Three new tetraphenylethene (TPE) push-pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2+2] cycloaddition - retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) as electron-deficient alkene. Only the starting TPE-alkyne displayed a significant AIE behavior, whereas for TPE-TCNE,a faint effect was observed and for TPE-TCNQ and TPE-F4-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV-Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F4-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F4-TCNQ with donor-substituted are promising candidates for PT applications.

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.

The study of phytotherapy in dentistry is relevant due to the low occurrence of research in the treatment of oral pathologies, such as caries and periodontal disease. Thus, the aim of this research was to characterize the chemical composition of extracts from the leaves of Couroupita guianensis Aubl, including toxicological evaluation and the antioxidant and antimicrobial potential against Staphylococcus aureus, Streptococcus mutans and Candida albicans. Three extracts were prepared using assisted ultrasound, originating the Crude Ultrasound Extract (CUE) and Soxhlet apparatus, originating the Crude Soxhlet Extract (CSE) and the Ethanol Soxhlet Extract (ESE). In the analysis of the chemical composition, the presence of flavonoids, tannins and saponins were detected. LC-DAD analysis revealed the presence of caffeic acid, sinapic acid, rutin, quercetin, luteolin, kaempferol and apigenin in all extracts. In the GC-MS analysis, stigmasterol and β-sitosterol were identified in CUE and CSE. The antioxidant potentials, determined by the DPPH• and ABTS•+ methods, the ESE showed higher antioxidant activity (2.98 ± 0.96 and 4.93 ± 0.90, respectively). In the evaluation of toxicity, the CUE 50µg/mL and the ESE 50 µg/mL presented growth stimulation of Allium cepa roots. At a concentration of 750µg/mL, all extracts inhibited root growth. None of the extracts showed toxicity against Artemia salina. Antibacterial action was detected in all extracts, mainly against the microorganisms S. aureus and S. mutans; however, the antifungal action against C. albicans was not detected. From the results, the extracts of C. guianensis have therapeutic potential for use in the control of microorganisms in the oral microbiota.

The research was conducted in the Kırklareli stream, which flows southwest through the city of the same name toward the village of Kavaklı. The aim of the study is to evaluate water analysis results and assess the potential that the European Union drinking water standard for lead can be achieved in the Kırklareli stream by reliance on the low solubility of lead phosphate minerals. The present study used Visual MINTEQ 3.1 for all water chemistry simulations. The European Union drinking water standard for lead, which is 10 μg L⁻¹, is exceeded at least once and as many as three times at seven of the ten sites during the 2018 sampling season. Although the database solubility of hydroxypyromorphite is exceeded in most samples, it appears this may be the result of major ion substitutions in the hydroxypromorphite that forms in the Kırklareli stream which increases the effective solubility of lead in the stream.

Evolutionary theory suggests that the origin, persistence, and evolution of biology is driven by the “natural selection” of characteristics improving the differential reproductive success of the organism in the given environment. The theory, however, lacks physical foundation, and, therefore, at best, can only be considered a heuristic narrative, of some utility for assimilating the biological and paleontological data at the level of the organism. On deeper analysis, it becomes apparent that this narrative is plagued with problems and paradoxes. Alternatively, non-equilibrium thermodynamic theory, derived from physical law, provides a physical foundation for describing material interaction with its environment at all scales. Here we describe a “natural thermodynamic selection” of characteristics of structures (or processes), based stochastically on increases in the global rate of dissipation of the prevailing solar spectrum. The different mechanisms of thermodynamic selection are delineated for the different biotic-abiotic levels, from the molecular level at the origin of life, up to the level of the present biosphere with non-linear coupling of biotic and abiotic processes. At the levels of the organism and the biosphere, the non-equilibrium thermodynamic description of evolution resembles, respectively, Darwinian and Gaia descriptions, although the underlying mechanisms and the objective function of selection are fundamentally very different.

Global pollution from fossil plastics is one of the top environmental threats of our times. The end-of-life scenarios of fossil plastic, including recycling, incineration and disposal result in mi-croplastic formation, elevated atmospheric CO2 levels, and littering of terrestrial and aquatic environments by plastic waste. Currently thought-out regulations centered around banning plastics production and use and only recycling on a regional, national and global level are impeding efforts to rapidly replace fossil plastics through the use of natural alternatives. In particular, this review demonstrates how mi-crobial polyhydroxyalkanoates (PHA), a class of intrinsically natural polymers, can easily remedy for the fossil and persistent plastic dilemma. PHA are bio-based, bio-synthesized, bio-compatible, bio-degradable, and home- and industrially compostable. Therefore, they are one of the perfect replacements for our fossil plastics pollution dilemma, providing us with the benefits of fossil plastics and meeting all requirements of a truly circular economy. PHA biopolyesters are natural and green materials in all aspects of their life cycle. The review elaborates in detail how PHA’s production, consumption, and end-of-life profile are perfectly embedded in the current topical 12 Principles of Green Chemistry, which constitute the basis for sustainable product manufacturing. It is shown that it is time for a paradigm shift in plastics manufacturing, use and disposal. Hu-mankind needs alternatives to fossil plastics, which, as recalcitrant xenobiotics, contribute to the increasing deterioration of our planet. Natural PHA biopolyesters represent that paradigm shift!

Cannabis sativa is one of the oldest plants utilized by humans for both economic and medical purposes. Although the use of cannabis started millennia ago in the Eastern part of the hemisphere, its use has moved and flourished in the Western Nations in more recent centuries. C. sativa is the source of psychoactive cannabinoids that are consumed as recreational drugs worldwide. The C21 aromatic hydrocarbons are restricted in their natural occurrence to cannabis (with a few exceptions). Delta-9-tetrahydrocannabinol (Δ9-THC) is the main psychoactive component in cannabis with many pharmacological effects and various approved medical applications. However, a wide range of side effects are associated with the use of Δ9-THC, limiting its medical use. In 1966, another psychoactive cannabinoid, Delta-8-tetrahydrocannabinol (Δ8-THC) was isolated from marijuana grown in Maryland but in very low yield. Δ8-THC is gaining increased popularity due to its better stability and easier synthetic manufacturing procedures compared to Δ9-THC. Passing the U.S. Farm Bill in 2018 led to an increase in the sale of Δ8-THC in the United States. The marketed products contain Δ8-THC from synthetic sources. In this review, methods of extraction, purification, and structure elucidation of Δ8-THC will be presented. The issue of whether Δ8-THC is a natural compound or an artifact will be discussed, and the different strategies for its chemical synthesis will be presented. Δ8-THC of synthetic origin is expected to contain some impurities due to residual amounts of starting materials and reagents as well as side products of the reactions. The various methods of analysis and detection of impurities present in the marketed products will be discussed. The pharmacological effects of Δ8-THC, including its interaction with CB1 and CB2 cannabinoid receptors in comparison with Δ9-THC, will be reviewed.

With the aim of profitable conversion of carbon dioxide (CO2) in an efficient, economical and sustainable manner, we developed a CuBr/ionic liquid (1-butyl-3-methylimidazolium acetate) catalytic system which could efficiently catalyze the three-component reactions of propargylic alcohols, 2-aminoethanols, and CO2 to produce 2-oxazolidinones and α-hydroxy ketones. Remarkably, this catalytic system employed lower metal loading (0.0125-0.5 mol%) but exhibited the highest turnover number (2960) ever reported, demonstrating its excellent activity and sustainability. Moreover, our catalytic system could efficiently work under 1 atm of CO2 pressure and recycle among the metal-catalyzed systems.

The accurate prediction of molecular properties such as lipophilicity and aqueous solubility are of great importance and pose challenges in several stages of the drug discovery pipeline. Machine learning methods like graph-based neural networks (GNNs) have shown exceptionally good performance in predicting these properties. In this work, we introduce a novel GNN architecture, called directed edge graph isomorphism network (D-GIN). It is composed of two distinct sub-architectures (D-MPNN, GIN) and achieves an improvement in accuracy over its sub-architectures employing various learning, and featurization strategies. We argue that combining models with different key aspects help make graph neural networks deeper and simultaneously increase their predictive power. Furthermore, we address current limitations in assessment of deep-learning models, namely, comparison of single training run performance metrics, and offer a more robust solution.

We have suggested that the abiogenisis of life around the beginning of the Archean may have been an example of microscopic dissipative structuring of UVC pigments (the fundamental molecules of life) under the prevailing surface UV solar spectrum. In a previous article in this series, we have describe the non-equilibrium thermodynamics and the photochemical mechanisms which may have been involved in the dissipative structuring of the purines adenine and hypoxanthine from the common precursor molecules of HCN and water under UVC light. In this article we extend our analysis to include the production of the other two important purines, guanine and xanthine, from these same precursors. The photochemical reactions are presumed to occur within a fatty acid vesicle floating on a hot ocean surface exposed to the prevailing UV light. Reaction-diffusion equations are resolved under different environmental conditions. Significant amounts of adenine (∼10−5 M) and guanine (∼10−6 M) are obtained within only a few months at 80 °C under plausible initial concentrations of HCN and cyanogen (a photochemical product of HCN).

