Spherical microparticles of TiO₂ were synthesized by the ionic liquid-assisted solvothermal method at different reaction time (3, 6, 12 and 24h). The properties of the prepared photocatalysts were investigated by means of UV-vis diffuse-reflectance spectroscopy (DRS), BET surface area measurements, scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). The results indicated that the efficiency of phenol degradation was related with a time of the solvothermal synthesis as determined for TiO₂_EAN(1:1)_24h sample. Microparticles of TiO₂_EAN(1:1)_3h formed during the only 3h of synthesis time revealed really high photoactivity under visible irradiation – 75%. This value increased to 80% and 82% after 12h and 24h, respectively. The photoactivity increase was accompanied by the increase of the specific surface area thus pores size, as well as ability to absorb UV-vis irradiation. The high efficiency of phenol degradation of IL-TiO₂ photocatalysts was ascribed to the interaction between the surface of TiO₂ and ionic liquid components (carbon and nitrogen).

Water borne pathogens present a threat to human health and their disinfection from water poses a challenge, prompting search for newer methods and newer materials. Disinfection of Gram-negative bacterium Escherichia coli and Gram-positive coccal bacterium Staphylococcus aureus in aqueous matrix was achieved within 60 and 90 minutes respectively at 35⁰C using solar-photocatalysis mediated by sonochemically synthesized Ag@ZnO core-shell nanoparticles. The efficiency of the process increased with increase in temperature and at 55⁰C the disinfection could be achieved in 45 and 60 min respectively for the two bacteria. A new ultrasound assisted chemical precipitation technique was used for the synthesis of Ag@ZnO core-shell nanoparticles. The characteristics of the synthesized material were established using physical techniques. The material remained stable even at 400o C. Disinfection efficiency of the Ag@ZnO core-shell nanoparticles was confirmed in case of real world water samples from pond, river, municipal tap and was found to be better than that of pure ZnO and TiO2 (Degussa P25). When the nanoparticle based catalyst was recycled and reused for subsequent disinfection experiments, its efficiency did not change remarkably even after three cycles. The sonochemically synthesized Ag@ZnO core-shell nanoparticles have a good potential for application in solar photocatalytic disinfection of water borne pathogens.

The Polyurethane (PU) mixture is a high−performance engineering material with different dynamic properties compared to a hot−mixed asphalt mixture (HMA). This paper analyzed whether the Kramers−Kronig (K−K) relation and thermo−rheological simple properties were applicable to the PU mixture. Based on the result discussion, the PU mixture exhibited thermo−rheological simple properties within the test conditions. The time−temperature superposition principle (TTSP) was applicable for the PU mixture to construct the dynamic modulus master curve using the standard logistic Sigmoidal (SLS) model, the generalized logistic sigmoidal (GLS) model, and the Havriliak−Negami (HN) model. The Hilbert integral transformed SLS and GLS models for the phase angle can accurately fit the measured phase angle data with newly fitted shift factors and predict the phase angle within the viscoelastic range. The Core−Core and black space diagrams both displayed single continuous smooth curves, which can be utilized to characterize the viscoelastic property of the PU mixture. The K−K relation is applicable for the PU mixture to obtain the phase angle master curve model, storage modulus, and loss modulus from the complex modulus test results. The phase angle of the PU mixture cannot be derived from the dynamic modulus data and currently needs to be derived from the laboratory measurement.

innate and adaptive immune responses lead to wound healing by regulating a complex series of events promoting cellular cross-talk. An inflammatory response is presented with its characteristic clinical symptoms: heat, pain, redness, and swelling. Some smart thermo-responsive polymers like chitosan can be used to create biocompatible and biodegradable scaffolds with 3D architectures similar to human structures, allowing their efficient and safe use as tissue engineering and drug delivery systems in chronic wounds. Locally heated tumors above polymer lower critical solution temperature can induce its conversion into a hydrophobic form, enhancing drug release until the thermal stimulus is gone, where a lower release is due to the swelling of the material. This paper integrates the relevant reported contributions of bioengineered scaffolds for thermo-responsive drug delivery in wound healing. Therefore, we present a comprehensive review that aims to demonstrate the capacity of these systems to provide spatially and temporally controlled release strategies for one or more drugs used in wound healing. In this sense, the novel manufacturing techniques of 3D-printing and electrospinning are explored for the tuning of their physicochemical properties to adjust therapies according to the patient’s convenience, as well as reduce drug toxicity and side effects.

