)14@DOX/SPIO) theranostic nanoparticles. In vitro drug release studies showed that approximately 100% of the DOX was released from disulfide bond-linked theranostic nanoparticles within 24 h under a reducing environment in the presence of 10.0 mM GSH. DOX and SPIO could be delivered into HepG2 cells efficiently, owing to folate receptor-mediated endocytosis process of the nanoparticles and GSH triggered disulfide-bonds cleaving.Moreover, (FA-Dex-SS)-βCD-(PCL)14@DOX/SPIO showed strong MRI contrast enhancement properties. In conclusion, folate-decorated reduction-sensitive star polymeric nanoparticles are a potential theranostic nanoparticle candidate for tumor-targeted MRI and chemotherapy.

Flaviviruses replicate in membrane factories associated with the endoplasmic reticulum (ER). Significant levels of flavivirus viral protein accumulation contribute to ER stress. As a consequence, the host cell exhibits an Unfolded Protein Response (UPR), subsequently stimulating appropriate cellular responses such as adaptation, autophagy or apoptosis. The correct redox conditions of this compartment are essential to form native disulfide bonds in proteins. ZIKA virus (ZIKV) has ability to induce persistent ER stress leading to activation of UPR pathways. In this study, we wondered whether ZIKV affects the redox balance and consequently the oxidative protein folding in the ER. We found that ZIKV replication influences redox state leading to aggregation of viral envelope protein as amyloid-like structures in the infected cells.

Considerable attention has been given to the research field of bioorganometallic chemistry, which is a hybrid chemistry field between biology and organometallic chemistry. The introduction of biomolecules, which have hydrogen bonding sites and chiral centers, into organometallic compounds is considered to be a promising strategy to construct chirality-organized bioorganometallic conjugates. This feature paper sketches an outline of induction of helical chirality into bioorganometallic conjugates. Topics covered include control of the helical chirality of 1,n’-disubstituted ferrocene moieties in ferrocene-dipeptide conjugates and the chirality induction of the Au(I)–Au(I) axis in the dinuclear organogold(I)-uracil conjugates.

We report the results of the characterization of local Monte Carlo (MC) dynamics of an equilibrium bond fluctuation model polymer matrix (BFM), in time interval typical for MC simulations of non-linear optical phenomena in host-guest systems. The study contributes to the physical picture of the dynamical aspects of quasi-binary mosaic states characterized previously in the static regime. The polymer dynamics was studied at three temperatures (below, above and close to the glass transition), using time-dependent generalization of the static parameters which characterize local free volume and local mobility of the matrix. Those parameters play the central role in the kinetic MC model of host-guest systems. The analysis was done in terms of the probability distributions of instantaneous and time-averaged local parameters. The main result is the characterization of time scales characteristic of various local structural processes. Slowing down effects close to the glass transition are clearly marked. The approach yields an elegant geometric criterion for the glass transition temperature. A simplified quantitative physical picture of the dynamics of guest molecules dispersed in BFM matrix at low temperatures offers a starting point for stochastic modeling of host-guest systems.

To date, Cartesian (x, y, z) coordinate system (CCS) has been the default approach to geometrically specify atomic spatial positions in protein structures since the launch of Protein Data Bank (PDB) in 1971. To this end, this paper proposes a local spherical coordinate system (SCS) approach as an alternative to the default approach and a previously reported global SCS approach. The local SCS approach here requires only two parameters (θ and φ), instead of x, y and z as required by the default CCS approach. Essentially, CCS and SCS are like the two sides of one coin, i.e., geometric coordinate system for three-dimensional position specification. Therefore, this paper furthermore argues that it is time to flip the coin over, and have a look at the other side of the coin, e.g., the local SCS approach, which possesses an intrinsically lower degree of descriptional complexity than that of the default CCS approach, and constitutes a potentially useful alternative perspective for all protein structural research field.

Dentin bonding is a key in restorative dentistry. Herein, we developed self-etching two-bottle adhesive system containing 10-methacryloyloxidecyl dihydrogen phosphate monomer (MDP) and the physical, mechanical, and biocompatible properties were evaluated. The characteristics of MDP were analyzed using nuclear magnetic resonance (NMR). The water sorption and solubility, the shear-bond strengths to dentin and enamel, and cytotoxicity tests were performed. The newly blended experimental group showed the lowest thickness and water sorption and solubility values. The shear bond strength to enamel and dentin were comparable to control groups (the three other products) all test groups showed 60% of cell viability. In this study, the properties of the newly synthesized adhesive are comparable with the others. The fundamental goal of this study is to get the MDP patent released, as it is intended for domestic production. For this purpose, this dentin adhesive was developed and compared with the commercial product.

To investigate the role of sulfhydryl groups and disulfide bonds in different protein-stabilized emulsions, N-ethylmaleimide (NEM) was used as sulfhydryl-blocking agent to be added in the emulsion. The addition of NEM to block the sulfhydryl groups resulted in a reduction of the content of disulfide bonds formation, which enabled destruction of the internal structure of the protein molecule, and then decreased the restriction of protein membrane on the oil droplets. Furthermore, with NEM content increasing in the emulsion, a reduction of protein emulsifying activity and emulsion stability also occurred. At the same time, the intermolecular interaction of the protein on the oil droplet interface membrane was destroyed, and the emulsion droplet size increased with the NEM content in the emulsion. Although NEM blocking sulfhydryl groups not to form disulfide bonds has similar effects on three types of protein emulsion, the degree of myofibrillar protein (MP), egg-white protein isolate (EPI), and soybean protein isolate (SPI) as emulsifier had a subtle difference.

The triangulation process represents a violation of the boundary between parental and child relational subsystems which, in turn, affects family dynamics and relationships. The paper, with distinct reference to marital conflict and divorced couples, describes the main causes of the triangulation process and its impact on children (and adolescents) as significant third participants within the parental conflict. Besides, it fo-cuses on long-term consequences associated with triangulation process to parental conflict exposure, that can adversely affect the well-being of children during their life-cycle, and even into adulthood. A data-search was carried out for articles to be included in the review and articles were retrieved from different electronic databases (first: Scopus and Web of Science, then: PsychINFO, Google Scholar, EBSCO and ScienceDirect,). After having initially considered 152 articles, 58 studies were selected for this research. A qualitative analysis was conducted on selected studies, focusing on: (1) different types of triangulation commonly used in intergenerational family relationships; (2) an updated summary of the research around the impact of triangulation on the well-being of children and the parent-child conflict; and (3) the main characteristics of successful intervention of preventative and psychotherapeutic treatments. In conclusion, the results, examining the long-term effects of the triangulation process, highlight the developmental paths of children that are more exposed and at risk, and focuses on the importance of preventing the intergenerational transmission of marital conflict, as a way to reduce mental health costs and to improve the well-being of children and families who are all involved in these conflicting and destructive dynamics.

A regularization approach to model selection, within a generalized HJM framework, is introduced which learns the closest arbitrage-free model to a prespecified factor model. This optimization problem is represented as the limit of a one-parameter family of computationally tractable penalized model selection tasks. General theoretical results are derived and then specialized to affine term-structure models where new types of arbitrage-free machine learning models for the forward-rate curve are estimated numerically and compared to classical short-rate and the dynamic Nelson-Siegel factor models.