Within this work we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength, after which cytotoxic reactive oxygen species (ROS) are generated. The metal coordination allows for the use of the heavy atom effect, which can enhance the triplet generation necessary for generation of ROS. Additionally, the flexibility of these complexes for metal ions, substitutions and ligands allows the possibility to tune their photophysical properties. A general overview of the mechanism of photodynamic therapy and the properties of the triplet photosensitizers is given, followed by further details of dipyrrinato complexes described in the literature that show relevance as photosensitizers for PDT. In particular, the photophysical properties of Re(I), Ru(II), Ir(III), Ni(II), Cu(II), Pd(II), Pt(II), Zn(II), Ga(III), In(III), Al(III), Sn(II), and P dipyrrinato complexes are discussed. The potential for future development in the field of (dipyrrinato)metal complexes is addressed and several new research topics are suggested throughout this work. We propose that significant advances could be made for heteroleptic bis(dipyrrinato)zinc(II) and homoleptic bis(dipyrrinato)palladium(II) complexes and their application as photosensitizers for PDT.

Arctic ozone amount in winter to spring shows large year-to-year variation. This study investigates Arctic spring ozone in relation to the phase of quasi-biennial oscillation (QBO)/the 11-year solar cycle, using satellite observations, reanalysis data, and outputs of a chemistry climate model (CCM) during the period of 1979–2011. For this duration, we found that the composite mean of the Northern Hemisphere high-latitude total ozone in the QBO-westerly (QBO-W)/solar minimum (Smin) phase is slightly smaller than those averaged for the QBO-W/Smax and QBO-E/Smax years in March. An analysis of a passive ozone tracer in the CCM simulation indicates that this negative anomaly is primarily caused by transport. The negative anomaly is consistent with a weakening of the residual mean downward motion in the polar lower stratosphere. The contribution of chemical processes estimated using the column amount difference between ozone and the passive ozone tracer is between 10–20% of the total anomaly in March. The lower ozone levels in the Arctic spring during the QBO-W/Smin years are associated with a stronger Arctic polar vortex from late winter to early spring, which is linked to the reduced occurrence of sudden stratospheric warming in the winter during the QBO-W/Smin years.

Generative artificial intelligence tools are flourishing across various sciences, particularly in the educational domain. ChatGPT, with its versions 3.5 and 4.0, stands out for its multilingual capabilities, catering to both students and educators. This research aimed to evaluate the performance differences between these versions, and importantly, to compare the accuracy of ChatGPT's responses in English versus Arabic. In our study, we presented ChatGPT with 39 chemistry problems related to 6th-7th grade curriculum, including twenty-five open questions and fourteen multiple-choice questions. Each response was categorized as accurate, partially accurate, or inaccurate. Our analysis, focused on trends across versions and languages, revealed significant enhancements in version 4.0, particularly in its ability to process Arabic. However, despite these improvements, our findings indicate that responses in English consistently outperformed those in Arabic in terms of accuracy. In light of this discrepancy, we suggest that ChatGPT either incorporates additional Arabic databases into its training regimen or develops a code that adopts the following strategy to ensure more accurate responses in science education: questions should first be translated from Arabic to English, addressed, and then retranslated into Arabic before being presented to the user. This approach takes advantage of the greater accuracy of responses in English to benefit Arabic-speaking users, and it may also improve outcomes for speakers of other languages who experience less precise answers in the fields of chemistry or science education.

We synthesized iron(II)-triazole spin crossover compounds of the type [Fe(atrz)3]X2 and incorporated and deposited them on electrospun polymer nanofibers. In view of possible applications, we chose iron(II)-triazole-complexes that are known to exhibit spin crossover close to ambient temperature. Therefore we used the complexes [Fe(atrz)3]Cl2 and [Fe(atrz)3](2ns)2 (2ns = 2Naphthalenesulfonate) and analyzed them with IR-, UV/Vis and Mossbauer spectroscopy and with a SQUID magnetometer. The synthesized complexes were then in one attempt deposited on fibers of polymethylmethacrylate (PMMA) and in another attempt incorporated into core-shell like PMMA fiber structures. This was done via two different electrospinning methods. Deposition was performed by uniaxial electrospinning and incorporation was performed by coaxial electrospinning. The obtained polymer-complex-composites were then further investitgated by the same methods as the pure complexes as well as by SEM pictures and EDX measurements. The analysis by UV/Vis spectroscopy, Mössbauer spectroscopy and temperature-depended magnetic measurements with the SQUID magnetometer showed that the spin crossover properties were maintained and were not changed after the electrospinning processes and that the complexes were not harmed during the procedure.

Successful fertilization treatments targeted to improve stand productivity while reducing operational complexities and cost depend on a clear understanding of soil nutrient availability under varying environmental conditions. Soil nutrient data collected from 154 forest sites throughout the Inland Northwest, USA were analyzed to examine soil nutrient characteristics on different geologic soil parent materials and to rank soil fertility. Results show that soil parent material explains significant differences in soil nutrient availability. Soils developed from volcanic rocks have the highest CEC and are relatively high in P, K, S, Mg, Cu, Ca, and B, but generally poor in N. Forest soils developed from plutonic rocks exhibit the lowest CEC and are low in N, S, K, Mg, Cu, and Ca, but higher in P. Some soils located on mixed glacial till are low only in K, Cu, Mg, and Ca, but many glacial soils are relatively rich in other nutrients, albeit the second lowest CEC. Soils developed from metasedimentary and sedimentary rocks are among those with lowest soil nutrient availability for P and B. Sulfur was found to have the highest concentrations in metasedimentary influenced soils and the least in sedimentary derived soils. Our results should be useful in designing site-specific fertilizer and nutrient management prescriptions for forest stands growing on soils developed from these major geologies within the Inland Northwest region of the United States.

Polyphenol ellagic acid (EA) possesses anti-oxidant, anti-inflammatory, anti-carcinogenic, anti-diabetic and cardio protection activities, remarking it an interesting multi-targeting profile. EA also controls the central nervous system (CNS) since it was proven to reduce the immobility time of mice in both the forced swimming and the tail-suspension tests, with an efficiency comparable to that of classic antidepressants. Interestingly, the anti-depressant-like effect was almost nulled by the concomitant administration of selective antagonists of the noradrenergic receptors, suggesting the involvement of these cellular targets in the central effects elicited by EA and its derivatives. By in silico and in vitro studies, we discuss how EA engages with human α2A-ARs and α2C-AR catalytic pockets, comparing EA behaviour with those ones of known agonist and antagonist. Structurally, the hydrophobic residues surrounding α2A-AR pocket confer specificity on the intermolecular interactions and hence lead to favourable binding of EA in the α2A-AR, with respect to α2C-AR. Moreover, EA seems to better accommodate within α2A-ARs into TM5 area, closely to S200 and S204 which play a crucial role for activation of aminergic GPCRs such as the α2-AR, highlighting its promising role as a partial agonist. Consistently, EA mimics clonidine in inhibiting noradrenaline exocytosis from hippocampal nerve endings in an yohimbine-sensitive fashion that confirms the engagement of naïve α2-ARs in the EA-mediated effect.

This paper presents the development of a cheap and rapid electrochemical sensor for ascorbic acid detection. In particular, the graphite ink working electrode of screen-printed cells was covered by a film of elecrosynthesized molecularly imprinted polypyrrole (e-MIP); differential pulse voltammetry (DPV) was the selected method for the analyte detection. The ascorbic acid molecules were suc-cessfully entrapped in the polypyrrole film, creating the recognition sites. The best results were obtained after polypyrrole overoxidation and performing the measurements in phosphate buffer solution 0.05 M/KCl 0.1M at pH 7.5. The comparison with the bare and the not imprinted polypyrrole-modified electrodes showed the highest selectivity and reproducibility of the e-MIP-based sensor. The developed method was applied to assess ascorbic acid in farmaceutical products obtaining values not significantly different from the declared content.

Despite the recent advances in melanoma therapy, the need for new targets and novel approaches to therapy is urgent. We previously reported melanoma actives that work via binding and downregulating spliceosomal proteins hnRNPH1 and H2 (Palrasu et al., 2019). Given lack of knowledge about side effects of using spliceosomal binders in humans, an acute toxicity study was conducted to evaluate these compounds in mice. Male and female mice were treated with compounds 2155-14 and 2155-18 at 50mg/kg/day via subcutaneous injections and the clinical signs of distress were monitored for 21 days and compared with control mice. Additionally, effect of the leads on blood chemistry, blood cell counts, and organs was evaluated. No significant changes were observed in the mice body weight, blood cell count, blood chemistry, or organs following the compound treatment. The results show that our compounds 2155-14 and 2155-18 are not toxic for the study period of three weeks.

I describe the non-equilibrium thermodynamics and the photochemical mechanisms which may have been involved in the dissipative synthesis, proliferation, and evolution of the fundamental molecules at the origin of life from simpler and more common precursor molecules such as HCN, H2O and CO2 under the impressed UVC photon flux of the Archean. The fundamental molecules absorb strongly in this UVC region and exhibit strong coupling between their electronic excited and ground states which endows them with efficient photon disipative capacity (broad wavelength absorption and rapid radiationless dexcitation) suggestive of dissipative structuring. The autocatalytic nature of the synthesized molecules in dissipating the same photochemical potential that directed their synthesis leads to their proliferation. The non-linearity in the photochemical and chemical reaction rates provides numerous stationary states which can be reached by amplification of a molecular concentration fluctuation near a bifurcation, promoting the system into states of generally higher photon disspative efficacy. An example is given of the UV photochemical dissipative structuring, proliferation, and evolution of molecules on route to the nucleobase adenine from the common precursor molecules HCN and H2O occurring within a fatty acid vesicle. The kinetic equations are resolved under different environmental conditions, providing a non-equilibrium thermodynamic analysis of the appearance of an early important molecule for the origin of life.

