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Although alkynes are one of the smallest functional groups, they are among the most versatile building blocks for organic chemistry, with applications ranging from biochemistry to material sciences. Alkynylation reactions have traditionally relied on the use of acetylenes as nucleophiles. The discovery and development of ethynyl hypervalent iodine reagents have allowed to greatly expand the transfer of alkynes as electrophilic synthons. In this feature article the progress in the field since 2018 will be presented. After a short introduction on alkynylation reactions and hypervalent iodine reagents, the developments in the synthesis of alkynyl hypervalent iodine reagents will be discussed. Their recent use in base-mediated and transition-metal catalyzed alkynylations will be described. Progress in radical-based alkynylations and atom-economical transformations will then be presented.

Atmospheric nucleation from precursor gases is a significant source of cloud condensation nuclei in the troposphere and thus can affect the Earth's radiative balance. Sulfuric acid, ammonia, and amines have been identified as key nucleation precursors in the atmosphere. Studies have also shown that atmospheric ions can react with sulfuric acid to form stable clusters in a process referred to as ion-induced nucleation (IIN). IIN follows similar reaction pathways as chemical ionization, which is used to detect and measure nucleation precursors via atmospheric pressure chemical ionization mass spectrometers. The rate at which ions form clusters depends on the ion-molecule rate constant. However, the rate constant varies based on the ion composition, which is often not known in the atmosphere. Previous studies have examined ion-molecule rate constants for sulfuric acid and nitrate ions but not for other atmospherically relevant ions like acetate. We report the relative rate constants of ion- molecule reactions between nitrate and acetate ions reacting with sulfuric acid. The ion- molecule rate constant for acetate and sulfuric acid is estimated to be a factor of 1.9-2.4 times higher than that of the known rate constant for nitrate and sulfuric acid. Using quantum chemistry, we find that acetate has a higher dipole moment and polarizability than nitrate. This may contribute to an increase in the collision cross-sectional area between acetate and sulfuric acid and lead to a greater reaction rate constant than nitrate. The ion- molecule rate constant for acetate with sulfuric acid will help quantify the contribution of acetate ions to atmospheric ion-induced new particle formation.

Atmospheric organic acids (OAs) are expected to enhance methanesulfonic acid (MSA)-driven new particle formation (NPF). However, the exact role of OAs in MSA-driven NPF remains unclear. Here, we employed a two-step strategy to probe the role of OAs in MSA–methylamine (MA) NPF. Initially, we evaluated the enhancing potential of 12 commonly detected OAs in ternary MA–MSA–OA cluster formation by considering the formation free energies of the (MSA)1(MA)1(OA)1 clusters and the atmospheric concentrations of the OAs. It was found that formic acid (ForA) has the highest potential to stabilize the MA–MSA clusters. The high enhancing potential of ForA results from its acidity, structural factors such as no intramolecular H bonds, and high atmospheric abundance. The second step is to extend the MSA–MA–ForA system to larger cluster sizes. The results indicate that ForA can indeed enhance MSA–MA NPF at atmospheric conditions (the upper limited temperature is 258.15 K), indicating that ForA might have an important role in MSA-driven NPF. The enhancing effect of ForA is mainly caused by an increased formation of the (MSA)2(MA)1 cluster, which is involved in the pathway of binary MSA–MA nucleation. Hence, our results indicate that OAs might be required to facilitate MSA-driven NPF in the atmosphere.

Systematic studies of acrolein oxidation and oxidative alkoxylation catalyzed by Se-modified microgel catalysts under mild reaction conditions were conducted. Se-modified microgels proved to be highly active colloidal catalysts and exhibited high performance for the oxidation of acrolein to acrylic acid and oxidative alkoxylation to the corresponding methyl/ethyl/butyl acrylates using hydrogen peroxide as a green oxidant. Methyl acrylate or acrylic acid can be synthesized in high yield (89-91%) and with high selectivity (97-99%) simply by regulating the solvent type and the concentration of selenium moieties in the microgel structure. Se-microgels exhibit exceptional catalytic activity compared with other Se-containing molecules of organic and inorganic nature. Due to the unique properties of the microgels that combine advantages from homogeneous and heterogeneous catalytic systems in terms of activity and selectivity as well as re-use possibilities, Se-microgel catalysts can be easily separated and reused in several catalytic cycles and remain highly active.

Ethynylbenziodoxolones (EBXs) are commonly used as radical traps in photocatalytic alkynylations. Herein, we report that aryl‐substituted EBX reagents can be directly activated by visible light irradiation. They act as both oxidants and radical traps, alleviating the need for a photocatalyst in several reported EBX‐mediated processes, including decarboxylative and deboronative alkynylations, the oxyalkynylation of enamides and the C−H alkynylation of THF. Furthermore, the method could be applied to the synthesis of alkynylated quaternary centers from tertiary alcohols via stable oxalate salts and from tertiary amines via aryl imines. A photocatalytic process using 4CzIPN as an organic dye was also developed for the deoxyalkynylation of oxalates., Aryl ethynylbenziodoxolones (ArEBXs) can be directly activated by visible light irradiation. In the excited state, ArEBXs act as strong oxidants, alleviating the need for a photocatalyst in decarboxylative and deboronative alkynylations, the oxyalkynylation of enamides, and the C−H alkynylation of THF.