In this study, we report a detailed experimental and theoretical investigation of three glycols, namely ethane-1,2-diol, 2-methoxyethan-1-ol and 1,2-dimethoxy ethane. For the first time, the X-Ray spectra of the latter two liquids was measured at room temperature, and they were compared with the newly measured spectrum of ethane-1,2-diol. The experimental diffraction patterns were interpreted very satisfactorily with molecular dynamics calculations, and suggest that in liquid ethane-1,2-diol most molecules are found in gauche conformation, with intramolecular hydrogen bond between the two hydroxyl groups. Intramolecular H-bonds are established in the mono-alkylated diol, but the interaction is weaker. The EDXD study also evidences strong intermolecular hydrogen-bond interactions, with short O···O correlations in both systems, while longer methyl-methyl interactions are found in 1,2-dimethoxy ethane. X-Ray studies are complemented by micro Raman investigations at room temperature and at 80°C, that confirm the conformational analysis predicted by X-Ray experiments and simulations.

Rubble stone masonry walls are widely diffused in most of the cultural and architectural heritage of historical cities. The mechanical response of such material is rather complicated to predict due to their composite nature. Vertical compression tests, diagonal compression tests, and shear-compression tests are usually adopted to experimentally investigate the mechanical properties of stone masonries. However, further tests are needed for the safety assessment of these ancient structures. Since the relation between normal and shear stresses plays a major role in the shear behavior of masonry joints, governing the failure mode, triplet test configuration was here investigated. First, the experimental tests carried out at the laboratory (LPMS) of the University of L'Aquila on stone masonry specimens were presented. Then, the triplet test was simulated by using the Total Strain Crack Model, which reflects all the ultimate states of quasi-brittle material such as cracking, crushing and shear failure. The goal of the numerical investigation was to evaluate the shear mechanical parameters of the masonry sample, including strength, dilatancy, normal and shear deformations. Furthermore, the effect of (i) confinement pressure and (ii) bond behavior at the sample-plates interfaces were investigated, showing that they can strongly influence the mechanical response of the walls.

This study identifies new Alkali Activated Composite Mud Mortar to alternate Cement Mortar used for laying masonry works. This study handles both experimental and numerical analysis of strength and durability for mortar, especially bond strength along mortar and brick joints have studied detail and compared with ANSYS. The bond strength has estimated through the triplet brick prism of shear behavior. The strength and deformation characteristics of masonry constituents obtained from these tests depend on the actual composite conduct of masonry. There is always a good reception for environmentally friendly, low energy, new construction materials, and used in preparing mortar/brick unit combinations all around the world. Also, this study fulfills those requirements. Especially, masonry laid with the mud mortar meets all. Fly Ash, Ground Granulated Blast furnace Slag, and Quarry Dust have utilized the new composites' preparation with 8Molority, 10Molority developed excellent strength. The composite specimens are having compression and bond strength, ranging from 4.84-5.14 and 0.12-0.18N/mm2. The mixed ratio of materials has taken (0.5 parts of Fly Ash, 0.5 parts of Steel Slag, 1.75 parts of Soil, and 0.25 parts of Quarry Dust). The samples tested resistance against acidic, sulfate, and alkalinity indicated PH values less than 7 and 9 simultaneously. Compression strength varied from 10-20% and gained more and fit composite used for mortar in masonry works.

Hydrogen-bond (H-bond) energies in 310-helices of short alanine peptides were systematically examined by precise DFT calculations with the negative fragmentation approach (NFA), a modified method based on the molecular tailoring approach. The contribution of each H-bond was evaluated in detail from the 310-helical conformation of total energies (whole helical model; WH3-10 model), and the results were compared with the property of H-bond in a-helix from our previous study. The H-bond energies of the WH3-10 model exhibited tendencies different from those exhibited by the -helix, in that they depended on the helical position of the relevant H-bond pair. H-bond pairs adjacent to the terminal H-bond pairs were observed to be strongly destabilized. The analysis of electronic structures indicated that structural characteristics cause the destabilization of the H-bond in 310-helices. We also found that the longer the helix length, the more stable the H-bond in the terminal pairs of the WH3-10 model, suggesting the action of H-bond cooperativity.

In this work, we have proposed two new methods for the synthesis of [TcO2L4]+ (where L = im-idazole (Im), methylimidazole (MeIm)) complexes using thiourea (Tu) and Sn(II) as reducing agents. The main and by-products of the reactions were determined, and possible reaction mechanisms were proposed. We have shown that the reduction of Tc(VII) with thiourea is ac-companied by the formation of the Tc(III) intermediate and further oxidation to Tc(V). The reac-tion conditions changing can lead to the formation of Tc(VII) and Tc(IV) salts. Seven new crystal structures are described in this work: Tc(V) complexes, salts with Tc(VII) and Tc(IV) anions. For halide salts of Tu the cell parameters were determined. In all obtained compounds, except for [TcO2(MeIm)4]TcO4, there are π-stacking interactions between aromatic rings. An increase in the anion size lead to weaken intermolecular interactions. Halogen bonds and anion-π interactions have also been found in hexahalide-containing compounds. The Hirshfeld surface analysis showed that the main contribution to the crystal packing is made by van der Waals interactions of the H···H type (42.5–55.1%), H···C/C ···H (17.7–21.3%) and hydrogen bonds, which contribute 15.7–25.3% in total.

The treatment of the bulky Rind-based dibromosilanes, (Rind)2SiBr2 (2) [Rind = 1,1,7,7-tetra-R1-3,3,5,5-tetra-R2-s-hydrindacen-4-yl: EMind (a: R1 = Et, R2 = Me) and Eind (b: R1 = R2 = Et)], with two equivalents of tBuLi in Et2O at low temperatures resulted in the formation of blue solutions derived from the diarylsilylenes, (Rind)2Si: (3). Upon warming the solutions above −20 °C, the blue color gradually faded, accompanying the decomposition of 3 and yielding the cyclic hydrosilanes (4) via intramolecular C−H bond insertion at the Si(II) center. The molecular structures of the bulky Eind-based 3b and 4b were confirmed by X-ray crystallography. Thus, at −20 °C, blue crystals were formed (Crystal-A), which were identified as mixed crystals of 3b and 4b. Additionally, colorless crystals of 4b as a singular component were isolated (Crystal-B), whose structure was also determined by an X-ray diffraction analysis. Although the isolation of 3 was difficult due to their thermally-labile nature, their structural characteristics and electronic properties were discussed based on the experimental findings complemented by computational results. We also examined the hydrolysis of 3b to afford the silanol, (Eind)2SiH(OH) (5b).

The hybrid bond graph has been studied in depth for scalar bond graphs, but how does this translate to the multi-bond graph? Here, the controlled junction – used to model structural switching such as contact – is extended to the multi-bond case. This is a simple process, assuming that all bonds switch simultaneously (which makes physical sense). A controlled 0-junction is applied to multi-bond graph of a car, which can lose contact with the ground in cornering. Dynamic causality features, but this can be accommodated using an equational submodel in 20-Sim (in a manner similar to that used with scalar bond graphs). The junction is proposed for subsequent work to develop a validated multi-body dynamics car model in cornering.