Seyfe Lake is an important part of the natural ecosystem of Central Anatolia and lies within a 1487 km² closed basin. Groundwater withdrawal for irrigation and recent climatic change have caused lake area to decrease for decades and to completely disappear briefly in August 2008. Groundwater quality is crucial for sustainable irrigation in the Seyfe Basin. A key finding of this study is the difference in the Hardie-Eugster alkalinity-to-calcium ratio of the lake water and that of most groundwater wells in the basin. This difference in the chemical signature of Seyfe Lake and basin groundwater means the evaporative salinization pathway of most groundwater discharged into the lake cannot account for the composition of Seyfe Lake. The ratio of actual evapotranspiration to precipitation will increase under current climate change projections. A second finding, with implications for soil salinization, is that most groundwater in Seyfe Basin has a Hardie-Eugster alkalinity-tocalcium ratio greater than unity, meaning soil alkalization will accompany soil salinization.

Visualization has always been a crucial part of the educational process. Implementing computer algorithms and virtual reality tools into it is vital for the new generation engineers, scientists and researchers. In the field of chemistry education, various software that allow dynamic molecular building and viewing are currently available. These software are now used to enhance the learning process and ensure better understanding of the chemical processes from the visual perspective. The present short communication provides a summary of these applications based on the NarupaXR program, which is a great educational tool that combines the functionality and simple design necessary for an educational tool. NarupaXR is used with a companion application “Narupa Builder'' which requires a different file format, therefore a converter that allows a simple transition between the two extensions has been developed. The converter sufficiently increases the efficiency of the educational process. The automatic converter is freely available on GitLab (https://gitlab.com/teamSCAMT/converter_mol2_to_xml). The current communication provides detailed written instructions that can simplify the installation process of the converter and facilitate the use of both the software and the hardware of the VR set.

The representation of aerosols in climate-chemistry models is important for air quality and climate change research, but it can require significant computational resources. To overcome this, simpler modules such as modal aerosol modules with three lognormal modes (MAM3) can be used. In this study, the coupling of the Carbon Bond Mechanism, version Z (CBMZ), and MAM3 chemistry modules in WRF-CAM5 was improved by adding biomass-burning emissions to both gas- and particle-phase chemistry and incorporating a conversion mechanism between volatile organic compounds (VOCs) and secondary organic carbons (SOCs). The study conducted six simulations over the western U.S. and northeastern Pacific region and compared the model’s performance with observational benchmarks such as reanalysis, ground-based, and satellite data. The results showed that the model with enhanced chemistry capabilities had a 31% and 58% reduction in root-mean-square errors (RMSE) for black carbon (BC) and organic carbon (OC) surface concentrations, respectively. The earlier release of the WRF-CAM5 version had two deficiencies that were addressed in this study. This research highlights the importance of accurate aerosol representation in climate-chemistry models for improving accuracy and reducing errors in simulations.

Nuclear technologies have a strong potential and a unique role to play in delivering reliable low carbon energy for a future net-zero society. However, to assure the sustainability required for the long-term success, nuclear will need to deliver innovative solutions as proposed in iMAGINE. One of the most attractive features, but also a key challenge for the envisaged highly integrated nuclear energy system is the need for a demand driven salt clean-up system. The work described provides an insight into the interplay between a potential salt clean-up system and the reactor operation in a plutonium started core in a dynamic approach. The results presented will help to optimize the parameters for the salt clean-up process as well as to understand the differences which appear between a core started with enriched Uranium and Plutonium as the fissile material. The integrated model is used to investigate the effects of the initial fissile material on core size, achievable burnup, and long term operation. Different approaches are tested to achieve a higher burnup in the significantly smaller Pu driven core. The effects of different clean-up system throughputs on the concentration of fission products in the reactor salt and its consequences are discussed for general molten salt reactor design. Finally, an investigation of how a plutonium loaded core could be used to provide fuel for future reactors through fuel salt splitting is presented with the outcome that one Pu started reactor of the same size as a uranium started core could deliver fuel for 1.5 new cores due to enhanced breeding. The results provide an essential understanding for the progress of iMAGINE as well as the basis for inter-disciplinary work required for optimizing iMAGINE.

As part of valorisation of agricultural waste into bioactive compounds, a series of structurally novel oleanolic acid ((3β-hydroxyolean-12-en-28-oic acid, OA-1)-phtalimidines (isoindolinones) conjugates 18a-v bearing 1,2,3-triazole moieties were designed and synthesized by treating a previously azide 4 prepared from OA-1 isolated from olive pomace (Olea europaea L.) with a wide range of propargylated phtalimidines using the Cu(I)-catalyzed click chemistry approach. OA-1 and its newly prepared analogues 18a-v were screened in vitro for their antibacterial activity against two Gram-positive bacteria, Staphylococcus aureus and Listeria monocytogenes; and two Gram-negative bacteria, Salmonella thyphimurium and Pseudomonas aeruginosa. Attractive results were obtained notably against L. monocytogenes. Compounds 18d, 18g and 18h exhibited the highest antibacterial activity when compared with OA-1 and other compounds in the series against tested pathogenic bacterial strains. Molecular docking study was performed to explore the binding mode of the most active derivatives against the target protein from L. monocytogenes. Results showed the importance of both hydrogen bonding and hydrophobic interactions with the target protein and are in favor to the experimental data.

Nuclear technologies have the potential to play a unique role delivering low carbon energy for a future net-zero society. However, for the long-term success, nuclear will need to deliver innovative solutions as proposed in iMAGINE. One of the key challenges for the envisaged highly integrated nuclear energy system is the need for a demand driven salt clean-up system. The work described provides an insight into the interplay between a potential salt clean-up system and the reactor operation in a dynamic approach. The results provided will help to optimize the parameters for the salt clean-up process by delivering a dynamically calculated priority list identifying the elements with high influence on reactor operation. The integrated model is used to investigate the ideal time for the initiation of the clean-up as well as the effect of different throughput through the clean-up system on criticality as well as on the concentration of the elements in the reactor salt. Finally, a staggered approach is proposed with the idea to phase in the chemical clean-up processes step by step to keep the reactor critical. The results provide an essential step for the progress of iMAGINE as well as the basis for the inter disciplinary work required to bring iMAGINE into real operation.

In this paper, a distinction is first made between environmental, sustainable and green chemistry; the last two are then examined in relation to the more general problem of the environmental education. A brief historical digression on the STS (Science, Technology and Society) movement tries to dissect the reasons why chemistry is seen by the general public as a problem, not as a decisive resource for the realization of the ecological transition. Although sustainable and green chemistry can be decisive in overcoming the insularity of chemical disciplines in the high school, it fails to effectively embed itself in educational practices. Specific operational goals, supporting a real scientifical and technological literacy in sustainable and green chemistry, can help chemical educators. They are provided at the end of an examination of the founding axes of sustainable and green chemistry, according to the criteria of scientific and technological literacy.

Metals are indispensable in the life of all organisms, in fact, their dysregulation causes various disorders caused by an interruption of their homeostasis. Nowadays different transition metals are incorporated into pharmaceutical products as diagnostic and therapeutic agents because of their electronic structure which gives them versatility in terms of tuning molecule properties, differently from organic molecules. Hence the interest in the study of metal-drug complexes from different points of view was born and many approaches were developed for the characterization, activation, delivery and molecular mechanisms clarification. The integration of these different approaches starting from chemoproteomics passing through nanoparticle systems to different activation strategies allows the understanding of the cellular responses of metallic drugs, which can be the basis for the design of new drugs and/or modification of drugs currently in use. This review aims to briefly summarize the recent advances in this area by describing the technological platforms and their possible applications to identify protein targets for discovering the mechanisms of action of metallodrugs, and to improve their efficiency in terms of administration.

The reaction of mercaptoacetic acid esters with pentachloro-2-nitro-1,3-butadiene provides appropriate precursors for the synthesis of 2,3,4-trisubstituted benzo[h]quinolines. These heterocycles are easily accessible via a single-step reaction with 1-naphthyl- or 1-anthracenylamine, respectively. Due to steric bulk and high electron density ring closure to benzo[h]quinolines takes place, exclusively. Such highly substituted annelated pyridine systems can be modified in subsequent, selective reactions to build up new N-heterocycles with promising microbiological properties. Antibacterial and antiproliferative assays against four cell mammalian cell lines demonstrate that some of the sulfur-substituted benzo[h]quinolines analogs display potent phenotypic bioactivities in the single-digit micromolar range.

We hereby describe an efficient method for the preparation of a series of new 1-substituted 1,2,3-triazole-based acetaminophen derivatives through a clean, good-yielding, simple, and expeditious procedure based on the O-propargylation reaction of the acetaminophen (APAP) obtained from expired commercial tablets and the CuBr(PPh3)3-catalyzed Huisgen reaction be-tween O-propargylated APAP and diverse organoazides prepared from commercially available anilines as available starting reagents. An interesting nitric oxide-releasing 1,2,3-triazole hybrid of APAP was also obtained easily using the developed method. The structures of the designed hybrid compounds, which are expected to be pharmacologically active, were fully characterized by FT-IR, 1H- and 13C-NMR and are reported for the first time. According to the in-silico studies performed in this work and literature analysis, these hybrids are interesting models in search of new pharmacological nontoxic agents endowed with anti-inflammatory and anticancer properties.