This work is the first part of a series of papers on a comprehensive analysis of the processes of prebiotic self-organization and protophotosynthesis on the surface of semiconductor minerals and in systems of natural dispersed semiconductors. Comprehensive analysis within the framework of the "semiconductor world" concept allows integrating a variety of models on a single physical basis - from ZnS world and FeS world (based on inorganic semiconductors) to the PAH world and aromatic world (including organic semiconductors). Thus, we do not put forward a new alternative hypothesis of chemical evolution - a new "chemical world", but only integrate the evolutionary and geochemical criteria of different "chemical worlds" into a single "physical world", which gives one the opportunity to reconstruct and predict the directions of chemical evolution according to the uniform principles of physical chemistry. In the first part of this series we consider photoinduced self-organization and "photo-controlled" evolution of the early protobiological systems performing solar energy conversion on the surface of dispersed semiconductor minerals capable of (photo)catalyzing and photosensitizing prebiological processes. The latter include a transition from the elementary cycles of photocatalytic reactions on the surface of semiconductors to protophotometabolic cycles and protophotosynthesis, from photophysical processes on the surface of mineral semiconductors to photoinduced membrane potentials, from photocontrolled sorption on the surface of such minerals to the formation of photosensitive protomembranes and selection of photosynthetic structures. The evolutionary approach to the analysis of protobiological mechanisms and protobioenergetics within the framework of the "semiconductor world" concept provides a new approach to the study of the last common point of divergence of protobiological systems, where the emergence principles of different energy supply schemes (like the energy source-specific photoautotrophy and substrate-specific chemoautotrophy) merge at the physicochemical level. The proposed integrating scheme is consistent with most biological, geological, and physicochemical concepts, which ensures its complete cross-checking and internal consistency.

Radially polymerized dendritic compounds are nowadays an established polymer category next to their linear, branched and cross-linked counterparts. Their uncommon tree-like architecture is characterized by adjustable internal cavities and external groups. They are therefore exceptional absorbents and this attainment of high concentrations into their interior renders them ideal reac-tion media. In this framework they are applied in many environmentally benign implementa-tions. One of the most important among them is water purification though pollutant decomposi-tion. Simple and composite catalysts and photo-catalysts containing dendritic polymers and ap-plied in water remediation will be discussed jointly with some unconventional solutions and fu-ture prospects.

The present study evaluates mold fungal resistance of newly developed loose-fill thermal insulation materials from wheat straw, corn stalk and water reed. Three different processing methods of raw materials was performed by mechanical crushing (Raw, ≤ 20 mm), thermal-mechanical pulping (TMP) using 4% NaOH and steam explosion pulping (SEP). An admixture of boric acid (8%) and tetraborate (7%) was applied to all processed substrates due to their anti-fungal properties. Additionally, the fourth sample group was prepared from SEPs of all raw species without boric acid and tetraborate (SEP*) as control. Samples from all treatments were separately inoculated by 5 different fungal species and incubated in darkness for 28 days at 28 ℃ and RH >90%. The highest resistance to the colonization of mold fungi was achieved by TMP and SEP processing coupled with addition of boric acid and tetraborate, where molds infest only around 35% to 40% of the inoculated sample area. The lowest mold fungi resistance was detected for Raw and SEP* samples, each ~75% that was affected by rich amount of accessible nutrients, suggesting that boric acid and tetraborate additives alone did not prevent mold fungal growth as effective as in combination with TMP and SEP treatments. Together, the achieved fungal colonization scores after combined fungicide and pulping treatments are acceptable for the application of various renewable materials in future thermal insulation product development.