: This study was aimed at assessing adaptation and bonding of discontinuous (short) glass fiber-reinforced composite to intraradicular dentin EverX Flow (GC Corporation, Tokyo, Japan), when used as intracanal composite filling and anchorage instead of traditional fiber posts. (2) Methods: Seventy intact extracted human teeth were endodontically treated and randomly divided into 6 groups (n=10), depending on the materials used in the post space. In Group 1, a 2-bottle universal adhesive G2 Bond Universal + EverX Flow were tested. In group 2, a single-component universal adhesive G-Premio Bond + EverX Flow were used. In groups 3 and 4 the same materials are tested, but after cleaning of the canal walls with 17% EDTA and final irrigation with 5.25% NaOCl Ultrasound Activated. In the last three Groups (5-7) traditional prefabricated GC Fiber Posts 1.6 mm silanized with G-Multi Primer for 1 minute are cemented with a dual-cured composite resin cement (GradiaCore), after ultrasonic irrigation in the groups 6 and 7. In each group, 1 mm-thick slices from each sample (n=10) were cut for light microscope and SEM inspection for study materials adaption to the dentin and for measuring push-out strength of post / cemement material to the dentin / prefabricated post. These results were statistically analyzed: as the data distribution was not normal, the Kruskal-Wallis Analysis of Variance by Ranks had to be applied. The level of significance was set at p<0.05. Results: Push-out forces varied between 6.66-8.37 MPa. No statistically significant differences were recorded among the groups. Microscopic examination showed that ultrasonic irri-gation increased adaptation of the materials to the dentin surface. There was a trend of higher bond strength among the tested groups when EverX Flow was used. Also, the type of failure was more often cohesive when ultrasonic irrigation and two-step adhesive system were used. Conclusions: Within the limitations of this in vitro study, it may be concluded that when EverX Flow was used for intracanal anchorage in the post-endodontic recon-struction, similar push-out retentive forces and strength to those of traditional fiber posts cemented with particulate filler resin composite cements were achieved. Although further studies are necessary, EverX Flow represents an effective alternative to traditional fiber post adhesion in particular when used in combination with the two-step adhesive system and ultrasonic activation.

Herdsmen use different techniques, as per varying geographies and cultures, to keep the cohesion within herds and avoid animals getting lost or predated. However, there is no study on the social behaviour of yaks and on herdsmen management practices. Therefore, this ethology study was initiated by ethnographic inquiries. In Manang, the success of the shepherd is dictated by his personal attribute of “Khula man” or open-heartedness. This attribute refers to good intentions and emotions such as empathy that allows the shepherd to focus more on others than on ownself. This cultural method of assessing the skills required to become a successful and knowledgable shepherd guided us to study the effect of cultural values on the herd’s social behavior. We collected data from two herds living at the same settlement (Yak kharka, 4,100 m altitude, Nepal) by equipping them with loggers. One of the herdsman used the tether rope while other did not. Moreover, the Thaku herd had a more proactive shepherd than the Phurba one. In each herd, 17 animals were equipped with one actigraph wgt3x-BT to measure activity using accelerometer and spatial associations using proximity recorder. One of the herds was equipped with GPS (N=11) as well. Using GPS locations and activity, we showed that the two herds were cohesive and synchronised their activities but the herd with the tether rope was more cohesive. The shepherds also have personal knowledge of the social relationships of their herds and use these relationships to keep the group cohesive and to well manage cattle.

Various factors, such as uncertainty of component parameters and uncertainty of sensor meas-urement values, contribute to the difficulty of fault detection in the landing gear retrac-tion/extension hydraulic system. In this paper, we introduce linear fractional transformation technology and uncertainty analysis theory for the construction of the diagnostic bond graph of the landing gear retraction/extension hydraulic system. In this way, interval analytical redundancy relations and fault signature matrix can be derived. Using the fault signature matrix, existing faults of the system can be preliminarily detected and isolated. Additionally, interval analytical re-dundancy relations can be used to detect system faults in detail, and cases analysis can be carried out to determine if the actuator is externally or internally leaky, and if the landing gear selector valve is reversing stuck. Compared to the traditional analytical redundancy relations, this method takes into account the negative factors of uncertainty; and compared to the traditional absolute diagnostic threshold, the interval diagnostic threshold is more accurate and sensitive.

2,3,5,6-Tetramethyl-1,4-diisocyanobenzene (1), 1,4-diisocyanobenzene (2), and 1,4-dicyanobenzene (3) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1·1,3,5-FIB, 2·2(1,3,5-FIB), and 3·2(1,3,5-FIB), which were studied by XRD. Common feature of the three structures is the presence of I···Cisocyanide or I···Nnitrile HaBs occurred between an iodine -hole and the isocyanide C- (or the nitrile N-) atom. The diisocyanide and dinitrile cocrystals, 2·2(1,3,5-FIB) and 3·2(1,3,5-FIB), are isostructural thus providing a basis for accurate comparison of the two types of noncovalent linkages of CN/NC groups in the composition of structurally similar entities and in one crystal environment. The bonding situation was studied by a set of theoretical methods. Diisocyanides are more nucleophilic than the dinitrile and they exhibit stronger binding to 1,3,5-FIB. In all structures, the HaBs are mostly determined by the electrostatic interactions, but the dispersion and induction components also provide a noticeable contribution and make the HaBs attractive. Charge transfer has a small contribution (<5%) to the HaB and it is higher for the diisocyanide than for the dinitrile systems. At the same time, diisocyanide and dinitrile structures exhibit typical electron-donor and -acceptor properties in relation to the HaB donor.

Background: Valid questionnaires to assess dogs’ health-related quality of life (HRQoL) in veterinary practice can improve canine health outcomes and communications between veterinarians and dog caretakers. The Canine HRQoL Questionnaire (HRQoL-Q) and the Human-Canine Bond Questionnaire (HCBQ) were developed and validated to fulfill this need. Methods: A literature review, interviews with veterinarians, and focus groups with caretakers were conducted to generate questionnaire items to develop draft questionnaires, piloted with caretakers to establish content validity. Measurement properties were evaluated using data from a prospective survey study (N = 327). Results: Draft Canine HRQoL-Q and HCBQ measures were developed, including a domain structure, items, recall period, and scale/response options. Refinements were made via iterative cognitive interviews with caretakers. When no additional revisions were indicated and content validity established, the questionnaires were psychometrically tested. Ceiling effects were observed for all items, and factor analyses indicated that pre-specified domains are appropriate. Internal consistency was demonstrated for the HCBQ (α = 0.79–0.86) and all but the canine HRQoL-Q social functioning domain (α = 0.60)). Test-retest reliability for the canine HRQoL-Q was generally moderate-to-good (intraclass correlation coefficients [ICCs] &gt; 0.79). Test-retest reliability for the HCBQ was moderate (ICCs: 0.70–0.79), except the trust domain (ICC: 0.58). Known-groups validity was demonstrated by significant differences (p &lt; 0.05) in scores by health/bonding groups. Convergent validity was supported (r &gt; 0.40) between all domains and the total score for both questionnaires. Conclusions: The Canine HRQoL-Q and the HCBQ are valid, reliable measures of canine HRQoL for use in veterinary clinics and appear to measure related but distinct concepts that contribute to canine health and wellness.

Fluorinated compounds and co-enzymes are being widely researched and employed throughout research community because of their versatile physical, chemical and biological properties. In this work, we synthesized NiS-NiO/S-g-C3N4, a highly effective photocatalyst for C(sp3)-F bond activation and the regeneration of coenzyme (1,4-NADH) employing a new and ecologically acceptable route. The obtained photocatalyst exhibited important photocatalytic properties, such as good solar light harvesting ability, suitability of the optical band-gap, and facilitating efficient charge migrations. As a result, the newly designed NiS-NiO/S-g-C3N4 photocatalyst shows the excellent yield for regenerations of 1,4-NADH (51%). Further, a method of combining C(sp3)-F bond activation with photocatalysis has been demonstrated that represents a very powerful and sustainable approach, that can be a major breakthrough for the field of pharmaceutical.