Graphene oxide has unique physiochemical properties and a large surface area. After functionalization, its shape, surface, adsorption capacity, and toxicity levels can change. The potential impacts of sulfonated graphene oxide (SGO, modified with the sulfonic group) on metabolic processes and biological pathways are unanswered questions concerning NO3- or NH4+ toxicity. To fill this gap of knowledge, in the present study, SGO (50-250-500 mg L-1) was applied to Triticum aestivum cv. Ekiz with/without 140 mM nitrate (NS stress) and 5 mM ammonium (AS stress). Both stress treatments suppressed the growth, water content, osmotic potential, and photosynthetic capacity, as detected by a decrease in the carbon assimilation rate (A), stomatal conductance (g(s)), intercellular CO2 concentration (C-i), and transpiration rate (E), and an increase in stomatal limitation. After stress exposure, SGO provided positive responses to these parameters. There were different responses in the antioxidant system under stress: superoxide dismutase (SOD) and peroxidase (POX) under NS stress; SOD, catalase (CAT) and POX under AS and NS + AS stresses. However, hydrogen peroxide (H2O2) and lipid peroxidation increased because lack of effective antioxidant activation. In response to NS or AS, SGO successfully regulated SOD, CAT, glutathione peroxidase (GPX) and the enzyme/non-enzymes related to the AsA-GSH cycle, attenuating the high levels of H2O2, lipoxygenase (LOX) and TBARS-based damage. Along with the antioxidant system, SGO controlled the contents of NO3- or NH4+ by regulation of NPF6.3 and AMT1.2 genes. Interestingly, under NS plus AS, the alleviation action of SGO varied in a concentration-dependent manner: (i) low SGO concentration (50 mg L-1) protected the regeneration of ascorbate (AsA) and glutathione (GSH) and the high activities of GST and GPX; (ii) 250 mg L-1 SGO maintained the GSH redox state and the induced activity of glutathione S-transferase (GST); (iii) the highest SGO concentration (500 mg L-1) did not eliminate H2O2 accumulation, which coincided with the increased levels of TBARS and LOX. The toxicity of the high SGO concentration was further increased in wheat with non-stress or NS plus AS stresses. Our findings specified that the damage stimulated by NS and/or AS stress was removed by SGO applications through the increased antioxidant activity and gas exchange parameters, resulting in the protection of the redox state., Selcuk University Scientific Research Projects Coordinating Office [20401149], The authors would like to acknowledge to Advanced Technology Research and Application Center of Selcuk University for their kind help regarding analysis studies (SEM, HR-TEM, EDS). This work was supported by Selcuk University Scientific Research Projects Coordinating Office (Grant Number 20401149).

Organic dyes have emerged as a reliable class of photoredox catalysts. Their great structural variety combined with the easy fine-tuning of their electronic properties has unlocked new possibilities for the generation of reactive intermediates. In this review, we provide an overview of the available approaches to access reactive intermediates that employ organophotocatalysis. Our contribution is not a comprehensive description of the work in the area but rather focuses on key concepts, accompanied by a few selected illustrative examples. The review is organized along the type of reactive intermediates formed in the reaction, including C(sp3) and C(sp2) carbon-, nitrogen-, oxygen-, and sulfur-centered radicals, open-shell charged species, and sensitized organic compounds.

In this study, cinnamic acid derivatives were synthesized from the reaction of benzaldehyde derivatives with malonic acid in the presence of pyridine and piperidine. These compounds were then respectively reacted with glycine and L-alanine methyl ester hydrochloride based on triazine methodology to obtain novel cinnamoyl-amino acid ester derivatives. The structure of these compounds were established via H-1, C-13 APT, FT-IR, MS and elemental analysis. The synthesized novel compounds were studied in terms of structure-activity relationship based on dielectric, thermal stability, and theoretical analysis. Dielectric analysis was carried out in terms of amino acid type and aromatic substituted group (electron-withdrawing or releasing group factor). Amino acid side chain differences make alanine conjugates have higher epsilon \" values compared to glycine conjugates. Thermal stability analysis was performed for the compounds (10 and 16) with the highest dielectric constants. Thermal decomposition activation energies were calculated as 95 kJ mol(-1) and 100 kJ mol(-1) for 10 and 16, respectively. HOMO-LUMO energy levels and other related properties of the target compounds were analyzed and a correlation was observed between HOMO-LUMO energy band gap and dielectric constant.

The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions., The efficiency of chemical reactions in biological systems is often connected to the properties of confined water, but the developments and applications of artificial mimicking systems are impeded by the complexity of the biological systems. Here, the authors show how surface bound water in nanoporous cellulosic fibers can increase the reaction rate of surface acetylation reactions and enable regioselectivity of the reaction

Integrated CO2 capture and hydrogenation to methanol may replace fossil resources for production of clean fuels, chemicals, and materials. As opposed to the classic concept of lowering the transiti...

We report an organophotocatalytic 1,2-oxyalkynylation of ene-carbamates and enol ethers using Ethynyl BenziodoXolones (EBXs). 1-Alkynyl-1,2-amino alcohols and diols were obtained in up to 89% yield. Photocatalytic formation of radical cations led to Umpolung of the innate reactivity of the alkenes, enabling addition of a nucleophilic benzoate followed by radical alkynylation., Photocatalytic Umpolung with organic dyes overcoming the innate nucleophilicity of enecarbamates and enol ethers for oxyalkynylation with EBX reagents to access 1-alkynyl-1,2-amino alcohols and diols.