Background: Wastewater represents a health risk for populations. For sanitary safety, it is important to know their physico-chemical and microbiological qualities in order to better understand the risks incurred by the population. Objective: The aim of this study is to analyse the microbiological and physico-chemical quality of domestic wastewater in Adétikopé. Methodology: 12 wastewater samples were collected in Adétikopé from December 2022 to February 2023. Physico-chemical parameters were determined in accordance with AFNOR T90-105/ T90-023 and French standard NF T 90101. In microbiology, AFNOR was used as a reference for the detection of germs contaminating wastewater. Results were assessed in relation to European Union Criteria 98/83/EC. Results: The wastewater analyzed had a pH close to neutral, with an average pH of 7.05. The pollutant load generated ranged from 32 mg/l to 201 mg/l for BOD5, from 660 mg/l to 900 mg/l for COD and from 408 mg/l to 2080 mg/l for suspended solids. Concentrations of fecal coliforms and fecal streptococci are very high, far exceeding WHO guidelines for population health safety.

In this work, the influence of catalyst reuse and reaction time on the yield and quality of organic liquid products (OLP) obtained in a cracking pilot plant at 450 °C and 1.0 atm has been systematically investigated. The distillation of OLP produced 04 (four) distilled fractions. The quality of the biofuels was certified by physical-chemical analysis, as well as FT-IR and GC-MS analysis. The experimental results showed the feasibility of applying the spent sodium carbonate twice in catalytic cracking of vegetable oils. The physical-chemical properties (density, viscosity, acid value, saponification value, and flash point) of OLP decrease as the reaction time increases. The distillation of OLP yields 62.35% (wt.), producing green-like gasoline, kerosene, and diesel fractions rich in hydrocarbons. Therefore, biofuels-like fractions produced by distillation of OLP have a great potential for replacing partially petroleum derived fuels.

The pharmaceutical industry is one of the largest pollutants and generator of toxic solvent resi-dues for the environment and human beings. In the last decade, there has been a huge evolution in the design and development of new environmentally friendly products and processes, in re-sponse to the global environmental concern and the growing demand for products with quality ingredients and manufacturing processes aimed at achieving sustainability. Consumers are looking for products with the benefits of natural products, with sustainable and environmentally friendly formulations with few synthetic molecules as possible. Thus, based on the origins of the pharmaceutical industry, it is important to return to Nature and enjoy the benefits that natural products bring to us. Deep eutectic solvents appear as an alternative to toxic solvents commonly used to extract bioactive compounds. These solvents are considered green solvents because they are made up of natural compounds such as sugars, amino acids, and carboxylic acids. In addition, they are simple to prepare, with an atomic economy of 100%, with attractive physicochemical properties. This paper is a comprehensive review in which is described the main properties, characteristics, and production methods of deep eutectic solvents as well as its application to extract from natural sources bioactive compounds with pharmaceutical interest.

In the context of global warming and reduction in fresh water availability is presented a study of the evolution of dew, rain and evapotranspiration in the NW of Africa. The time periods are concerned with the years 2005-2020, using existing data, and years 2020-2100, using the low and high emissions representative concentration pathway scenarios RCP 2.6/8.5 from the Cordex database. A continuous decrease in rain precipitation is observed, on order of -14 mm/decade for the more credible scenario RCP 8.5. The amplitude is maximum on the coast and on the foothills of Atlas. A clear decrease in dew yields is also observed along a NW/SE axis, strongly correlated with a corresponding decrease in relative humidity (up to 7%). Chemical dew and rain data in the representative site of Mirleft correspond to the major cations Na+ > Ca2+ > Mg2+ > K+, similar to a local spring water. Concentrations in rain are about two times less than in dew water. Ionic concentrations are compatible with WHO standards. The seasonal variations of the ionic concentrations in dew and rain follow a volume dilution dependence. The expected diminution in dew and rain volumes according to the RCPs 2.6 and 8.5 should increase the dew and rain ionic concentrations in the future.

Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule is a seemingly improbable event, on a closer look, it is almost inevitable that homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic “ocean”. Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure, would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth.

Activated Corrosion Products (ACPs) formation and deposition pose a critical safety issue for nuclear fusion reactors. The working fluid transports the ACPs towards regions accessible to worker personnel. Predicting ACPs formation deposition and transport is fundamental for source term identification, reduction of radiation exposure assessment, maintenance plan definition, design optimization, and waste management. The code OSCAR-Fusion has been developed by the CEA (France) to evaluate the ACPs generation and transport in closed water-cooled loops for fusion application. This work aims at assessing the impact of water chemistry on the transport, precipitation, and deposition of corrosion products for the EU-DEMO divertor Plasma Facing Unit Primary Heat Transfer System. Sensitivity analyses and uncertainty quantification are needed due to the multi-physics phenomena involved in ACPs formation and transport. The OSCAR-Fusion/RAVEN code coupling developed by the Sapienza University of Rome and ENEA has been used. This work presents the perturbation results of different parameters chosen for a closed water-cooled loop considering a continuous scenario of 1888 days. The aim of this work is to assess the variation of build-up of ACPs, perturbing the alkalizing agent concentration into the coolant and the corrosion and release rates of different materials.

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 effective treatment of human immunodeficiency virus (HIV), also known as acquired immunodeficiency syndrome (AIDS), has transformed a highly lethal disease into a chronic and manageable condition. However, better methods need to be developed for eliminating the virus from reservoirs, enhancing patient access and adherence to therapy, and improving treatment in the long term to reduce adverse effects. From the perspective of drug discovery, one promising strategy is the development of anti-HIV prodrugs. This approach aims to enhance the efficacy and safety of treatment, promoting the development of more appropriate and convenient systems for patients. In this review, we discussed the use of the prodrug approach for HIV antiviral agents and emphasized nucleoside reverse transcriptase inhibitors. We comprehensively described various strategies that are used to enhance factors such as water solubility, bioavailability, pharmacokinetic parameters, permeability across biological membranes, chemical stability, drug delivery to specific sites/organs, and tolerability. These strategies might help researchers conduct better studies in this field. We also reported successful examples from the primary therapeutic classes while discussing the advantages and limitations. In this review, we highlighted the key trends in the application of the prodrug approach for treating HIV/AIDS..

Atmospheric turbulence, which produces chaotic motions in the planetary boundary layer, can inhibit mixing between fast-reacting species produced or released at different locations. This segregation process modifies the effective rate at which reactions occur between these species, and are not appropriately accounted for in coarse resolution models since these models assume complete mixing of tracers within each gridbox. Here we present a few examples of LES-based simulations applied to chemically reactive species in a forested area with high emissions of biogenic hydrocarbons, an urban area rich in anthropogenic emissions; and a maritime area with high emissions of reduced sulfur species.

With the growing of university chemistry experiment projects, scientific research personnel, specialized equipment, laboratory accident is increasing yearly. And accident data lacks a safety platform to store related information and cannot be guaranteed for efficient conditional sharing. To solve these problems, we designed a laboratory accident system to store, share related data and predict risk level. In this paper, we manually collected chemistry laboratory accidents by python software and class assignments, then analyses risk factor variables using Spsspro, finally established a prediction model using Stata. We intended to register laboratory related data into proposed chemistry accident system based on data ownership safety architecture. The chemistry accident system can break data barriers using confirmation and authorization key technology to trace non-tampered data source in real time when emergency accident happens. Meanwhile, our proposed system can use our designed accident risk model to predict risk level of any experiment project. It can also recommend appropriate safety education models.

Polycyclic aromatic hydrocarbons (PAHs) have emerged as promising materials for organic electronics, including organic photovoltaics (OPVs), organic field-effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Particularly, non-hexagonal ring-fused PAHs are highly desirable due to their unique optoelectronic properties. Herein, a new redox-active azulene-perylene diimide triad 1 and its ring-fused counterpart, diazulenocoronene diimide 2, were synthesized and fully characterized by a combination of NMR, cyclic voltammetry, spectroelectrochemistry, and UV-visible absorption spectroscopy. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to gain further insight into various electronic transitions. Interestingly, we found that the adaptive response to acids and bases manifests itself in a reversible two-color-change that can be attributed to changes in the chemical structures.

: Flotation performance in plants can significantly be affected by seasonal variations in different parts of the world. This is generally attributed to the changes in water temperature and pulp temperature in flotation plants, type and concentration of dissolved ions in process water. Extreme temperature conditions may be the major factor affecting flotation performance and mask the influence of water chemistry. Therefore, the interactive effects of the temperature and water chemistry should be taken into consideration, particularly for mine sites experiencing extreme temperature conditions. In this paper, effects of temperature, sulphate (SO42-), thiosulphate (S2O32-) and calcium (Ca2+) ions on the flotation performance of a Cu-Pb-Zn complex sulfide ore were investigated using a statistical experimental design and modelling approach. Batch scale kinetic flotation tests were conducted using the sequential flotation flowsheet of a bulk Cu-Pb flotation stage followed by a zinc rougher flotation stage. The results of the zinc flotation section were used for the statistical evaluation since the zinc concentrate was the product with an economic value for the mine. The results were evaluated using ANOVA analysis and regression analysis to determine the significant parameters and derive individual regression models for each flotation response with Design Expert software version 6.0.8. Individual regression models were developed using the significant main effects and their interactions for each flotation response. Then, the models were used to determine the concentration of the dissolved ions and pulp temperature required to achieve the maximum zinc recovery, maximum zinc grade or the optimum zinc grade and recovery. The details of statistical experimental design, discussions on the effects of the experimental factors and their interactions on the flotation performance and development of regression models are discussed in this paper.