Azapeptides have gained much attention due to their ability to enhance the stability and bioavailability of peptide drugs. Their structural preferences, essential to understanding their function and potential applica-tion in the peptide drug design, remain largely unknown. In this work, we systematically investigated the conformational preferences of three azaamino acid residues in tripeptide models, Ac-azaXaa-Pro-NHMe [Xaa= Asn (4), Asp (5), Ala (6)], using the popular DFT functionals, B3LYP and B3LYP-D3. A solvation model density (SMD) was used to mimic the solvation effect on the conformational behaviors of azapep-tides in water. During the calculation, we considered the impact of the amide bond in the azapeptide mod-els on the conformational preferences of models 4-6. We analyzed the effect of the hydrogen bond be-tween the side-chain main chain and main-chain main-chain on the conformational behaviors of azapep-tides 4-6. We found that the predicted lowest energy conformation for the three models differs depending on the calculation methods. In the gas phase, B3LYP functional indicates that the conformers tttANP-1 and tttADP-1 of azapeptides 4 and 5 correspond to the type I of -turn, the lowest energy conformation with all-trans amide bonds, respectively. Considering the dispersion correction, B3LYP-D3 functional predicts the conformers tctANP-2 and tctADP-3 of azapeptide 4 and 5, which contain the cis amide bond preceding the Pro residue, as the lowest energy conformation in the gas phase. The results imply that azaAsx and Pro residues may involve cis-trans isomerization in the gas phase. In water, the predict-ed lowest energy conformer of azapeptides 4 and 5 differs from the gas phase results and depends on the calculational method. For azapeptide 6, regardless of calculation methods and phases, tttAAP-1 (-I turn) is predicted as the lowest energy conformer. The results imply that the effect of the side chain that can form hydrogen bonds on the conformational preferences of azapeptides 4 and 5 may not be negligible. We compared the theoretical results of azaXaa-Pro models with those of Pro-azaXaa models, showing that in-corporating azaamino acid residue in peptides at different positions can significantly impact the folding patterns and stability of azapeptides.

In recent years, various optical measurement technologies such as far-infrared spectroscopy, low-frequency Raman spectroscopy, optical Kerr effect spectroscopy, and two-dimensional Raman-terahertz spectroscopy have developed vigorously. By comparing the complementary aspects detected by various linear and nonlinear spectroscopic techniques, a coherent picture emerges from studies of dynamics in water. Numerous molecular dynamics experiments and theoretical investigations have demonstrated low-frequency molecular motions in liquid water. For example, intermolecular hydrogen bond vibration, molecular reorientation motion, and the interaction between molecule/ionic solute and hydrogen bond all occur in the THz region, which are closely related to their physical/chemical properties and structural dynamics. However, precise probing of various modes of motion is difficult due to the complexity of the collective and cooperative motion of molecules and the spectral overlap of related modes. With the development of THz optical technology, current state-of-the-art THz sources can generate pulsed electric fields with peak intensities on the order of ~MV/cm. Such strong fields make it possible to use THz waves as the driving light source for nonlinear polarization of the medium, which in turn leads to the development of the emerging terahertz Kerr effect (TKE) spectroscopy technique. Many low-frequency molecular motion modes, such as the collective directional motion of molecules and the cooperative motion under the constraint of weak intermolecular interactions, are resonantly excited to unprecedentedly strong amplitudes driven by the THz electric field. Thereby the collected responses are increased. The TKE technique thus creates an interesting prospect for investigating low-frequency dynamics in these media. In view of this, this paper firstly summarizes the research work on the measurement mechanism of TKE spectroscopy by taking the solid material without low-frequency molecular dynamics process as an example. Starting from the principle of TKE technology and the exploration of the properties of solid matter using this technology, its application in the exploration of low-frequency molecular dynamics of liquid water and aqueous solutions is introduced. Liquid water is considered the building block of life and possesses many extraordinary physical and biochemical properties. Its hydrogen bonding network plays a crucial role in these properties. It is generally believed that the ability of water to form complex hydrogen-bonding networks is the main reason for its various kinetic and thermodynamic properties that are different from other liquids. However, the exact structure of the hydrogen-bonding network, the spatial extent of its existence, and the associated timescale are not known. And the relevant spectral information of the basic properties of the reaction water is still not known. Therefore, it is of great significance to evaluate the hydrogen bond-related kinetic properties of liquid water by optical means.

In this study, seven mortar mixes were prepared by replacing natural sand by crumb rubber ,CR, (10%, 25%, 50%, 60%, 75% and 100%). The properties of mortars, both in their fresh and hardened states, were studied. Key characterisitcs, including density, water absorption coefficient, porosity, thermal conductivity, heat capacity, shrinkage/swelling, elastic modulus, compressive strength, flexure strength, fracture energy and performance after exposure to heat, were evaluated. The results obtained showed that as the CR fraction increased, density, initial setting time, and workability decreased but mortars with CR fractions ranged between 25% and 50% are lightweight and can be used for repairing as they fulfill satndards. It was observed that strengths and stiffness decreased with higher CR content while shrinkage increased for CR percentage higher than 60%. However, up to 50% of CR content the mortars obey to the standards for repair. Interestingly, incorporating up to 50% waste tires proved to improve comfort and thermal resistance without affecting thermal inertia. A slight increase in the mass loss is observed when mortars are exposed to high temperatures. Mortars containing CR between 25% and 50% can be classified as lightweight and thermally insulating mortars, suitable for repairing concrete structures in accordance with industry standards.

Background: Radiotherapy is an important part of the medical therapy concept treating tumors in the head and neck region; however, the impact on the field of dentistry could be im-mense. The objective of this study was to evaluate the microtensile bond strength (µTBS) of uni-versal adhesives and to compare the results of different application modes (etch-and-rinse and self-etch) on irradiated and sound human dentin. Methods: Dentin specimen of 180 extracted human wisdom teeth were divided in two superordinate groups. Ninety teeth received either no irradiation (control group) or the high-level therapeutic dose of 60 Gy (test group) applied frac-tionally (2 Gy/day, 5 days/week, 6 weeks). Samples from each group were randomly divided in-to six subgroups assigned to three established universal adhesives (Futurabond® U, VOCO; AdheSE® Universal, Ivoclar Vivadent; Xeno® Select, Dentsply) in both conceivable application modes: etch-and-rinse and self-etch (n = 15). Bond strength was assessed with a universal testing machine immediately after application and light curing of the adhesive materials. Statistical analysis was performed using two-way ANOVA (p<0.01) and Tukey's test (p<0.05). Results: The effect of dentin irradiation and application mode for the adhesive restoration was found to be significant (p<0.01, ANOVA). In all groups, a decrease of µTBS could be observed when used on irradiated dentin. However, no significant influence of high level radiation on the bond strength of Futurabond® U and AdheSE® Universal in both modes could be evaluated (p>0.05, Tukey´s test). Solely in the case of the adhesive system Xeno® Select, significantly reduced bond strength could be determined in self-etch mode after irradiation (group 60 Xse) compared to the control group (0 Xse) (p<0.05, Tukey´s test). Conclusions: Within the limitations of an in vitro study, some effects of high-level tumor irradiation on the bond strength of universal adhesives can be detected. However, these effects were strongly depending on the used material and application mode.

Collagen is a triple-helical protein unique to the extracellular matrix, conferring rigidity and stability to tissues such as bone and tendon. For the [(PPG)10]3 collagen-mimetic peptide at room temperature, our molecular dynamics simulations show that these properties result in a remarkably ordered first hydration layer, of water molecules hydrogen-bonded to the backbone-carbonyl (bb-CO) oxygen atoms. This originates from the following observations. The radius of gyration attests that the PPG triplets are organized along a straight line, so that all triplets (excepting the ends) are equivalent. The solvent accessible surface area (SASA) for the bb-CO oxygens shows a repetitive regularity for every triplet. This leads to bb-CO⋯HOH occupancy following a similar regularity, similar also to the crystal-phase 0-2-1 water occupancy in the P-P-G triplet. The regularity is maintained in spite of the sub-nsec water exchange rate, because the bb-CO sites rarely remain vacant. The manifested ordered first-shell water molecules are expected to produce a cylindrical electrostatic potential around the peptide, that might guide cation diffusion in its vicinity.