The contribution aims to bring forth a novel synthesis route in developing transparent UV-LED curable coatings accounting various exposure options. A selection of perfluoropolyether (PFPE)-urethane methacrylate and acrylate resins, free-radical photo-initiator Omnirad 2100, and two distinct silane based crosslinking agents were blended under a weight ratio of 75:20:5 (without crosslinker) and 70:15:5:10, respectively. The coatings were cured under a UV-LED 4 x 3 matrix light emitting source, in a chamber under controlled atmosphere, by means of an in-house developed conveyor belt type platform, at different conveyor belt speed (5, 50, 150, 250, and 500 mm/s). The morphologies of fabricated coatings were characterized by FTIR revealing high conversion rates (e.g., from 98 to 100%) for increased exposure time as resulted from the 5 or 50 mm/s values, on all combinations. Dynamic-mechanical and optical properties of UV-LED cured transparent coatings were also investigated. A negative shift of a glass transition temperature values with a decrease in exposure time, in all combinations, from about 60 °C to 30 °C, along with storage moduli lowering in the glassy plateau further favor on higher exposure times for curing. The refractive indices of polymers were from 1.38 to 1.40, whereas the thermo-optic coefficients are showing minor changes around value of 2.55∙10-4 K-1.

The aspirated hypersonic air-breathing propulsion system requires a large amount of power generation, but its special structure makes it impossible to adopt common power generation methods. The high-temperature gaseous hydrocarbon fuel thermal power generation (TPG) system was developed to solve the power generation problem for hypersonic air-breathing propulsion system. But off-design operating conditions of the hypersonic propulsion system results in a more complex process for both propulsion system and the TPG system. To better analyzing the dynamic thermos-physical characteristics of hypersonic airbreathing propulsion system considering thermal-mechanical coupling process among cooling/TPG system, a dynamic analytical model was developed, and the dynamic thermos-physical characteristics of TPG system under different off-design working conditions were conducted. It can be concluded from the analytical results that the dynamic process of thermos-physical characteristics shows a complex trend under the flight Mach number and fuel equivalence ratio off-design working conditions. Such complexity of dynamic characteristics brings difficulties in fuel supply for the propulsion system.

Titanium dioxide (TiO₂) micro and nano architectures have been intensively studied in the past years because of many varied applications in environmental, energy conversion, and storage fields, such as heterogeneous catalysis, dye-sensitized solar cells, lithium/sodium ion batteries, lithium-sulfur (Li-S) batteries, and bio-nanotechnology, etc. Especially the surface and interface structures in the TiO₂ structures play important roles in those applications. This mini review article focuses on TiO₂ micro and nano architectures with the prevalent crystal structures (anatase, rutile, brookite, and TiO₂(B)), and summarizes major advances in the surface and interface engineering and applications in environmental and electrochemical applications. We present the principles and growth mechanisms of TiO₂ nanostructures via different strategies, with an emphasis on rational control of the surface and interface structures. We further discuss the applications of TiO₂ micro and nano architectures in photocatalysis, lithium/sodium ion batteries, and Li-S batteries. Throughout the discussion, the relationship between the device performance and the surface structures of TiO₂ micro/nano structures will be highlighted. Then we discuss the phase transitions of TiO₂ nanostructures and possible strategies of improving the phase stability. The review concludes with a perspective on the current challenges and future research directions.

A heterograft copolymer with an alginate backbone, hetero-grafted by polymer pendant chains displaying different Lower Critical Solution Temperatures (LCSTs), combined with a pH-responsive Poly(2-vinyl pyridine)-b-poly(ethylene oxide) (P2VP-b-PEO) diblock copolymer forming micellar nanoparticles, was investigated in aqueous media at various pH. Due to its thermoresponsive side chains, the copolymer forms hydrogels with thermo–induced sol–gel transition, above a critical temperature, Tgel (thermo–thickening). However, by lowering pH of the medium in acidic regime, a remarkable increase of the elasticity of the formulation was observed. This effect was more pronounced in low temperatures (below Tgel) suggesting secondary physical crosslinking, which induces significant changes in the hydrogel thermoresponsiveness, transforming the sol–gel transition to soft gel–strong gel. Moreover, the onset of thermothickening shifted to lower temperatures followed by broadening of the transition zone, implying intermolecular interactions between the uncharged alginate backbone with the PNIPAM side chains, likely through H–bonding. The shear–thinning behavior of the soft gel in low temperatures provides injectability, which allows 3D–printing potential applications. Furthermore, the heterograft copolymer/nanoparticles composite hydrogel, encapsulating a model hydrophobic drug in the hydrophobic cores of the nanoparticles, was evaluated as pH-responsive drug delivery system. The presented tunable drug delivery system might be useful for biomedical potential applications.