The environmental and economic challenges currently faced by the wax market may be addressed by the use of sustainable bio-based alternatives. Hereto, ketonization of vegetable oils and animal fats is a potential clean reaction route towards ketone bio-waxes. In the presence of a heterogeneous TiO2 catalyst, palm fatty acid distillate (PFAD) and other commercial feedstock are selectively coupled to bio-waxes in a solvent-less liquid phase ketonization process. The resulting ketone bio-waxes show similar, if not better water repellence properties than the current benchmark paraffin waxes when tested as hydrophobization agents in aqueous wax emulsions for wood composite materials. Despite the efficient utilization of biomass carbon in accord with the prescribed Green Chemistry principles in the catalytic ketonization reaction, sustainable end products are not always guaranteed. Depending on the substrate and system scenario, the comparative life cycle assessment (LCA) shows significantly lower or higher carbon footprints in comparison to fossil paraffin. Cultivation of biomass feedstock, catalyst production and the end-of-life phase are identified as the three major hotspots in the life cycle, while the gate-to-gate impact of the proposed ketonization process design itself is rather limited. Advice is formulated to considerably improve LCA of ketone bio-waxes, achieving sustainable waxy products with appreciably lower CO2 footprints than the fossil paraffin waxes.

Despite being one of the most frequently carried out chemical reactions in industry, there is currently no amidation protocol that is regarded as safe, high yielding, environmentally friendly and inexpensive. The direct amidation of a carboxylic acid with an amine is viewed as an inherently good solution for developing such a protocol. Since the 1960s, there has been a gradual development in the use of silicon reagents for direct amidation. This review covers the methods published to April 2021 for silicon reagent mediated direct amidation of a carboxylic acid with an amine. This review also covers the use of polymeric SiO2 to promote direct amidation.

Background The current shift from a fossil-resource based economy to a more sustainable, bio-based economy requires development of alternative production routes based on utilization of biomass for the many chemicals that are currently produced from petroleum. Muconic acid is an attractive platform chemical for the bio-based economy because it can be converted in chemicals with wide industrial applicability, such as adipic and terephthalic acid, and because its two double bonds offer great versatility for chemical modification. Results We have constructed a yeast cell factory converting glucose and xylose into muconic acid without formation of ethanol. We consecutively eliminated feedback inhibition in the shikimate pathway, inserted the heterologous pathway for muconic acid biosynthesis from 3-dehydroshikimate (DHS) by co-expression of DHS dehydratase from P. anserina, protocatechuic acid (PCA) decarboxylase (PCAD) from K. pneumoniae and oxygen-consuming catechol 1,2-dioxygenase (CDO) from C. albicans, eliminated ethanol production by deletion of the three PDC genes and minimized PCA production by enhancing PCAD overexpression and production of its co-factor. The yeast pitching rate was increased to lower high biomass formation caused by the compulsory aerobic conditions. Maximal titers of 4 g/L, 4.5 g/L and 3.8 g/L muconic acid were reached with glucose, xylose, and a mixture, respectively. The use of an elevated initial sugar level, resulting in muconic acid titers above 2.5 g/L, caused stuck fermentations with incomplete utilization of the sugar. Application of polypropylene glycol 4000 (PPG) as solvent for in situ product removal during the fermentation shows that this is not due to toxicity by the muconic acid produced. Conclusions This work has developed an industrial yeast strain able to produce muconic acid from glucose and also with great efficiency from xylose, without any ethanol production, minimal production of PCA and reaching the highest titers in batch fermentation reported up to now. Utilization of higher sugar levels remained conspicuously incomplete. Since this was not due to product inhibition by muconic acid or to loss of viability, an unknown, possibly metabolic bottleneck apparently arises during muconic acid fermentation with high sugar levels and blocks further sugar utilization.

Meteorites contain organic matter that may have contributed to the origin of life on Earth. Carbonyl compounds such as aldehydes and carboxylic acids, which occur in meteorites, may be precursors of biologically necessary organic materials in the solar system. Therefore, such organic matter is of astrobiological importance and their detection and characterization can contribute to the understanding of the early solar system as well as the origin of life. Most organic matter is typically sub-micrometer in size, and organic nanoglobules are even smaller (50-300 nm). Novel analytical techniques with nanoscale spatial resolution are required to detect and characterize organic matter within extraterrestrial materials. Most techniques require powdered samples, consume the material, and lose petrographic context of organics. Here, we report the detection of nanoglobular aldehyde and carboxylic acids in a highly primitive carbonaceous chondrite (DOM 08006) with similar to 20 nm spatial resolution using nano-FTIR spectroscopy. Such organic matter is found within the matrix of DOM 08006 and is typically 50-300 nm in size. We also show petrographic context and nanoscale morphologic/topographic features of the organic matter. Our results indicate that prebiotic carbonyl nanoglobules can form in a less aqueous and relatively elevated temperature-environment (220-230 degrees C) in a carbonaceous parent body. RISE2 node of NASA's Solar System Exploration Research Virtual Institute (SSERVI) We thank the associate editor and the reviewers for their constructive comments, which significantly improved this manuscript. We thank NASA-JSC for providing the meteorite samples. This work was also supported in part by the RISE2 node of NASA's Solar System Exploration Research Virtual Institute (SSERVI; PI: T.D. Glotch).