The preparation of transition metal salt ammine complexes having oxidizing anions is a great challenge due to the reaction between the ammonia and oxidizing anions during the synthesis of these materials. However, they have an important role in the development of new oxidants in organic chemistry and especially as precursors in the preparation of mixed metal oxides and alloys in controlled temperature thermal decomposition reactions. Therefore, the synthetic procedures to prepare the complexes of transition metal permanganate, pertechnetate, and perrhenate (VIIB group tetraoxometallates) salts with ammonia as ligand or co-ligand have been comprehensively reviewed. The available data about the structure and spectroscopic properties of these compounds, including the hydrogen bonds that act as redox reaction centers under their thermal decomposition are given and evaluated. Their thermal decomposition processes and products have been summarized. The available pieces of information about their role in organic oxidation reactions like the oxidation of benzyl alcohols, and regeneration of oxo-compounds from oximes and phenylhydrazones including the kinetics of these processes have also been collected.

A four-step synthesis of bifunctional, noncovalent organocatalysts based on the chiral (1R,2R)-cyclohexane-1,2-diamine scaffold containing a 1,2-benzenediamine H-bond donor was developed. Nucleophilic aromatic substitution of the 2-fluoronitrobenzene derivative with the commercial (1R,2R)-cyclohexane-1,2-diamine was followed by selective alkylation of the primary amino group, reduction of the aromatic nitro group and final derivatization of the primary aromatic amino group, i.e. acylation, sulfonation, reductive alkylation and arylation, leading to the four subtypes of organocatalysts. All new compounds were fully characterized. The prepared organocatalysts (32 examples) were tested in the Michael addition of acetylacetone to trans-β-nitrostyrene, yielding the addition product with incomplete conversions (up to 93%) and enantioselectivities of up to 41% ee.

In the past few decades, N-heterocyclic carbenes (NHCs) open the new field of organocatalysis in synthetic organic chemistry. This review highlights the dramatic progress in the NHC-catalyzed C−O bond formation based on the activation of aldehyde C(sp2)−H bonds. The oxidative and redox transformations for the synthesis of various molecules with structural diversity and complexity are summarized. Furthermore, new methods and strategies for NHC catalysis are emerging continuously; thus, cooperative catalysis with Brønsted acid, hydrogen-bonding catalyst, transition-metal catalyst, and photocatalyst is also described.

The bond index is an indicator of the grindability of the material and is widely used in the preparation of mineral raw materials and the cement industry. Paper offers new, abbreviated and simplified procedure to determine Bond work index that relies on first-order kinetics law and can be performed with any number of grinding cycles, depending on the desired accuracy of the required data. The parameters G and P80 of each grinding cycle are multiplied by the newly founded coefficients giDT and piDT to obtain values approximately equal to these parameters of the last grinding cycle when the equilibrium state is reached in the standard test. The paper presents comparative results obtained by standard Bond and new shortened procedure on individual samples of andesite, limestone, copper-ore and smelter slag and on composite samples of andesite from limestone and copper-ore with smelter slag in different mass ratios. As the number of grinding cycles increases, the precision of the shortened procedure increases, and the mean square error decrease 3.59%, 2.61% and 1.74% for two, three and four grinding cycles.

A The aim of this study is to analyze the effect of different endodontic irrigants and adhesive systems on resin bond strength of fiber post cementation. 144 single-rooted, unrestored human teeth were endodontically treated and randomly divided into 12 groups according to 4 endodontic irrigants (distilled water as control; EDTA 17%; NaOCl 5%; clorhexidine 2%) and 3 different adhesive/resin cement systems (etch-and-rinse: ortofosforic acid, Parabond® A+B/Paracore®; self-etch: ParaBond® Non-Rinse Conditioner, Parabond® A+B /Paracore®; Universal: ClearfilTM Universal Bond/ ClearfilTM DC Core Plus). 48 h after post cementation ten teeth from each group were cross sectioned into 3 discs (cervical, middle and apical regions). 30 specimens of each group (n=30) were submitted to push-out test at a crosshead speed of 1 mm/min. The remaining 2 teeth of each group were sectioned in the same manner and the resin-dentin interface was evaluated using scanning electron microscopy (SEM). The results were statistically analyzed with the ANOVA and Tukey’s test (< 0,01). The adhesive protocols and post space region showed no significant effect on bond strength (> 0.01). The combination of NaOCl 5% and ClearfilTM Universal Bond reduced the adhesive strength (< 0.01). The NaOCl 5%, in relation with other irrigants, significantly decreased the push-out bond strength.

Companion animals play a central role in many families and are especially valued by those who are socially isolated. Crisis situations such as acute hospitalizations, homelessness and natural disasters can make it difficult to preserve the human-animal bond and can result in animals being surrendered or euthanized. Social support programs like the RSPCA NSW Emergency Boarding and Homelessness program support people experiencing crisis situations with emergency pet boarding, access veterinary treatment and individualized case management. This study aimed to estimate the social return on investment (SROI) for this program using standard SROI methodology. In-depth interviews were conducted with 13 program stakeholders and questionnaire responses were received from 29 program clients. Outcomes were quantified for four stakeholder groups: program clients, client’s animals, RSPCA Inspectors, animal pounds and shelters. Clients and their animals experienced the bulk of the benefit from the program, estimated to have a combined value of over $5 million AUD for the 2020-21 financial year. The estimated social return on investment was $8.21 for each $1 invested. The study demonstrates that keeping people together with their companion animals, or ensuring they are reunited as soon as possible, can reduce stressors, and improve outcomes for people and animals.

A enantioselective tandem transformation concerning asymmetric allylic decarboxylative addition and cyclization of N-nosylimines with vinylethylene carbonates (VECs) in the presence of [Rh(C2H4)2Cl]2, chiral sulfoxide-N-olefin tridentate ligand has been developed. The reaction of VECs with various substituted N-nosylimines proceeded smoothly under mild conditions, giving highly functionalized oxazolidine frameworks in good to high yields with good to excellent enantioselectivity.

H-bonding, including H-bond donor (HBD) with electron-rich part of a substrate and H-bond acceptor (HBA) with electron-deficient part of a substrate, has achieved massive success. Faster transformation often correlates with more donicity of HBD. Besides the positive charge are employed to enhance the donicity of HBD, the electron withdrawing groups become a dissimilar approach for increasing the donicity of HBD. We describe newly designed H-bond donor catalysts, tris(monoalkylamino)cyclopropenium, implemented by vicinal positive charged on the cyclopropenium core. The counter anion became potential HBA to activate the electron-deficient part of a substrate. The tris(phenylamino)cyclopropenium chloride (TPAC·Cl) as a representative catalyst was applied in Friedel–Crafts alkylation of indoles with nitroalkenes. X-ray analyses of a single crystal of TPAC·Cl described the 3D architecture and the delocalized cationic charge in the solid state. Unit formal positive charge turned N–H moieties into H-bond donor (HBD) and the counter chloride anion exhibited potential H-bond acceptor (HBA). The HBD and HBA displayed cooperative organocatalysis in Friedel–Crafts alkylation of indoles with nitroalkenes. A new class of hydrogen bonding catalysis and working mechanism were proposed.