Fe[C5H5N]2[N(CN)2]2 (1) was synthesized from a reaction of stoichiometric amounts of NaN(CN)2 and FeCl2·4 H2O in a methanol/pyridine solution. Single-crystal and powder diffraction show that 1 crystallizes in the monoclinic space group I2/m (no. 12), different from Mn[C5H5N]2[N(CN)2]2 (P21/c, no. 14) due to tilted pyridine rings, with a = 7.453(7) Å, b = 13.167(13) Å, c = 8.522(6) Å, β = 114.98(6)° and Z = 2. ATR-IR, AAS, and CHN measurements confirm the presence of dicyanamide and pyridine. Thermogravimetric analysis shows that π-stacking interactions of the pyridine rings play an important role in structural stabilization. Based on DFT-optimized structures, a chemical bonding analysis was performed using a local-orbital framework by projection from a plane-wave basis. The resulting bond orders and atomic charges are in good agreement with the expectations based on the structure analysis. SQUID magnetic susceptibility measurements show a high-spin state FeII compound with predominantly antiferromagnetic exchange interactions at lower temperatures.

RNA, as an important substance for regulating biological growth and development, has significant implications for visualization research. However, many spontaneously fluorescent substances in plants greatly interfere with the effectiveness of plant bioimaging. Aggregetion- induced emission luminogens (AIEgens), due to their luminescent properties, tunable molecular size, high fluorescence intensity, good photostability, and low cell toxicity, have been widely applied in the animal and medical fields. We have found that AIEgens have great potential as RNA fluorescent probes for efficient imaging in plants. In this review, we first introduce several common RNA labeling forms and point out their pros and cons. We briefly describe the development of AIEgens and the AIE mechanism, and then present various practical applications of AIEgens, including detailed examples of their use as biological markers. To further promote the application of AIE in the field of RNA, we suggest the use of AIEgens to modify target RNA via techniques such as click chemistry or CRISPR/Cas, to achieve RNA visualization in plants. highly possible to modify target RNA with AIEgens in vivo for RNA visualization.

Halide perovskite materials gain enormous attention for their semiconducting properties, higher power conversion efficiency and potential applications in a wide range field of studies along with their two key limitations: stability and toxicity. In spite of great progress made on the halide perovskites and many promising research developments, overcoming these limitations is not realized yet. Therefore, coordination engineering of new framework for obtaining alternative new halide perovskite materials and fundamental understanding of the coordination chemistry and electronic interactions forming the structure of these newly engineered halide perovskite materials might be one way in order to overcome the issues related to both stability and toxicity. In this review, the current development of halide perovskite families, both lead halide perovskites and lead free halide perovskites followed by coordination engineering of the new frameworks to engineer new halide perovskite materials will be reviewed comprehensively. Moreover, all the concerns of the fundamental ideas of coordination chemistry and electronic interactions that are keys in forming the halide perovskite structures are discussed in detail and form the main aim of this review. Interestingly, we also discuss recent potential energy applications beyond photovoltaic and this review has completed with an essential and open question: ‘what could happen in the future of halide perovskites?’ in order to excite commercial enterprises and research institutions again as well as to get motivating new predictions on the future continuity of this field.

Iron-based materials are widely applied in Fenton chemistry and they have promising prospects in the processing of wastewater. The composition complexity and rich chemistry of iron and/or oxides, however, hamper the precise understanding on the active sites and the working mechanism which still remain highly controversial. Herein, iron oxides of four different model systems are designed through a conventional precipitation method plus H2 reduction treatment. These systems feature Fe@Fe3O4 with abundant oxygen vacancy, Fe0 and Fe3O4 particles with interface structures, and Fe3O4-dominated nanoparticles of different sizes. These materials are applied in the decomposition of methyl orange as a model reaction to assess the Fenton chemistry. The Fe@Fe3O4 with core-shell structures exhibited significantly higher decomposition activity than the other Fe3O4-rich nanoparticles. A thin Fe3O4 layer formed by auto-oxidation of iron particles when exposing to air can boost the activity as compared with the Fe0 and Fe3O4 particles with interface structures but poor oxygen vacancy. The unique hetero-structure with the co-existence of both metallic iron and oxygen vacancy displayed excellent redox propensity which might account for the superior Fenton activity. This finding provides a new perspective to understand and design highly efficient iron-based Fenton catalysts.

Theories on life’s origin generally acknowledge the advantage of a semi-permeable vesicle (protocell) for enhancing the chemical reaction-diffusion processes involved in abiogenesis. However, more and more evidence indicates that the origin of life concerned the photo-chemical dissipative structuring of the fundamental molecules under UV-C light. In this paper, we analyze the Mie UV scattering properties of such a vesicle made from long chain fatty acids. We find that the vesicle could have provided early life with a shield from the faint, but dangerous, hard UV-C ionizing light (180-210 nm) that probably bathed Earth’s surface from before the origin of life and until perhaps 1,500 million years after, until the formation of a protective ozone layer as a result of the evolution of oxygenic photosynthesis.

Cratylia argentea is a leguminous shrub with a great potential for livestock feeding in tropical areas. However, time consuming and labor-intensive methods of chemical analysis limits the understanding of its nutritive value. Near infrared spectroscopy (NIRS) is a low-cost technology that has been widely used in forage crops to fasten the assessment of its chemical composition. The objective of this study was to develop prediction models to assess crude protein (CP), neutral detergent fiber (NDF), acid detergent fiber (ADF) and dry matter (DM) of Cratylia based on NIRS and partial least square analysis. A total of 155 samples were harvested at different maturity levels and used for model development, whereas 107 were used for calibration and 48 for external validation. The cross-validation presented Root Mean Square Error of Prediction of 0.77, 2.56, 3.43, and 0.42; a Ratio of Performance to Deviation of 4.8, 4.0, 3.8, and 3.4; an R2 of 0.92, 0.92, 0.87, and 0.84 for CP, NDF, ADF, and DM, respectively. Based on the obtained results, we conclude the ability to predict chemical parameters of Cratylia with the current model was accurate. This way, livestock producers and researchers may use it to fasten the assessment of Cratylia’s nutritive value.

Stellatolides are natural compounds that have shown promising biological activities, including antitumor, antimicrobial, and anti-inflammatory properties, making them potential candidates for drug development. Chemical Reactivity Theory (CRT) is a branch of chemistry that explains and predicts the behavior of chemical reactions based on the electronic structure of molecules. Conceptual Density Functional Theory (CDFT) and Computational Peptidology (CP) are computational approaches used to study the behavior of atoms, molecules, and peptides. In this study, we present the results of our investigation of the chemical reactivity and ADMET properties of Stellatolides A-H using a novel computational approach called Conceptual DFT-based Computational Peptidology (CDFT-CP). Our study uses CDFT and CP to predict the reactivity and stability of molecules and to understand the behavior of peptides at the molecular level. We also predict the ADMET properties of the Stellatolides A-H to provide insight into their effectiveness, potential side effects, and optimal dosage and route of administration. This study sheds light on the potential of Stellatolides A-H as promising candidates for drug development and highlights the potential of CDFT-CP for the study of other natural compounds and peptides.

Cheese consumption provides humans with minerals, proteins, carbohydrates, and vitamins. In Mexico, several cheese varieties are produced, each with its texture, scent, and flavor. The artisanal cheeses made in the states of Tabasco and Chiapas —including, among others, the varieties named crema (cream), doble crema (double cream), oaxaca, panela, fresco, bola, poro, Cotija, and asadero— have a high demand in the domestic and foreign markets. The intensification of anthropic activity in these states causes an increased emission to the environment of contaminants like heavy metals, which could reach human foodstuffs through the food chains. In particular, heavy metal contents in cheeses consumed daily by these states' local population might represent a public health risk. Because of that, our objectives in this work were to determine the concentrations of lead, cadmium, nickel, copper, zinc, and iron in artisanal cheeses produced in the states of Tabasco and Chiapas, and to determine the values of the Hazard Quotient (HQ), Total Hazard Quotient (THQ), and Cancer Risk Total (CRT) for adult and young men and women. The results of our analyses of cheese samples from the states of Tabasco and Chiapas showed that the average concentrations (mg kg-1) of cadmium (0.0023±0.002, 0.0023±0.002 mg kg-1, respectively for each state), lead (0.0047±0.00, 0.0051±0.002), nickel (0.0039±0.0046, 0.0031±0.0039), copper (0.0199±0.021, 0.0202±0.022), zinc (0.1611±0.18, 0.194±0.21), and iron (61.84±4.23, 65.76±6.61 mg kg-1), the first three values lower than the limits established by the FAO/WHO and Codex Alimentarius. The value of THQ that we obtained was less than one, and that of CRT was within the limits established by the US-EPA, which means that the consumption of artisanal cheeses from Tabasco and Chiapas by humans does not imply a risk of disease or cancer.