We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and alpha, omega-dicarboxylic acids and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water-water and acid-water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C-5-C-8), while for monocarboxylic acids (C-1-C-6) and smaller dicarboxylic acids (C-2-C-4), hydrate formation is more favorable, especially in dilute solutions.

Salt formation is a well-established method to increase the solubility of ionizable drug candidates. However, possible conversion of salt to its original form of free acid or base - disproportionation - can have a drastic effect on the solubility and consequently the bioavailability of a drug. Therefore, during the salt selection process, the salt dissolution behavior should be well understood. Improved understanding could be achieved by a method that enables simultaneous screening of small sample amounts and detailed dissolution process analysis. Here, we use a machine-vision-based single-particle analysis (SPA) method to successfully determine the pH-solubility profile, intrinsic solubility, common-ion effect, pKa, pHmax, and Ksp values of three model compounds in a fast and low sample consumption (

A straightforward methodology for the decarboxylative cross-coupling of aryl bromides and phenylpropiolic acid using a Pd(II)-NHC catalyst has been developed. Various aryl bromides have been successfully transformed into the corresponding di-substituted alkynes using environmentally benign conditions (weak base and ethanol as solvent). This efficient catalytic system also proved useful for the copper-free Sonogashira coupling of aryl and alkenyl bromides with various terminal alkynes. The synthetic utility of these methodologies was highlighted in the synthesis of a polyaromatic compound and various fluoroenynes.

This review explores the alkynylation of radicals as approach for the flexible and efficient synthesis of alkynes., The alkynylation of radical intermediates has been known since a long time, but had not been broadly applied in synthetic chemistry, in contrast to the alkynylation of either electrophiles or nucleophiles. In the last decade however, it has been intensively investigated leading to new disconnections to introduce versatile triple bonds into organic compounds. Nowadays, such processes are important alternatives to classical nucleophilic and electrophilic alkynylations. Efficient alkyne transfer reagents, in particular arylsulfones and hypervalent iodine reagents were introduced. Direct alkynylation, as well as cascade reactions, were subsequently developed. If relatively harsh conditions were required in the past, a new era began with progress in photoredox and transition metal catalysis. Starting from various radical precursors, alkynylations under very mild reaction conditions were rapidly discovered. This review covers the evolution of radical alkynylation, from its emergence to its current intensive stage of development. It will focus in particular on improvements for the generation of radicals and on the extension of the scope of radical precursors and alkyne sources.

Amides are ubiquitous molecules in nature and in synthetic chemistry. Here we report a convenient and efficient method to synthesize N-aryl amides via amidation of esters with nitroarenes. In the presence of manganese metal, this amidation proceeded smoothly without the need for additional catalysts or ligands. Various esters and nitroarenes are suitable substrates to afford a wide range of N-aryl amides, including bio-active molecules and intermediates to drug molecules.

Water addition to alpha,beta-unsaturated nitriles would give facile access to the -hydroxy-nitriles, which in turn can be hydrogenated to the gamma-amino alcohols. We have previously shown that alcohols readily add in 1,4-fashion to these substrates using Milstein's Ru(PNN) pincer complex as catalyst. However, attempted water addition to alpha,beta-unsaturated nitriles gave the 3-hydroxynitriles in mediocre yields. On the other hand, addition of benzyl alcohol proceeded in excellent yields for a variety of -substituted unsaturated nitriles. Subsequent treatment of the benzyl alcohol addition products with TMSCl/FeCl3 resulted in the formation of 3-hydroxy-alkylnitriles. The 3-benzyloxy-alkylnitriles obtained from oxa-Michael addition also could be hydrogenated directly in the presence of acid to give the amino alcohols as their HCl salts in excellent yields. Hydrogenation under neutral conditions gave a mixture of the secondary and tertiary amines. Hydrogenation in the presence of base and Boc-anhydride gave the orthogonally bis-protected amino alcohols, in which the benzyl ether can subsequently be cleaved to yield Boc-protected amino alcohols. Thus, a variety of molecular scaffolds with a 1,3-relationship between O- and N-functional group is accessible starting from oxa-Michael addition of benzyl alcohol to alpha,beta-unsaturated nitriles.

Deep eutectic solvents (DESs) constitute a new class of ionic solvents that has been developing at a fast pace in recent years. Since these solvents are commonly suggested as green alternatives to organic solvents, it is important to understand their physical properties. In particular, polarity plays an important role in solvation phenomena. In this work, the polarity of different families of DESs was studied through solvatochromic responses of UV-vis absorption probes. Kamlet-Taft α, β, π* and ETN parameters were evaluated using different solvatochromic probes, as 2,6-dichloro-4-(2,4,6-triphenyl-N-pyridino)-phenolate (Reichardt's betaine dye 33), 4-nitroaniline, and N,N-diethyl-4-nitroaniline for several families of DESs based on cholinium chloride, dl-menthol and a quaternary ammonium salt ([N4444]Cl). In addition, a study to understand the difference in polarity properties between DESs and the corresponding ILs, namely ILs based on cholinium cation and carboxylic acids as anions ([Ch][Lev], [Ch][Gly] and [Ch][Mal]), was carried out. The chemical structure of the hydrogen bond acceptor (HBA) in a DES clearly controls the dipolarity/polarizability afforded by the DES. Moreover, Kamlet-Taft parameters do not vary much within the family, but they differ among families based on different HBA, either for DESs containing salts ([Ch]Cl or [N4444]Cl) or neutral compounds (dl-menthol). A substitution of the HBD was also found to play an important role in solvatochromic probe behaviour for all the studied systems.