The aim of this study was to investigate the effect of laser irradiation to computer-aided de-sign/computer-aided fabrication (CAD/CAM) resin blocks coated with a silane coupling agent on the bond strength between the resin blocks and composite resin. The CAD/CAM resin blocks used in this study were Cerasmart 300 (GC) and Vita Enamic (Vita); they were cut into plates and then subjected to a series of treatments. After processing with a silane coupling agent, treatment with a semiconductor laser was performed at 3.0, 5.0, and 7.0 W, followed by the bonding procedures. The control group included those exposed to silane and bonded without laser application. After bonding, a mold with a simulated cavity was formed on the specimen and filled with flowable composite resin, and they were stored for 24 h or stressed by thermal cycling for subsequent testing that assessed the shear bond strength (n = 10). The results revealed that the bond strength was significantly enhanced by laser irradiation after applying a silane coupling agent, whereas significant effect was not detected between the materials. Particularly, 7 W laser irradiation had a significant effect on the bond strength between the composite resin and Cerasmart block after thermal cycling.

The UHPC grouted bellow is an innovative technology for connecting assembled buildings, where the anchorage performance of the rebar and UHPC filled in bellows plays a critical role in determining the overall connection effectiveness. To ascertain a dependable anchorage length and establish a bond-slip relationship between the rebar and UHPC within the bellow, we conducted tests on 8 groups of 16 specimens of metal corrugated pipes filled with UHPC and rebar under tension. The tests considered varying parameters such as the aperture ratio D/d and anchorage length L. By analyzing the failure modes, load versus deflection curves, and steel strain data, we gained valuable insights into the influence of the aperture ratio and anchorage length on the anchorage performance. Furthermore, we calculated the experimental curve of the bond-slip relationship between the rebar and the UHPC interface grouted in the bellows and derived a bond-slip model through fitting. These findings serve as a crucial foundation for the force analysis of assembled structures connected using UHPC grouted bellows.

By using the Black-Derman-Toy (BDT) model, we predict the future trend of the riskless rate, and then we build an equation that relates the market price of zero-coupon bonds and the theoretical price of zero-coupon bonds calculated using a binomial option pricing model. Based on this, we can find the implied daily return μ, implied natural upturn probability p, and implied daily volatility σ with respect to different time-to-maturity values of zero-coupon bonds. With these results, we can give some suggestions to bond traders.

Based on the marine natural products piperafizine B, X334 and our previously reported compound 4m, fourteen novel 3,6-diunsaturated 2,5-diketopiperazine (2,5-DPK) derivatives (1-2, 4-6, 8-16), together with two known ones (3 and 7), were designed and synthesized as anticancer agents against cell lines A549 and Hela. The MTT assay results showed that the derivatives 6, 8-12 and 15 had moderate to good anticancer capacities with the IC50 values ranging from 0.7 to 8.9 μM. Among them, compound 11 with naphthalen-1-ylmethylene and 2-methoxybenzylidene functions at the 3- and 6-positions of 2,5-DPK ring, respectively, displayed good inhibitory activities to both cancer cells A549 (IC50 = 1.2 μM) and Hela (IC50 = 0.7 μM). It could also induce apoptosis and obviously block the cell cycle progression at G2/M phase in both cells at 1.0 μM. The electron withdrawing functions might not be favorable for the derivatives with high anticancer activities. Additionally, compared to piperafizine B and X334, these semi-N-alkylated derivatives have high liposolubilities (&gt; 1.0 mg•mL-1). Compound 11 can be further developed aiming to the discovery of novel anticancer candidate.

Amylin, also known as islet amyloid polypeptide (IAPP), is a metabolic homeostasis-related hormone that is produced and released by the β cells of the pancreas, the same cells that produce insulin. Insulin-degrading enzyme (IDE) is a protease enzyme that plays an essential role in the breakdown and degradation of various peptides, including insulin and amylin. Direct binding & interaction between amylin and IDE is inextricably linked to the degradation of amylin, and research and development effort in this area is crucial to understand the potential therapeutic implications of disrupting the IDE-amylin interaction in the context of conditions where metabolic homeostasis needs to be regulated, such as diabetes and obesity. Here, this article incorporates currently available experimental complex structure of amylin and IDE, and delves deep into the interstructural biophysics underlying the binding interface of the two interacting partners. With a set of comprehensive structural biophysical analysis, this article identified an intriguing region of high electrostatic potential indicative of strong binding sites between the first N-terminal lysine (Lys1, K1) residue of amylin and Glu341 (E341) of IDE. This unique electrostatic hotspot presented herein paves the way for the rational design of drug-like small molecules that can selectively disrupt this interaction, offering a targeted therapeutic strategy for improved metabolic homeostasis, particularly for patients with diabetes and obesity.

Support effect is an important issue in heterogeneous catalysis while the explicit role of a catalytic support is often unclear for catalytic reactions. A systematic density functional theory computational study is reported in this paper to elucidate the effect of a model boron nitride (BN) support on the first N-H bond activation step of NH3 on Run (n =1, 2, 3) metal clusters. Geometry optimizations and energy calculations were carried out using density functional theory (DFT) calculation for intermediates and transition state from the starting materials undergoing the N-H activation process. The primary findings are summarized as follows. The involvement of the model BN support does not significantly alter the equilibrium structure of intermediates and transition state in the most favorable pathway (MFP). Moreover, the involvement of BN support decreases the free energy of activation, ΔG≠, thus improving the reaction rate constant. This improvement is more obvious at high temperatures like 673 K than low temperatures like 298 K. The BN support effect leading to the ΔG≠ decrease is most significant for the single Ru atom case among all three cases studied. Finally, the involvement of model BN may change the spin transition behavior of the reaction system during the N-H bond activation process. All these findings provide a deeper insight into the support effect on the N-H bond activation of NH3 for supported Ru catalyst in particular and for supported transition metal catalysts in general.

In this paper, a quick and efficient method for preparation of scopolamine hydrobromide with high purity was introduced, named as magnetic field induced crystallization. Based on the solubility difference between scopolamine and scopolamine hydrobromide, salifying crystallization was selected and then treated with the synergistic effect of magnetic field to achieve the aim of scopolamine purification. The effects of crystallization solvents and magnetic field intensity on the crystallization process of scopolamine hydrobromide, as well as the influnence of magnetic field on the crystal growth direction were investigated. The results revealed that after treatment under magnetic field, the shortened induction time (25.64%-75.46%), the increased purity of crystals (0.95%-2.92%) and the improved recovery rate (4.51%-10.78%) were achieved. Furthermore, we also found that magnetic field could destroy the hydrogen bond in the solution, and change the physical properties of the mother liquid, so as to promote the nucleation formation and crystal growth. The above experiments suggested that the external magnetic field has the potential to be a feasible method for scopolamine preparation.

The fusion of surface-modified steel with tungsten carbide (WC) and NiCrBSi powder through laser metal deposition has emerged as a formidable strategy for fortifying components against wear and corrosion in extreme operating environments. Meticulous selection of WC content, innovative pre-alloying techniques, and precise control of laser metal deposition profoundly influence the mechanical properties and microstructural evolution of WC-NiCrBSi coatings applied to surface-enriched commercial alloy steel (805M2, 832M13, and 827M40). These tailored coatings exhibit exceptional resilience, ideal for harsh industrial settings in Oil and gas drilling, petrochemical, and Mining sectors. Advanced materials testing techniques, including scanning electron microscopy, light optical microscopies, and microhardness testing, unveil the innate hardness attributes, with findings highlighting the unassailable fortitude of the Mixed matrix layer's side face. The amalgamation of these testing methodologies with laser metal deposition promises an unparalleled path to extend the operational lifespan of critical components in challenging working conditions. The research horizon for WC-NiCrBSi coatings remains broad, with the potential to enhance durability, operational efficiency, and cost-effectiveness across diverse applications.