Gestational diabetes mellitus (GDM) is a hyperglycemia state that is typically diagnosed by an oral glucose tolerance test (OGTT), which is unpleasant, time-consuming, poorly reproducible, and tardy. The machine learning (ML) predictive models that have been proposed to improve GDM diagnosis are usually based on instrumental methods that take hours to get a result. Near-infrared (NIR) spectroscopy, a simple, fast and low-cost analytical technique has never been assessed for the prediction of GDM. This study aims to develop ML predictive models for GDM based on NIR spectroscopy, and to evaluate their potential as early detection or alternative screening tools according to their predictive power and time of analysis. Serum samples from the first (before GDM diagnosis) and the second (at the time of GDM diagnosis) trimester of pregnancy were analyzed by NIR spectroscopy. Four spectral ranges were considered, and 80 pretreatments were tested for each. NIR data-based models were built with single- and multi-block ML techniques. Every model was subjected to double cross-validation. The best first and second trimester models got areas under the receiver operating characteristic curve of 0.5768 ± 0.0635 and 0.8836 ± 0.0259, respectively. This is the first study reporting NIR spectroscopy-based methods for the prediction of GDM. The developed methods allow to predict GDM from 10 µL of serum in only 32 minutes. They are simple and fast, and have a great potential to be applied in clinical practice, especially as alternative screening tools to the OGTT at the time of GDM diagnosis.

Towards better understanding of factors controlling carbon (C) exchange between inland waters and atmosphere, we addressed inorganic carbon cycle in semi-arid lakes of Central Eurasia, subjected to strong impact of on-going climate change. For this, we assessed the hydrochemical vari-ability and quantified its control on formation of authigenic carbonate minerals, occurring within the upper layer of sediments in 43 semiarid lakes located in the southwest of Western Siberia (Central Eurasia). Based on measurements of pH, total dissolved solids (TDS), cationic and anionic composition, dissolved organic and inorganic C, as well as textural and mineralogical characterization of bottom sediments using X-ray diffraction and scanning electron microscopy, we demonstrate that lake water pH and TDS are primarily controlled by both lithological and climatic context of the lake watershed. We have not revealed any direct relationships between lake morphology and water chemistry. The most common authigenic carbonates scavenging atmospheric CO2 in the form of insoluble minerals in lake sediments were calcite, aragonite, Mg-calcite, dolomite and hydro-magnesite. The calcite was the most common component, aragonite mainly appears in lakes with sediments enriched in gastropod shells or artemia cysts, while hydromagnesite was most common in lakes with high Mg/Ca molar ratios, as well at high DIC concentrations. The relationships between mineral formation and water chemistry established in this study can be generalized to a wide suite of arid and semi-arid lakes in order to characterize current status of inorganic C cycle and predict its possible modification under on-going climate warming such as water temperature rise and change of hydrological connectivity, primary productivity and nutrient regime.

In green chemistry, filamentous fungi are regarded as a kind of robust microorganism for the biotransformation of natural products. Nonetheless, the screening of microorganisms is crucial for the effective biotransformation of natural products such as phenazine compounds. The precursor metabolite of most phenazine derivatives in Pseudomonas spp. is phenazine-1-carboxylic acid (PCA), the key constituent of shenqinmycin, widely used to control rice sheath blight in southern China. In this study, a new fungus strain Aspergillus sclerotiorum was isolated, which can efficiently convert PCA into 3-hydroxy-phenazine 1-carboxylic acid (3-OH-PCA). Moreover, an effective whole cells biotransformation system was constructed by screening optimal reaction conditions and carbon sources. Hence, Aspergillus sclerotiorum exhibited desirable adaptation by consumption of different carbon sources and maximum whole cell biomass (10.6 g/L DCW) was obtained as a biocatalyst from glucose. Optimal conditions for whole-cell biocatalysis of PCA were evaluated, including PCA concentration of 1120 mg/L, pH 7.0, temperature of 25°C, rotation rate 200 rpm and dry cell weight 15 g/L for 60 h, thus 1060 mg/L of 3-OH-PCA was obtained and the conversion efficiency of PCA was 94%. Hence, the results of repeated batch mood revealed that the biotransformation efficiency of fungus pellets reduced with each subsequent cycle but remained stable in all five cycles with the provision of glucose supplement. These findings open the prospective of using filamentous fungi for the whole cell biocatalysis of phenazine in enormous amount and efficient production of 3-OH-PCA. Moreover, these results laid the foundation for further research to disclose the genetic based mechanism of the strain responsible for PCA biotransformation.

As the world faces unprecedented environmental challenges and the rapid advancements of artificial intelligence (AI), it is crucial for universities to adapt their chemistry education to remain relevant and contribute to sustainability and the United Nations' Sustainable Development Goals (SDGs). This report offers critical insights into the development of university chemistry education over the next 10-20 years, forecasts its development over the next 10-20 years, and offers recommendations for the Ministry of Education and universities to ensure the continued relevance of chemistry programs in the face of AI.

We describe the development and validation of a HPLC-MS/MS method to assess the pharmacokinetics and tumour distribution of ZST316, an arginine analogue with inhibitory activity towards dimethylarginine dimethylaminohydrolase 1 (DDAH1) and vasculogenic mimicry, and its active metabolite L-257 in a xenograft model of triple negative breast cancer (TNBC). The method proved to be reproducible, precise, and highly accurate for the measurement of both compounds in plasma and tumour tissue following acute and chronic (five days) intraperitoneal administration of ZST316 (30mg/Kg daily) in six-week-old SCID mice inoculated with MDA-MB-231 TNBC cells. ZST316 was detected in tumour tissue and plasma after 1 hour (6.47 and 9.01M, respectively) and 24 hours (0.13 and 0.16M, respectively) following acute administration, without accumulation during chronic treatment. Similarly, the metabolite L-257 was found in tumour tissue and plasma after 1 hour (15.06 and 8.72M, respectively) and 24 hours (0.17 and 0.17M, respectively) following acute administration of ZST316, without accumulation during chronic treatment. The half-live after acute and chronic treatment ranged between 4.4-7.1hrs (plasma) and 4.5-5.0hrs (tumour) for ZST316, and 4.2-5.3hrs (plasma) and 3.6-4.9hrs (tumour) for L-257. The results of our study demonstrate the a) capacity to accurately measure ZST316 and L-257 concentrations in plasma and tumour tissue in mice using the newly developed HPLC-MS/MS method, b) rapid conversion of ZST316 into L-257, c) good intra-tumour penetration of both compounds, and d) lack of accumulation of both ZST316 and L-257 in plasma and tumour tissue during chronic administration. The new HPLC-MS/MS method is useful to investigate the in vivo effects of ZST316 and L-257 on vasculogenic mimicry, tumour mass, and metastatic burden in xenograft models of TNBC.

This comprehensive review explores recent advancements in heavy metal remediation techniques, focusing on the utilization of cellulose-silica composites and tailored surface modification techniques. We examine the synthesis strategies and properties of cellulose-silica adsorbents, highlighting their enhanced adsorption capacities and structural robustness for removing heavy metal pollutants from aqueous environments. The review investigates various surface modification approaches, including thiol-functionalization, amino acid grafting, and silane coupling agents, for optimizing the surface chemistry and morphology of cellulose-silica composites. Mechanistic insights into the adsorption processes and kinetics of modified adsorbents are discussed, along with considerations for optimizing adsorption performance under different environmental conditions. This review provides valuable perspectives on the development of effective adsorbent materials for sustainable heavy metal remediation applications.

High surface area carbon was obtained from -carrageenan – urea cryogels doped with 1.25 – 5 wt% graphene oxide (GO). Incorporation of GO resulted in multifaceted modification in the textural and chemical properties of the carbon cryogel. The thermal decomposition of GO facilitated the formation of micropores resulted in a substantial increase in the apparent surface area (up to 1780 m2/g). The annealing at 1000 °C removed part of the heteroatoms but left behind a high number of defects. While the volatile thermal degradation products of GO affected the porous texture and the surface chemistry in a complex way, its reduced residue resulted in a gradually increasing electrical conductivity. The influence of GO was studied in oxygen reduction reaction (ORR) and in Li-ion storage application. GO affected the electron transfer mechanism in the ORR tests and challenged the stability of the electrodes. Even if the electrode has been stabilized under oxygen-free conditions, later may undergo destabilization processes during the ORR. The 5 wt% GO doped sample was the most sensitive under oxidative conditions, but finally it exhibited the highest capacitance. In the Li-ion battery tests the coulombic efficiency of all the samples was consistently above 98 %, indicating the great potential of such carbons for efficient Li-ion insertion and reinsertion during the charge – discharge process, thereby providing a promising alternative for graphite-based anodes. The cell from the 1.25% sample showed an initial discharge capacity of 313 mAh/g, 95.1 % capacity retention and 99.3 % coulombic efficiency after 50 charge – discharge cycles.

A sustainable reversed-phase chromatographic method has been developed and validated for the simultaneous determination of three active pharmaceutical ingredients, dorzolamide, brinzolamide, and timolol, used to treat glaucoma. The eco-friendly solvent isopropanol has been used as an organic mobile phase constituent. According to the Hansen space green solvent selection tool, isopropanol has a G score of 6.5, comparable to ethanol, which has a G score of 6.6. The mobile phase consists of isopropanol: aqueous sodium acetate buffer (0.1 M, pH 4.25) in the ratio of 10:90 (v/v). The flow rate was maintained at 1 mL/min. Dorzolamide and brinzolamide were detected at 254 nm, and timolol was detected at 295 nm. A high-purity silica with a polymeric C18 modification column (5 µm,150 x 4.6 mm) was used for this separation. The three compounds were eluted within 8 min. The method was validated according to ICH guidelines. The calibration curves were linear in the range of 20-70 µg/mL, 40-140 µg/mL, and 20-70 µg/mL for dorzolamide, brinzolamide, and timolol, respectively. The LODs were found to be 1.61 µg/mL, 1.60 µg/mL, and 3.16 µg/mL for dorzolamide, brinzolamide, and timolol, respectively. Good accuracy and precision were obtained for the three compounds. The greenness and whiteness of the method were indicated using the AGREE and RGB12 tools, respectively.