Ab initio molecular dynamics simulations of formic acid (FA) dimer colliding with liquid water at 300 K have been performed using density functional theory. The two energetically lowest FA dimer isomers were collided with a water slab at thermal and high kinetic energies up to 68k(B)T. Our simulations agree with recent experimental observations of nearly a complete uptake of gas-phase FA dimer: the calculated average kinetic energy of the dimers immediately after collision is 5 +/- 4% of the incoming kinetic energy, which compares well with the experimental value of 10%. Simulations support the experimental observation of no delayed desorption of FA dimers following initial adsorption. Our analysis shows that the FA dimer forms hydrogen bonds with surface water molecules, where the hydrogen bond order depends on the dimer structure, such that the most stable isomer possesses fewer FA-water hydrogen bonds than the higher energy isomer. Nevertheless, even the most stable isomer can attach to the surface through one hydrogen bond despite its reduced hydrophilicity. Our simulations further show that the probability of FA dimer dissociation is increased by high collision energies, the dimer undergoes isomerization from the higher energy to the lowest energy isomer, and concerted double-proton transfer occurs between the FA monomers. Interestingly, proton transfer appears to be driven by the release of energy arising from such isomerization, which stimulates those internal vibrational degrees of freedom that overcome the barrier of a proton transfer.

The polymorphic behaviour of a co-crystal composed of neutral suberic acid and 1,2-bis(4-pyridyl)ethane is reported. A multidisciplinary approach has been employed, using thermal analysis methods (differential scanning calorimetry and polarized light thermomicroscopy), spectroscopic methods (infrared spectroscopy) and X-ray single crystal and powder diffraction. Two new polymorphs, Land III; have been identified, and for one of them the crystal structure has been elucidated and compared to that of a known polymorph, form II, showing that the assembling of the molecules in chains via H-bonds is a common feature of both polymorphs. Polymorph II, obtained by crystallization from an aqueous or ethanol solution or by grinding, undergoes a solid-solid transition to polyniorph I, which melts at 180.5 degrees C. Upon cooling from the melt, polymorph I is obtained, and a solid-solid transformation also occurs, to poly morph III'. Polymorph III was obtained serendipitously in an attempt to prepare a Nd(III) complex. The relative stability of the three polymorphic forms was established. (C) 2017 Elsevier B.V. All rights reserved.

[EN] Biowaxes are interesting materials for pharmaceutical industry and consumer goods. Here the production of waxes from alternative renewable resources has been evaluated on the basis of the ketonic decarboxylation of fatty acids. The latter converts carboxylic acids (or their derivatives) into ketones with almost double chain length. Hence, sunflower oil was employed as starting material and passed over monoclinic zirconium. A wax fraction of 43% yield was obtained, though high content of molecules with more than 30 carbon atoms was not achieved due to prevalent carbon chain degradation. However, reaction of methyl stearate over zirconium oxide gave 60% wax fraction. Together with the waxes, an almost oxygen-free diesel fraction was obtained in more than 25% yield. Labeling experiments showed that the ketone intermediate is degraded by a radical chain mechanism. It is further concluded that methyl stearate radical formation is induced by carbon carbon bond scission at high temperature whereas the glycerol part of the triglyceride may act as radical initiator. As a consequence, long linear alkane waxes should be produced in the absence of glycerol (moieties). The exploitation of the side-product as high quality diesel together with the waxes improves the economic feasibility of the process., The authors thank MINECO (CTQ2015-67591-P and Severo Ochoa program, SEV-2016-0683) and Generalitat Valenciana (PROMETEO II/2013/011 Project) for funding this work. B.O.-T. is grateful to the CSIC (JAE program) for his Ph.D. fellowship.

In this study, single crystals of urea ninhydrin monohydrate (UNMH) have been grown by slow evaporation method. The grown crystals were characterized by FT-IR, FT-Raman and UV-Vis-NIR spectroscopies. The Kurtz and Perry powder method was employed to confirm the near-zero SHG efficiency of the as-grown centrosymmetric UNMH crystal. The third order nonlinearity of the crystal has been studied by the open aperture Z-scan method. The nonlinear absorption coefficient is calculated and the potentiality of UNMH in optical limiting applications is identified. The molecular geometry and the origin of optical non-linearity at the molecular level have been investigated by the density functional theory. The normal coordinate analysis was carried out to assign the molecular vibrational modes. Vibrational spectral studies confirms the presence of weak O-H ... O and moderate O-H ... O type hydrogen bonds in the molecule as well as O-H ... O, N-H ... O and blue-shifted C-H ... O type H-bonds in the crystal. The intramolecular charge transfer interactions and the electronic absorption mechanisms have been discussed. The static and the dynamic values of hyperpolarizabilities for UNMH were estimated theoretically by DFT methods. (C) 2017 Elsevier B.V. All rights reserved.