This research is completed in development of researches devoted to relations between elastic modulus (MoE) and thermal expansivity (CTe) of different materials. This study experimentally confirmed the relation of MoE and CTe for thermosetting polymers and FRPs both under normal and heating temperatures. As the thermosetting polymers, the epoxy compositions were used and glass fiber and mineral additives for FRP. The experiment was based on dilatometric and elastic deformations’ testing. Also, the relaxation model of MoE/CTe was proposed, that is based on physical properties of polymers’ supramolecular structures. The comparative analyzing of MoE/CTes’ different models is done. The most accurate models are determined, and the relaxation model has demonstrated the high accuracy.

Antibody-mediated targeting is an efficient strategy to enhance the specificity and selectivity of polymer nanomedicines towards the target site, typically a tumor. However, direct covalent coupling of an antibody with a polymer usually results in a partial damage of the antibody binding site accompanied with a compromised biological activity. Here, an original solution based on well-defined non-covalent interactions between tris-nitrilotriacetic acid (trisNTA) and hexahistidine (His-tag) groups, purposefully introduced to the structure of each macromolecule, is described. Specifically, trisNTA groups were attached along the chains of a hydrophilic statistical copolymer based on N-(2-hydroxypropyl)methacrylamide (HPMA), and at the end or along the chains of thermo-responsive di-block copolymers based on N-isopropylmethacrylamide (NIPMAM) and HPMA; His-tag was incorporated to the structure of a recombinant single chain fragment of an anti-GD2 monoclonal antibody (scFv-GD2). Static and dynamic light scattering analyses confirmed that mixing of polymer with scFv-GD2 led to the formation of polymer/scFv-GD2 complexes; those prepared from thermo-responsive polymers formed stable micelles at 37 °C. Flow cytometry and fluorescence microscopy clearly demonstrated antigen-specific binding of the prepared complexes to GD2 positive murine T-cell lymphoma cells EL-4 and human neuroblastoma cells UKF-NB3, while no interaction with GD2 negative murine fibroblast cells NIH-3T3 was observed. These non-covalent polymer protein complexes represent a new generation of highly specific actively targeted polymer therapeutics or diagnostics.

A major advance of drug discovery and targeted therapy directed to cancer cells may be achieved by exploitation and immunomodulation of their unique biological property. This re-view summarizes our efforts to develop novel chemo-thermo-immuno-therapy (CTI therapy) by conjugating a melanogenesis substrate, N-propionyl cysteaminylphenol (NPrCAP: amine analog of tyrosine), with magnetite nanoparticles (MNP). In our approach, NPrCAP provides a unique drug delivery system (DDS) because of its selective incorporation into melanoma cells. It also functions as a melanoma-targeted therapeutic drug because of its production of highly reactive free radicals (melanoma-targeted chemotherapy). Moreover, utilization of MNP is a platform to develop thermo-immunotherapy because of heat shock protein (HSP) generation upon exposure to an alternating magnetic field (AMF). The feasibility of our approach was successfully shown in experimental in vivo and in vitro mouse melanoma models and in preliminary clinical trials to a limited number of advanced melanoma patients.