Bimetallic (or multimetallic) catalysis has emerged as a powerful tool in modern chemical synthesis, offering improved reaction control and versatility. This review focuses on the recent de-velopments in bimetallic sequential catalysis for the synthesis of nitrogen heterocycles, essential building blocks in pharmaceuticals and fine chemicals. The cooperative action of two (and sometimes more) different metal catalysts enables intricate control over reaction pathways, enhancing selectivity and efficiency of N-heterocyclic compounds synthesis. By activating less reactive substrates, this multimetal catalytic strategy opens new synthetic possibilities for challenging compounds. The use of catalytic materials in bimetallic systems reduces waste and improves atom efficiency, aligning with green chemistry principles. With a diverse range of metal combinations and reaction conditions, bimetallic catalysis provides access to a broad array of N-heterocyclic compounds with various functionalities. This paper highlights the significant progress made in the past decade in this topic, emphasizing the promising potential of bimetallic catalysis in drug discovery and the fine chemical industries.

The research community has shown significant interest in the aqueous synthesis of nanomaterials due to its ability to eliminate the need for complex organic solvents. This synthesis approach aligns with the principles of green chemistry, attracting considerable attention. Aqueous solution technology in fabricating nanostructures has gained recognition for its potential to create ultrasensitive, low-energy, and ultrafast optoelectronic devices. This report focuses on synthesizing lead iodide (PbI2) nanoplates using a water-based solution technique and fabricating a planar photodetector. The photodetectors with a planar type of device structure (ITO/PbI2 NPs/Au) demonstrated a remarkable photosensitivity of 3.9×103 and a photoresponsivity of 0.51 mA/W at a wavelength of 405 nm. Notably, the asymmetrical output properties of ITO/PbI2 NPs/Au detector deliver additional evidence of the effective creation of a Schottky contact. Thus, the photodetector exhibited a photoresponse even at 0 V bias, leading to the realization of self-powered photodetectors. Additionally, the device exhibited a rapid photoresponse of 0.21/0.38 s (−5 V) in the visible range. This study has expanded the horizons for the aqueous-phase synthesis of nanoplate nanostructures, enabling the large-area fabrication of high-performance photodetectors.

Reactions in water between the Cu2(µ-EGTA) chelate (EGTA = ethylene-bis(oxyethyleneimino)tetraacetate(4-) ion) and 2,6-diaminopurine (Hdap) in molar ratios 1:1 and 1:2 yield only blue crystals of the ternary compound [Cu4(μ-EGTA)2(μ-H(N3)dap)2(H2O)2]·7H2O (1) that has been studied by single crystal X-ray diffractometry, various physical methods (thermal stability, spectral and magnetic properties), as well as DFT theoretical calculations. In the crystal, uncoordinated water is disordered. The tetranuclear complex molecule also has some irrelevant disorder in an EGTA-ethylene moiety. In the complex molecule, both bridging organic molecules act as binucleating ligands. There are two distorted five- (type 4+1) and two six- (type 4+1+1) Cu(II) centres. Each half EGTA acts as a tripodal tetradentate Cu(II) chelator, with mer-NO2+O(ether, distal) conformation. Hdap exhibits the tautomer H(N3)dap, with the dissociable H-atom on its less basic N-heterocyclic atom. These features favour the efficient cooperation between Cu-N7 or Cu-N9 bonds with appropriate O-EGTA atoms, as N6-H···O or N3-H···O interligand interactions respectively. Bridging role of both organics determines the tetranuclear dimensionality of the complex in 1. In this crystal, such molecules associate in zig-zag chains, built by alternating ,-interactions between the five- or six-atom rings of Hdap ligands of adjacent molecules. DFT theoretical calculations (using two different theoretical models and characterized by the quantum theory of “atoms in molecules”) reveal the importance of these ,-interactions between Hdap ligands, as well as that corresponding to the referred hydrogen bonds in the contributed tetranuclear molecule.

To understand the biological relevance and mode of action of artificial protein ligands, crystal structures with their protein targets are essential. Here, we describe and investigate all known crystal structures that contain a so-called “molecular tweezer” or one of its derivatives with an attached natural ligand on the respective target protein. The aromatic ring system of these compounds is able to include lysine and arginine side chains, supported by one or two phosphate groups that are attached to the half-moon shaped molecule. We analyse the corresponding crystal structures with 14-3-3 proteins in complex with mono- and diphosphate tweezers. Furthermore, we solved crystal structures of two different tweezer variants in complex with the enzyme 1-Pyrroline-5-carboxyl-dehydrogenase (P5CDH), and found that the tweezers are bound to a lysine and methionine side chain, respectively. The different binding modes and their implications for affinity and specificity are discussed, as well as the general problems in crystallizing protein complexes with artificial ligands.

With the rapid development of urbanization, the chemical evolution of groundwater is significantly affected by human activities. However, the driving mechanisms of groundwater chemical evolution at different stages of urbanization remain unclear, severely impacting the implementation of groundwater protection. This study investigated the driving mechanisms of groundwater chemical evolution based on the long-term series (from 1985 to 2015) of hydrochemical data from 19 groundwater monitoring sites in rapidly urbanizing areas (Shijiazhuang, Hebei Province, China). The results show that the concentrations of various chemical components in groundwater gradually increase with the acceleration of urbanization process, especially NO3-, which has increased from 13.7 mg/L in the primary stage of urbanization (PSU) to 65.1mg/L in the advanced stage of urbanization (ASU), exceeding the WHO drinking water standard (50mg/L), indicating that the groundwater chemistry has been significantly affected by human activities. It is interesting to find that the main hydrochemical types have changed from HCO3•SO4-Ca•Mg type water in the PSU to SO4•HCO3-Ca•Mg type water in the ASU. It is worth noting that there were obvious differences in driving factors of groundwater chemical evolution at different urbanization stages. In the PSU, the driving factors of groundwater chemical evolution were carbonate and rock salt dissolution, cation exchange, and industrial activities. However, in the intermediate stage and advanced stage, the driving factors of groundwater chemical evolution were changed to carbonate and gypsum dissolution, groundwater over-exploitation, agricultural fertilization, and domestic sewage. Based on the above conclusions, it is suggested that future groundwater management should control the amount of agricultural fertilizers, apply scientific fertilization, and prohibit the discharge of various types of non-compliant sewage, while strengthening the supervision of groundwater extraction to reduce the impact of urbanization development on the groundwater chemical evolution process.

Following on from work already carried out in our laboratory on a new biomass-derived green solvent, eucalyptol, we are now turning our attention to sabinene as a new green solvent. Sabinene is also derived from biomass. We have shown that it can be used as such or distilled to synthesize thiazolo[5,4-b]pyridine heterocycles by thermal or microwave activation. This new solvent was compared with various conventional and green solvents. The conditions were optimized to enable us to carry out the syntheses in good yields, and we were able to show that sabinene, a natural bicyclic monoterpene, could be used effectively as a solvent.

XPS and ARXPS characterization of surface layers resulting from the functionalization of polymers such as PVC modified with MPTMS and APTES is challenging due to the signals overlap, deriving both from the substrate and the functionalized layers. In this work, a freshly cleaved, ideally flat gold surface was used as carbon-free model substrate functionalized with MPTMS and subsequently grafted with APTES. Avoiding the overlap of signals from carbon atoms present in the substrate, the signals in the C1s, O1s, Si2p, S2p and N1s high-resolution spectra could be assigned to the MPTMS / APTES functionalized layer only and the curve fitting parameters could be determined. Quantitative analysis was in very good agreement with the expected stoichiometry of the functionalized layer, confirming the adopted curve fitting procedure. In addition, it was found that one molecule of APTES grafted two MPTMS via silane groups. ARXPS allowed determining the thickness of the functionalized layers: MPTMS thickness was found to be 0.5 (0.2) nm, MPTMS + APTES thickness 1.0 (0.2) nm in good agreement with Avogadro model calculations. This approach can be considered a powerful tool for characterising functionalized surfaces of more complex systems by XPS.

The atomic nucleus contains protons and neutrons surrounded by a structured electron cloud. Some combinations of protons and neutrons induce the nucleus to behave like a microscopic magnet, possessing a unique magnitude and orientation known as the nuclear magnetic moment (µ). When the numbers of protons and neutrons are both even then µ=0, but otherwise each nu-clide’s nuclear magnetic moment is unique. A second unique nuclear physical property relates to the nucleon binding energy (BE), which can be thought of as the energy between protons and neu-trons bound within the nucleus. The sequence of stable nuclides increases one nucleon at a time through 36Ar. The binding energy associated with the addition of each successive nucleon (∆BE) through this progression is unique. The hypothesis here is that the unique non-zero magnetic mo-ment and ∆ binding energy of each nuclide derive from its respective microscopic nuclear struc-ture, analogous to the way that the atomic physical properties of an element ultimately derive from its unique electron orbital structure. By extension, the identification of nuclear periodic pat-terns might eventually inform a theory of nuclear structure. The light, stable nuclides through 36Ar were arranged in ascending order according to atomic mass, and their nuclear magnetic mo-ments and binding energies were evaluated for periodic patterns. Fixed-period lengths from 4 through 18 nuclides per period were considered. These fixed periods, each of equal length, were stacked one upon the other and analyzed for vertical trends. The best evidence of periodicity in both µ and ∆BE converges precisely at the fixed 12-nuclide period. Implications for nuclear structure are discussed.