We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low-pH (i.e., pH < pKa) electrolyte solutions. The effects of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (?80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ?30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

A series of transition metal-based double metal cyanides (DMCs) were studied as catalysts for the synthesis of nitriles via acid-nitrile exchange reaction. The best nitrile yields were obtained with Co3[Co(CN6)]2 DMC, which proved to be a versatile, stable, reusable and highly active catalyst, exhibiting an activity comparable to that of homogeneous Lewis acid catalysts. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:86 pages:12984-12987 ispartof: location:England status: published

We report experiments on the extraction of acids and bases from an aqueous phase to a pseudoprotic ionic liquid phase consisting of an equimolar mixture of trihexylamine and octanoic acid. We observed the extraction of a wide range of acids and bases, and investigated the mechanism of extraction in detail. Our results confirmed the observation of the Hofmeister effect in these systems reported in our previous work, where the extent of the extraction of copper salts was significantly influenced by the interactions between extracted inorganic anions and the organic phase. Our results further demonstrated that the organic layer served as a &ldquo, floating buffer&rdquo, capable of stabilizing the pH of an acidic or alkaline aqueous phase. The results tie current interest in protic and pseudoprotic ionic liquids to earlier work on the extraction of acids using amine and acid&ndash, base couples as extraction agents in an inert organic solvent.

Reactive extraction of pentanedioic acid using Amberlite LA-2 in different diluents, such as hexane, methylbenzene, kerosene, 4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone, n-hexanone, 3-methyl-1-butanol, n-octanol, nnonanol, and n-decanol, respectively, was studied. At lower amine concentrations, K-D values of less than 1 were obtained but it improves as amine concentration was raised. Increase in amine concentration was found to increase the KD by 80-85% in inert diluents (hexane, methylbenzene and kerosene). In the chosen ketones, the extraction percentage follows the following trend 4-methyl-2-pentanone > DIBK > n-hexanone. Among the various diluents used, higher KD was obtained when alcohols were used as diluents. Mass action equilibria, linear solvation energy relationship modeling, and differential evolution (DE) was applied for estimating the model parameter and compare the model values with the experimental results of extraction equilibria.

Background:Despite the progress in the discovery of antiretroviral compounds for treating HIV-1 infection by targeting HIV integrase (IN), a promising and well-known drug target against HIV-1, there is a growing need to increase the armamentarium against HIV, for avoiding the drug resistance issue.Objective:To develop novel HIV-1 IN inhibitors, a series of 3-hydroxy-pyrane-4-one (HP) and 3- hydroxy-pyridine-4-one (HPO) derivatives have been rationally designed and synthesized.Methods:To provide a significant characterization of the novel compounds, in-depth computational analysis was performed using a novel HIV-1 IN/DNA binary 3D-model for investigating the binding mode of the newly conceived molecules in complex with IN. The 3D-model was generated using the proto-type foamy virus (PFV) DNA as a structural template, positioning the viral polydesoxyribonucleic chain into the HIV-1 IN homology model. Moreover, a series of in vitro tests were performed including HIV-1 activity inhibition, HIV-1 IN activity inhibition, HIV-1 IN strand transfer activity inhibition and cellular toxicity.Results:Bioassay results indicated that most of HP analogues including HPa, HPb, HPc, HPd, HPe and HPg, showed favorable inhibitory activities against HIV-1-IN in the low micromolar range. Particularly halogenated derivatives (HPb and HPd) offered the best biological activities in terms of reduced toxicity and optimum inhibitory activities against HIV-1 IN and HIV-1 in cell culture.Conclusion:Halogenated derivatives, HPb and HPd, displayed the most promising anti-HIV profile, paving the way to the optimization of the presented scaffolds for developing new effective antiviral agents.

From corrosion inhibition to lubrication, a detailed understanding of the interactions between surfactants and iron oxide surfaces is critical for a range of industrial applications. However, there is still limited understanding of this behavior at the atomic-level, which hinders the design of improved surfactant molecules. In this study, the adsorption of three surfactants which are commonly employed as lubricant additives (carboxylic acid, amide, monoglyceride) on a α-Fe2O3(0001) surface is studied with density functional theory. The nature and strength of the adsorption for the different surfactants, as well as their propensity to deprotonate on the surface, is studied at a range of surface coverages. In agreement with the available experiments, strong chemisorption on α-Fe2O3(0001) is observed for all cases considered. Dissociation is energetically favorable for carboxylic acid and glyceride surfactants through the formation of a surface hydroxyl group, whereas this is not the case for amides. Glycerides form the most strongly adsorbed films at both low and high surface coverage due to the presence of multiple functional groups, which can all act as binding sites. However, the large size of the glyceride headgroup also means that adsorption is stronger at low coverage, where the formation of multiple bonds with the surface is possible, than at high coverage. Conversely, carboxylic acid films have similar stability at low and high coverage, where van der Waals forces between proximal tailgroups stabilize the adsorption structures. The results of this study provide atomic-level insights which help to explain friction results from previous macroscopic tribology experiments and classical molecular dynamics simulations. They also facilitate the molecular design of new surfactants to maximize the adsorption energy, surface coverage, and ultimately friction reduction on iron oxide surfaces.