Our environment has been impacted by man-made pollutants mainly industries make substantial use of synthetic dyes which exhibit cytotoxicity and have significant environmental consequences. Effective photocatalyst-based approaches for degrading synthetic dyes into less toxic chemical are of great interest. Synthesizing NPs using biological approaches, particularly plant-based approaches offer advantages, decreasing the risk of NPs losing biocompatibility during synthesis, cost-effectiveness, and eco-friendliness. In this study, we employed a green synthesis method to produce manganese oxide nanoparticles (MnO NPs) utilizing leaf extract from the Lathyrus Aphaca plant. The synthesized MnOx NPs were characterized through various techniques; X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), and UV–visible spectroscopy. XRD analysis showed distinct peaks, indicated the presence crystallographic planes within the MnO₂ nanoparticles, thus confirming their crystalline structure. SEM study highlighted closely packed configurations with average size of approximately ≥ 50-70 nm, with well-defined boundaries. EDX analysis showed the presence of elemental manganese (Mn) in the samples, with peaks corresponding to Mn detected at lower energy levels, predominantly represented by MnO. FTIR, showed the presence of the O-O stretching mode at a frequency of 719 cm^-1, the presence of MnO₆ oxides of manganese, and peak at 548 cm^-1 corresponded to the Mn-O stretching mode. Furthermore, the green-synthesized manganese oxide nanoparticles exhibited promising photocatalytic and adsorption capabilities against Methylene Blue (MB) dye, leading to approximately 93.21% degradation of MB when treated with the green-synthesized MnO nanoparticles derived from plant extract. This highlights the efficacy and potential of these nanoparticles in environmental remediation applications, particularly in the degradation of methylene blue contaminants.

Radical reactions in water or aqueous media are important for organic synthesis, realizing high yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to organic chemistry in water and aqueous media, (ii) synthetic approaches in-, on- and with-water as well as in heterogeneous phase, (iii) reaction of carbon-centered radicals with water (or deuterium oxide) activated through coordination with various Lewis acids, (iv) photocatalysis in water and aqueous media, and (v) synthetic applications bioinspired from naturally occurring processes. A wide range of chemical processes and synthetic strategies under different experimental conditions have been reviewed that lead to important functional group translocation and transformation reactions, leading to the preparation of complex molecules. These results reveal how water as a solvent/medium/reagent in radical chemistry has matured over the last two decades and how further discoveries are foreseen to come in the near future.

Ti-aluminosilicate gels were used as supports for immobilization of Fe, Co and Ni oxides (5%) by impregnation, and synthesis of efficient photocatalysts in degradation of β-lactam antibiotic from water. Titanium oxide (1 and 2%) was incorporated into zeolite network by modifying the gel during the zeolitation process. The formation of the zeolite Y structure and its microporous structure were evidenced by X-ray diffraction and N2 physisorption. The structure, composition, reduction and optical properties were studied by X-ray difraction, H2-TPR, XPS, Raman, photoluminiscence and UV-Vis spectroscopy. The obtained results indicated a zeolite Y structure for all photocatalysts with tetra-coordinate Ti4+ sites. The immobilized metals from group VIII are both in the form of metal oxides such as Fe2O3, Fe3O4, CoO, Co3O4 , NiO and also in the me-tallic state (Fe0, Co0, and Ni0). A red shift of the absorption edge was observed in UV-Vis spectra of photocatalysts upon addition of Fe, Co or Ni species. The photocatalytic performances were evaluated in degradation of cefuroxime from water under visible light irradiation. The best results were obtained for iron immobilized photocatalysts. Scavenger experiments explained the photocatalytic results and their mechanisms. A different contribution of the active species to the photocatalytic reactions was evidenced.

Ground-based high-power lasers enable to, in principle, deorbit any kind of space debris object from the low Earth orbit (LEO) by remotely inducing laser-ablative momentum. However, the assessment of efficiency and operational safety depends on many factors like atmospheric constraints or the risk of debris disintegration during irradiation. We analyze laser momentum for a great variety of target geometries and sizes, and – for the first time in a large-scale simulation – include thermal constraints for laser irradiation configuration. Using a coherently coupled 100 kJ laser system at 1030 nm wavelength, 5 ns pulse duration in an optimized pointing elevation angle range, the pulse frequency should amount to less than 10 Hz to prevent fragment meltdown. For mechanically intact payloads or rocket bodies, repetition rates should be even lower. Small debris fragments sized between 10 and 40 cm can be de-orbited by around 100 to 400 station passes with head-on irradiation while objects exceeding 2 m typically require far more than 1000 irradiations for deorbit. Hence, laser-based debris removal cannot be considered a prime space sustainability measure tackling the top-risk large debris, yet it can provide for remediation of a multitude of small-sized debris using small networks of globally distributed laser sites.