Photophysical properties of a series of bis(arylydene)cycloalkanone dyes with various donor substituentns are studied by quantum chemistry. Their capacity for luminescence and nonradiative relaxation through trans-cis isomerization is related to their structure, in particular, to the donor capacity of the substituents and the degree of conjugation due to the central cycloalkanone moiety. It is shown that cyclohexanone central moiety introduces distortions and disrupts the conjugation, thus leading to a nonmonotonic change in their properties. The increasing donor capacity of the substituents causes increase in the HOMO energy (raise of the oxidation potential) and decrease in the HOMO-LUMO gap, which results in the red shift of the absorption spectra. The ability of the excited dye to relax through fluorescence or through trans-cis isomerization is governed by the height of the barrier between the Franck–Condon and S1-S0 conical intersection regions on the potential energy surface of the lowest π-π* excited state. This barrier also correlates with the donor capacity of the substituents and the degree of conjugation between the central and donor moieties. The calculated fluorescence and trans-cis isomerization rates are in good agreement with the observed fluorescence quantum yields.

We describe the development and validation of a HPLC-MS/MS method to assess the pharmacokinetics and tumour distribution of fenretinide, a synthetic retinoid chemically related to all-trans-retinoic acid, after administration of a novel oral nanoformulation of fenretinide, called bionanofenretinide (BNF). BNF was developed to overcome the major limitation of fenretinide: its poor aqueous solubility and bioavailability due to its hydrophobic nature. The method proved to be reproducible, precise, and highly accurate for the measurement of the drug and the mains metabolites. The lower limit of quantification resulted 1 ng/mL. The curve range of 1-500 ng/mL and 50-2000 ng/mL, for plasma and tumor homogenate respectively, was appropriate for the analysis, as demonstrated by the accuracy between 96.8% and 102.4% for plasma and 96.6-102.3% for tumor. The inter-days precision and accuracy determined on quality controls at 3 different levels were in ranges of 6.9%-7.5% and 99.3-101.0% and 0.96-1.91% and 102.3-105.8% for plasma and tumour, respectively.

The brown pelican (Pelecanus occidentalis) is a species often affected by natural and man-made disasters such as hurricanes and oil spills as well as general human activities; that subsequently receives medical care and rehabilitation. During rehabilitation, blood may be collected for various testing to help with diagnosis, treatment, and monitoring. Reference intervals for this species are limited, dated, and typically from small sample sizes. Seventy one presumed healthy brown pelicans were sampled as a part of their pre-release examination from rehabilitation at the Wildlife Center of Texas after a large volume stranding in December 2014 to January 2015, and various venous analytes were measured to establish updated reference intervals for Brown Pelicans. Fibrinogen was measured via heat precipitation and the Abaxis VSPro equine Fibrinogen cartridge to determine reference intervals, and in an attempt to validate the VSPro for use in avian species. Abaxis VS2 Avian/Reptile Chemistry panel, iSTAT CG4+, and iSTAT Chem8+ results in addition to body condition score, spun PCV, cloacal temperature and fibrinogen were measured. Proposed reference intervals for brown pelicans are presented. Fibrinogen results were not comparable between the gold standard method and the VSPro, indicating that the VSPro is not appropriate for use in brown pelicans.

Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique's specific application. Furthermore, the review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact.

Several chemistry-climate models (CCM) underestimate the total column ozone (TCO) over the polar region in the Southern Hemisphere during wintertime. To evaluate potential causes of the problem, we exploit CCM SOCOLv3 to study the TCO over Antarctica sensitivity to the: (1) photo-dissociation rates of ozone for large solar zenith angles; (2) rates of the stratospheric heterogeneous reactions, and (3) intensity of the meridional flux into the polar regions due to sub-grid scale mixing processes in the model. Comparisons of the model results with the satellite-based IASI (Infrared Atmospheric Sounder Interferometer) sensor measurements showed that the most important processes for the improvement of the polar ozone simulation results are photolysis and horizontal mixing. The reasonable tuning of these factors has allowed us to improve the model representation of the ozone annual cycle over the southern polar region. The proposed increase of the horizontal mixing can be recommended for the CCMs with relatively low horizontal resolution.

The fine chemical and pharmaceutical sectors are starting to advocate the use of flow chemistry due to reasons such as EHS, environmental, efficiency, cost saving and regulatory compliance. The use of trickle bed or fixed bed system could replace a batch autoclave typically used for hydrogenation reactions. However, there are few studies which detail the process from laboratory proof of concept through design to commercial realization. This study, using the production of 1,3-cyclohexanedione from catalytic hydrogenation of resorcinol as a case study demonstrates how the laboratory-scale recycle trickle bed can be used for catalyst screening and selection. Further, design data are generated by operation over a range of design superficial velocities and operating pressure that are used to derive a design correlation that is then used to specify a single stream plant at a level of definition consistent with a Preliminary Design for capital cost estimation. Finally, the further actions required in terms of data generation to increase the level of definition and confidence to a Sanction Grade or Final Design are discussed.

Synthesis of heterodinuclear 3d transition metal complexes in which two metal ions are introduced in equivalent coordination sites of a ligand is quite uncommon. We have previously shown that the application of the cis-trans isomerization of the oxamido group was able to furnish such a possibility. In the present paper we demonstrate that this synthetic pathway, relying on the possibility of changing the conformation (cis vs trans) of the oxamido group, can be extended to other ligands. Although we have not been able to structurally characterize these complexes, EPR and magnetic data do confirm the efficiency of this reaction pathway. We also demonstrate that the cis-trans isomerization of the oxamido group is not due to a particular property of the ion involved in the reaction. In fact, isomerization is governed by the basicity of the reaction medium. According to the reaction condition, it is possible to favor or not this phenomenon, and to increase the accessibility to a larger number of novel genuine complexes. But the oxophilic character of the lanthanide ions impedes this isomerization in 3d-4f complexes. The very weak magnetic interactions observed in these Cu-Gd complexes can be explained thanks to spin polarization.

Why did inanimate materials evolve into complex organisms and societies on Earth? This is a fundamental scientific question that has captivated humans for millennia. Here we propose the Carbon-Based Evolutionary Theory (CBET) to provide novel, direct, explicit, and relatively comprehensive answers to this question. The CBET identifies three key mechanisms based on some well-known principles of physics and chemistry (e.g., laws of thermodynamics) and some features of Earth and carbon-based entities (CBEs): the driving force mechanism that provides energy, the structural mechanism that generates new functions, and the natural selection mechanism that accumulates orderliness, all for the evolution of CBEs. These mechanisms lead to the progression from chemical to biological and social evolution, marked by the escalating hierarchy of CBEs and the increase in the quantity, diversity, and orderliness of high-hierarchy CBEs. The CBET clarifies the natural roots of multiple pivotal and seemingly paradoxical social notions, such as inclusiveness and competition, altruism and selfishness, freedom and restriction, as well as inherited advantages and acquired strengths. It advocates for the balanced, harmonious, and peaceful development of human society as well as the integration of all countries into a single harmonious social collective. The CBET unifies biology with physics and chemistry and could be a basic theory shared by the natural sciences and the social sciences. It could also be significant in the rational development of human society.

Supramolecular structures with specific applications are a pillar in several areas of science. Thus, from a contemporary point of view, there are several reasons to feel inclined to cover a systematic, or historic critique of the supramolecular concept itself. First, the idea of a supramolecular material seems more secure now than it was decades ago. Second, updating the interacting of MOFs and supramolecular chemical and conversely, supramolecularity to assemble MOFs and to make ef-ficient complex systems in multiple cutting-edge applications. Third, we should here simply confine to a consideration of how workers in this field have tried to correlate the notion of the idea of supramolecular systems linking self-assembly considerations. Thereby, this is clearly an ad-vantage that optimized geometries obtained on the conductive bases described that undoubtedly, some of these systems have substantial applications and create a significant practical interest. The outline of this review encompasses a general introduction to MOFs and supramolecularity, the key unit of the study presented here, followed by a survey of recent advances in supramolecular chemistry in confined space, relationships of MOFs with the supramolecular chemistry, electro-chemical synthesis of MOFs, and switchable MOFs. Finally, some discussion on possible future perspectives of this field is given.

Metastatic melanoma patients have a poor prognosis with poor responsiveness to chemotherapy. BRAF V600E mutations have been detected in ~40% of melanoma patients. Vemurafenib is an oral agent licensed for patients with BRAF V600E mutation-positive inoperable and metastatic melanoma, which already presents resistance that leads to patient relapse and the serious side effects. In our study, we synthesized 5 new vemurafenib analogs, RF-86A, RF-87A, RF-94A, RF-94B and RF-96B, with structural improve-ments, in order to increase the anti-proliferative and anti-metastatic effect on human melanoma. We showed that the analogs were efficient in inducing cell death and reducing the migration of A375 cells, by inhibition of MMP-2 and MMP-9 activity, indicating that this action may be longer lasting comparing to the action of Vemurafenib.