Chiral tertiary and quaternary amine solvating agents for NMR spectroscopy were synthesized from the wood resin derivative (+)-dehydroabietylamine (2). The resolution of enantiomers of model compounds [Mosher's acid (3) and its n-Bu4N salt (4)] (guests) by (+)-dehydroabietyl-N,N-dimethylmethanamine (5) and its ten different ammonium salts (hosts) was studied. The best results with 3 were obtained using 5 while with 4 the best enantiomeric resolution was obtained using (+)-dehydroabietyl-N,N-dimethylmethanaminium bis(trifluoromethane-sulfonimide) (6). The compounds 5 and 6 showed a 1:1 complexation behaviour between the host and guest. The capability of 5 and 6 to recognize the enantiomers of various -substituted carboxylic acids and their n-Bu4N salts in enantiomeric excess (ee) determinations was demonstrated. A modification of the RES-TOCSY NMR pulse sequence is described, allowing the enhancement of enantiomeric discrimination when the resolution of multiplets is insufficient.

Deep eutectic solvents (DES) are mixtures of hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD) with a melting point much lower than that of either of its components. They have been the focus of interest in past years due to their unique properties, low cost, and wide range of applications. Despite the attention given to DES and their claimed benignity when compared with ionic liquids, their environmental impact is poorly characterized and understood. In this work, the toxicity of some DES prepared with cholinium chloride ([Chol]Cl) as HBA and organic acids, namely acetic, citric, lactic, and glycolic acids, as HBD was measured with the Microtox toxicity test. These DES showed an intermediate toxicity when compared with the respective starting materials and can be considered as \"moderately toxic,\" their toxicity being clearly dominated by the concentration of the acid. They are also shown to be more toxic than their corresponding ionic liquids, namely cholinium glycolate, cholinium acetate, cholinium dihydrogencitrate, and cholinium lactate. Further studies are necessary on the ecotoxicology and biodegradability of DES, namely to evaluate their capability to both classic solvents and ionic liquids. green\" character and their alternative capability to both classic solvents and ionic liquids.

The scope of this work is to study at atomistic level the mechanism of hydrogen spillover promoted by metal particles on oxide surfaces. By means of Density Functional Theory calculations with Hubbard correction (DFT+U) we have analyzed the adsorption and dissociation of molecular hydrogen on anatase titania, a-TiO2 (101), and tetragonal zirconia, t-ZrO2 (101), surfaces in the presence of a supported Ru10 nanocluster. The role of the supported metal particle is essential as it favors the spontaneous dissociation of H2, a process which does not occur on the bare oxide surface. At low hydrogen coverage, the H atoms prefer to stay on the Ru10 particle, charge accumulates on the metal cluster, and reduction of the oxide does not take place. On a hydroxylated surface, the presence of a Ru nanoparticle is expected to promote the reverse effect, i.e. hydrogen reverse spillover from the oxide to the supported metal. It is only at high hydrogen coverage, resulting in the adsorption of several H2 molecules on the metal cluster, that it becomes thermodynamically favorable to have hydrogen transfer from the metal to the O sites of the oxide surface. In both TiO2 and ZrO2 surfaces the migration of an H atom from the Ru cluster to the surface is accompanied by an electron transfer to the empty states of the support with reduction of the oxide surface.

Oral bioavailability of a drug molecule requires its effective delivery to the target site. In general, majority of synthetically developed molecular entities have high hydrophobic nature as well as low bioavailability, therefore the need for suitable delivery vehicles arises. Self-assembled structures such as micelles, niosomes, and liposomes have been used as effective delivery vehicles and studied extensively. However, the information available in literature is mostly qualitative in nature. We have quantitatively investigated the partitioning of antibiotic drug streptomycin into cationic, nonionic, and a mixture of cationic and nonionic surfactant micelles and its interaction with the transport protein serum albumin upon subsequent delivery. A combination of calorimetry and spectroscopy has been used to obtain the thermodynamic signatures associated with partitioning and interaction with the protein and the resulting conformational changes in the latter. The results have been correlated with other class of drugs of different nature to understand the role of molecular features in the partitioning process. These studies are oriented toward understanding the physical chemistry of partitioning of a variety of drug molecules into suitable delivery vehicles and hence establishing structure-property-energetics relationships. Such studies provide general guidelines toward a broader goal of rational drug design.

The phase behaviour of equimolar mixtures of 6-(4'-cyanobiphenyl-4-yl)hexyloxybenzoic acid (CB6OBA) with either 1-(4-butylazobenzene-4'-oxy)-5-(4-oxypyridine)pentane (BuABO5OPyr) or 1-(4-butylazobenzene-4'-oxy)-6-(4-oxypyridine)hexane (BuABO6OPyr) is reported. CB6OBA shows a monotropic twist-bend nematic phase and an enantiotropic nematic phase whereas the two pyridyl-based components do not exhibit liquid crystallinity. Both equimolar mixtures (CB6OBA/BuABOnOPyr) show enantiotropic nematic phases. The nematic-isotropic transition temperature and associated entropy change are higher for the CB6OBA/BuABO6OPyr mixture than for the CB6OBA/BuABO5OPyr mixture. This may be accounted for in terms of the average shapes of the hydrogen-bonded 1:1 complexes formed between the two differing components in the mixtures. However, Fourier transform infrared spectroscopy reveals that this complex is not formed quantitatively, but instead a complex mixture exists over the complete temperature range studied, involving the 1:1 complex, both cyclic and open acid dimers, free acid and hence, free BuABOnOPyr molecules.