By this contribution we would like to briefly highlight the problems in conceiving the “Hydrogen Bond” (HB) as a real short-range, directional, electrostatic, attractive interaction and to reframe its nature through the non-approximated view of condensed matter offered by a Quantum Electro-Dynamic (QED) perspective. We focus our attention on water, as the paramount case to show the effectiveness of this 40-years’ old theoretical background, which depicts water as a two-fluid system (where one of the two phases is coherent). The HB emerge to be the result of the electromagnetic field gradient in the coherent phase of water, whose vacuum level is lower than the non-coherent (gas-like) fraction. Thus, the HB can be properly looked at, i.e. no more as a “dipolar force” among molecules, but as the phenomenological effect of their collective thermodynamic tendency to occupy a lower ground-state, compatibly with temperature and pressure. This perspective allows to account for many “anomalous” behaviours of water and to understand why the calculated energy associated to HB should change when considering two molecules (water-dimer), or the liquid state, or the several kinds of ice. The emergence of a condensed, liquid, phase at room temperature is indeed the consequence of the boson condensation as described in the framework of spontaneous symmetry breakings (SSB). The switch from a still semi-classical Quantum Mechanical (QM) in the 1st quantization to a Quantum Field Theory (QFT) view embedded in the 2nd quantization is advocated for a more realistic and authentic description of water, condensed matter and living systems.

We present here a theory of Majorana excitons, photo-excited conduction electron-valence band hole pairs, interacting with Majorana Fermions in a Kitaev chain of semiconductor quantum dots embedded in a nanowire. Using analytical tools and exact diagonalisation methods we identify the presence of Majorana Zero Modes in the nanowire absorption spectra.

The quinoline derivative, N-(7-chloro-4-morpholinoquinolin-2-yl)benzamide, was synthesized in a conventional three-step procedure from 4,7-dichloroquinoline using N-oxidation reaction/C2-amidation reaction/C4 SNAr reaction sequence. The structure of the compound was fully characterized by FT-IR, 1H‐, 13C-NMR, DEPT-135°, and ESI-MS techniques. Its physicochemical parameters (Lipinski’s descriptors) were also calculated using the online SwissADME database. Such derivatives are relevant therapeutic agents exhibiting potent anticancer, antibacterial, antifungal, and antiparasitic properties.

Minerals are the chief constituents of rocks and they have varied properties such as surface area, surface charge, site densities etc. Hence, numerous interactions are bound to occur in the reservoir during rock-fluids (i.e., rock, crude oil and brine) interactions. This study seeks to assess the role of mineralogical composition on the wettability of Sandstone Rocks (SR) and Mineral Mixture (MM) using both Surface Complexation Modelling (SCM) and flotation test. From the considered sandstone rocks, both the experimental results and its simulated counterpart revealed that, the SR were preferentially hydrophilic. For the MM, when the mass fraction of the hydrophobic mineral was increased, the affinity of the MM became slightly hydrophobic and vice-versa. For the dominant sandstone reservoir rock minerals with predominantly negatively charged surfaces, negligible oil adsorption took place due the interfacial repulsive forces at the oil-brine and mineral-brine interfaces. For the MM with low calcite content, the wetting preference was influenced by the mineral with prominent surface area. Our developed model portrayed that the main mechanism for oil adhesion onto sandstone minerals was divalent cations bridging. Nonetheless, adhesion of carboxylate (&gt;COO-) onto the illite, montmorillonite and calcite sites also took place with the latter being more pronounced.

The current study explores the problem of illiquidity in the corporate bond market and examines a broad set of liquidity proxies through empirical investigation. Purpose: The purpose of this paper is to give solution to the global issue of illiquidity in the corporate bond market. The problem is identified by many researchers and this paper attempts to find out the viable solution of the "fungibility route" as an alternative to the "liquidity route". Design/ Methodology: An Analysis of a sample size of 2,34,772 trade data of corporate bonds and a sample size of 2,00,607 trade data of G-securities is done to identify the problem. Findings / Solution proposed: A mathematical model based on credit risk differential and sensitivity differential is proposed to find out the fair value at which an illiquid bond can be swapped by a liquid bond. To arrive at the fair value of the illiquid bond, we have calculated risk adjusted discount rate using modified duration and credit risk differential. With our solution, it is possible to enhance the liquidity of the bond not directly but through fungibility route. Originality: the research is first of its kind in which solution is given to the global problem of corporate bond illiquidity. To execute the trade in the fungibility route, proposed parties involved are the Fungibility platform, the initiator, and the bidder. The derived fair value would facilitate trade and serve as an exit strategy for illiquid bond holders worldwide.

A mixture of nonlabeled (14N2H4) and 15N labeled hydrazine (15N2H4) in an aqueous solution is oxidized to 15N2, 14N2, and 14N15N molecules, indicating the intermediate existence of the 14NH2-14NH-15NH-15NH2 with subsequent hydrogen transfers and splitting of side N-N bonds. Structures, thermodynamics, and electron characteristics of various N4H6 molecules in aqueous solutions are investigated using theoretical treatment at the CCSD/cc-pVTZ level of theory to explain the crucial part of the hydrazine oxidation reaction. Most N4H6 structures in aqueous solutions are decomposed during geometry optimization. Splitting the bond between central nitrogen atoms is the most frequent, but the breakaway of the side nitrogen is energetically the most preferred. The N-N fissions are enabled by suitable hydrogen rearrangements. Gibbs free energy data indicate the dominant abundance of NH3... N2... NH3 species. The side N atoms have very high negative charges, which should support hydrogen transfers in aqueous solutions. The only stable cyclo-(NH)4…H2 structure has a too high Gibbs energy and breaks the H2 molecule. The remaining initial cyclic structures are split into hydrazine and HN≡NH or H2N≡N species, and their relative abundance in aqueous solutions is vanishing.

Present research focus on the effect of different processing routes on physical and mechanical properties of nano Ti(CN) based cermet’s with metallic binders. Tungsten carbide (WC) is added as secondary carbide and Ni-Co are added as metallic binders in nano Ti(CN) based cermet processed via Conventional and Spark Plasma Sintering (SPS). Systematic comparison of composition and sintering conditions for different cermet’s’ systems is done to design the novel composition and sintering conditions. Nano TiCN powder was prepared by 30hr of ball milling. Highest density of >98.5% percent was achieved for SPS processed cermet’s sintered at 1200°C and 1250°C for 3 min. at 60 MPa pressure in comparison to conventionally sintered cermet’s at 1400°C for 1hr with two stage compaction process, uniaxially at 150 MPa and isostatically at 300 MPa pressure respectively. Comparison of XRD analysis of milled powders of different time intervals was done to understand the characteristics of the as received and milled powders. Peak broadening was observed after 5 hr. of ball milling, and it increased till 30hr. Also, peak broadening and refined carbide size was observed in XRD and SEM micrograph of SPS processed cermet. TEM analysis of milled powder showed internal structure having regular periodic arrangement of planes. SEM (BSE) images of all cermets primarily showed three major microstructural phases of core-rim-binder with black, grey and white contrast respectively. In the present sintering conditions high hardness of ~16 GPa and fracture toughness of ~9 MPa m1/2 was obtained for SPS processed cermets sintered at higher temperature.

Concrete cracks and local damage can affect the bond performance between concrete and steel bars, thereby reducing the durability of reinforced concrete structures. Compared with general concrete crack repair methods, biomineralization repair not only has effective bonding capabilities but is also particularly environmentally friendly. In view of this, this study aimed to apply biomineralization technology to repair damaged fiber-reinforced lightweight aggregate concrete (LWAC). Two groups of LWAC specimens were prepared. The control group used lightweight aggregates (LWAs) without bacterial spores and nutrient sources, and the experimental group used LWAs containing bacterial spores and nutrient sources. These specimens were first subjected to compression tests and pull-out tests, respectively, and thus were damaged. After the damaged specimen healed itself in different ways for 28 days, secondary compression and pull-out tests were conducted. The self-healing method of the control group involved placing the specimens in an incubator. The experimental group was further divided into experimental group I and experimental group II. The self-healing method of experimental group I was the same as that of the control group. The self-healing method of experimental group II involved soaking the specimen in a mixed solution of urea and calcium acetate for two days, and then taking it out and placing it in an incubator for two days, with a cycle of four days. The test results showed that, compared with the control group specimens, the relative bond strength ratio of the experimental group II specimens increased by 17.9%. Moreover, the EDS and XRD analysis results confirmed that the precipitate formed at the crack was calcium carbonate, which improved the compressive strength and bond strength after self-healing. This indicates that the biomineralization maintenance method used in experimental group II is more effective.

Bond Properties were performed on Ag-2.35Au-0.7Pd-0.2Pt-0.1Cu alloy wire with a diameter of 25 µm under different process parameters. Effects of electrical flaming off (EFO) current and EFO time on deformability of the free air ball (FAB) were investigated using scanning electron microscopy (SEM) as well as the effects of ultrasonic power and bonding force on the bond characteristic. The experimental results showed that, FAB grows from a preheated tip to a small ball, a regular ball and finally to a golf ball with increasing either the EFO current or the EFO time, and the FAB presented optimal shape at 25 mA and 650 μs. Moreover, a nonlinear relationship between FAB diameter and EFO time is obtained at the EFO current of 25 mA, which could be expressed by a cubic equation. Further, at a constant bonding force, as the ultrasonic power increased, the mashed ball diameter grew larger and larger, the capillary hole imprint became more and more obvious, and the tail width also increased larger and larger, and vice versa. The optimal ultrasonic power and bonding force are 70 mW and of 45 gf for ball bond and 90 mW and 75 gf for wedge bond, respectively. Finally, for all the bonded wire samples prepared under optimal process parameters, no ball and wedge bond lifts happened after destructive pull test, and full intermetallic compound coverage with perfect morphology occurred on the bond pad after ball shear test, which meant that the bonded wire samples have high bond strength, and hence improved the reliability of microelectronic products.

The purpose of water treatment through ultraviolet (UV) radiation is to interrupt the development and multiplication of microorganisms by preventing their growth and reproduction.Ultraviolet treatment has become a very affordable solution to produce clean water of optimal quality in regions where access to drinking water is essential. The experimental water treatment unit is powered by a photovoltaic (PV) source. It incorporates a discharge lamp used to generate ultraviolet radiation, which is harnessed to address bacteriological issues related to water quality. This lamp is continuously powered by a photovoltaic (PV) source through an inverter and an electronic ballast. The water treatment system also includes a motor pump designed to draw contaminated water from the input reservoir, a flow control valve to adjust flow rates as needed, and a filter aimed at enhancing the quality of the contaminated water. The water circulates between the input reservoir (contaminated water) and the output reservoir (treated water) through the UV lamp. The relationship between the intensity of the UV lamp and the water flow rate can ensure an adequate water quality.

The aim of the study was to examine the influence of different irrigation protocols on the shear bond strength (SBS) of self-adhesive resin composite cement (SARC) to primed radicular dentin. Radicular dentin slabs (N=58) were sectioned from extracted intact third molars, embedded in acrylate, polished, and randomly assigned to five experimental groups (N=8-12) and one control group, CG (N=8). Irrigation solutions used were sodium hypochlorite (H), ethylene-diamine-tetra acetic acid (EDTA), etidronic acid with hypochlorite (HEDP), saline solution (SS), and chlorhexi-dine (CHX). Each experimental group underwent different irrigation protocol for two minutes: 1) H/EDTA/H, 2) HEDP, 3) H/EDTA/CHX, 4)H/EDTA/SS, and 5) HEDP/SS. The CG samples were not treated with any irrigation solution. After drying, adhesive enhancing primer (AEP) and du-al-curing SARC were applied to the radicular dentin using molds corresponding to the Ultra Tester. Specimens were stored at 37°C in distilled water and fractured in shear mode after 10 days. The results were analyzed using the ANOVA statistical test and Post-hoc Games-Howell test, α=0.05. CG exhibited the highest SBS. Except for HEDP and HEDP/SS, all experimental groups showed significantly lower SBS compared to the control group (p< 0.05). HEDP seems to be ad-equate solution for root canal cleaning before dentin priming and fiber post cementation with self-adhesive resin cement. Cleaning protocols with H, EDTA and CHX cause a significant de-crease in bond strength.

In this work, a novel single crystal (3-(4-chlorophenyl)-4,5-dihydroisoxazol-5-yl)methyl benzenesulfonate has been synthetized via a one-pot sequential strategy under sonication. A single crystal X-ray diffraction analysis was reported. In the crystal, a layer structure is generated by C—H···O and C—H···N hydrogen bonds. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H···H (28.9%), H···O/O···H (26.7%) and H···C/C···H (15.8%) interactions. The optimized structure calculated using density functional theory at the B3LYP/6–311 G+(d,p) level is compared with the experimentally determined structure in the solid state. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap is 4.6548 eV.

This study aimed to use biomineralization technology to improve the bond strength of fiber-reinforced lightweight aggregate concrete (LWAC) after exposure to temperatures of 300 °C and 500 °C. The specimens of a control group (Group A) and two experimental groups (Group B and Group C) were prepared. These specimens healed themselves in different ways after exposure to high temperatures and pull-out tests. The self-healing method of Group A involved placing the specimen into an incubator. The self-healing method of Group B was the same as that of Group A. The self-healing method of Group C involved immersing the specimen in a mixed solution of urea and calcium acetate for two days, then taking it out and placing it in an incubator for two days. A cycle of four days was undertaken until the desired age was reached. After the specimens were healed to the planned age, the first and secondary pull-out tests and repair compound identification were carried out. After exposure to a temperature of 300 °C and self-healing for 90 days, compared with the specimens in Group A, the relative bond strength ratios of the secondary pull-out tests of the specimens in Group C increased by 20.3%. This indicates that biomineralization can effectively improve the bond strength of LWAC after high-temperature damage.

Conclusion: When applied to the air-abraded Filtek™ Bulk Fill Flowable Restorative composite surface, 10-MDP-containing adhesives perform better than 10-MDP-free adhesives. The binding strength was unaffected by the 10-MDP-containing adhesives' chemical makeup. The bond strength endurance of adhesives containing 10-MDP decreases with age. Keywords: keyword 1; keyword 2; keywords: low-viscosity bulk fill composite, universal adhesives, self-etch adhesive, 10-MDP, aging, bond strength.

The research object was the stress-strain state of shear stud bonds in the contact joint of steel-concrete beams. The work diagrams for three types of anchors are given. Based on the analysis of numerical and full-scale experiments, analytical dependencies are proposed that reflect the actual operation of anchor ties. Comparisons of the calculation results by analytical formulas and comparisons with numerical and full-scale experiment data are given. Numerical studies have revealed the pattern of the stress-strain state of the contact joint, the stages of development of cracks in the concrete flange, and the sequence of development of deformations in anchor ties. It was revealed that vertical shear studs bonds have an increased bearing capacity, although displacements are 1.5-2 times greater than those of loop-shaped anchor ties.

Sumatriptan is a serotonin receptor agonist approved by FDA in 1992 to treat migraines. Its’ solid form used in commercially available drugs Imitrex, Treximet, Onzetra Xsail and Zembrace symtouch is sumatriptan succinate. Herein we report on crystal structure of sumatriptane succinate hemi(ethanol solvate), HSum+·HSucc–·0.5EtOH, its comparison with previously reported solids containing derivatives of sumatriptan.