Cocrystal formation of chlorothiazide (ctz) was screened with a variety of coformers with carboxyl, amide, hydroxyl, sulfonamide, pyridine, amidine, and amine functional groups. New cocrystals with acetamide (aca), benzamide (bza), propionamide (ppa), caprolactam (cap), carbamazepine (cbz), nicotinamide (nia), isonicotinamide (ina), hexamethylenetetramine (hma), 4,4'-bipyridine (bipy), 1,2-di(4-pyridyl)ethylene (ebipy), 2-hydroxypyridine (hyp), 1,3-di(4-pyridyl)propane (pbipy) and pyrazine (pyr) as well as a benzamidinium (bzamH(+)) salt were obtained by mechanical grinding and liquid-assisted grinding and identified by powder X-ray diffraction. The structures of ctz-bza, ctz-cbz, ctz-ina, ctz-nia, ctz-hma, ctz-bipy, ctz-ebipy, ctzpbipy, and (bzamH(+)) (ctz(-)) were determined by single-crystal X-ray diffraction. Analysis of the hydrogen bonding motifs showed that in all cocrystal structures except for ctz-bipy, the NHsuifonamide center dot center dot center dot N (SO2)=C catemer synthon of ctz form I is replaced by ctz-coformer heterosynthons. The dissolution behavior and relationship between dissolution rate, packing index, and lattice energy of the cocrystals is described. To understand why no cocrystals with carboxylic acids formed, a motif search of the Cambridge Structural Database (CSD) was carried out. This work was supported by Science Foundation Ireland under Grant No. 12/RC/2275 as part of the Synthesis and Solid State Pharmaceutical Centre (SSPC). M.A. acknowledges the Royal Embassy of Saudi Arabia for a Saudi Arabia Government Scholarship. peer-reviewed 2018-09-01

The generally accepted monoacyloxyboron mechanism of boron-catalysed direct amidation is brought into question in this study, and new alternatives are proposed., The generally accepted monoacyloxyboron mechanism of boron-catalysed direct amidation is brought into question in this study, and new alternatives are proposed. We have carried out a detailed investigation of boron-catalysed amidation reactions, through study of the interaction between amines/carboxylic acids and borinic acids, boronic acids and boric acid, and have isolated and characterised by NMR/X-ray crystallography many of the likely intermediates present in catalytic amidation reactions. Rapid reaction between amines and boron compounds was observed in all cases, and it is proposed that such boron–nitrogen interactions are highly likely to take place in catalytic amidation reactions. These studies also clearly show that borinic acids are not competent catalysts for amidation, as they either form unreactive amino-carboxylate complexes, or undergo protodeboronation to give boronic acids. It therefore seems that at least three free coordination sites on the boron atom are necessary for amidation catalysis to occur. However, these observations are not consistent with the currently accepted ‘mechanism’ for boron-mediated amidation reactions involving nucleophilic attack of an amine onto a monomeric acyloxyboron intermediate, and as a result of our observations and theoretical modelling, alternative proposed mechanisms are presented for boron-mediated amidation reactions. These are likely to proceed via the formation of a dimeric B–X–B motif (X = O, NR), which is uniquely able to provide activation of the carboxylic acid, whilst orchestrating the delivery of the amine nucleophile to the carbonyl group. Quantum mechanical calculations of catalytic cycles at the B3LYP+D3/Def2-TZVPP level (solvent = CH2Cl2) support the proposal of several closely related potential pathways for amidation, all of which are likely to be lower in energy than the currently accepted mechanism.

Biomass burning is a major source of greenhouse gases and influences regional to global climate. Pre-industrial fire-history records from black carbon, charcoal and other proxies provide baseline estimates of biomass burning at local to global scales spanning millennia, and are thus useful to examine the role of fire in the carbon cycle and climate system. Here we use the specific biomarker levoglucosan together with black carbon and ammonium concentrations from the North Greenland Eemian (NEEM) ice cores (77.49° N, 51.2° W; 2480 m a.s.l) over the past 2000 years to infer changes in boreal fire activity. Increases in boreal fire activity over the periods 1000–1300 CE and decreases during 700–900 CE coincide with high-latitude NH temperature changes. Levoglucosan concentrations in the NEEM ice cores peak between 1500 and 1700 CE, and most levoglucosan spikes coincide with the most extensive central and northern Asian droughts of the past millennium. Many of these multi-annual droughts are caused by Asian monsoon failures, thus suggesting a connection between low- and high-latitude climate processes. North America is a primary source of biomass burning aerosols due to its relative proximity to the Greenland Ice Cap. During major fire events, however, isotopic analyses of dust, back trajectories and links with levoglucosan peaks and regional drought reconstructions suggest that Siberia is also an important source of pyrogenic aerosols to Greenland.

Although the understanding of ion specific effects on the aqueous solubilities of biomolecules is crucial for the development of many areas of biochemistry and life sciences, a consensual and well-supported molecular picture of the phenomena has not yet been established. Mostly, the influence of cations and the nature of the molecular interactions responsible for the reversal of the Hofmeister trend in aqueous solutions of amino acids and proteins are still defectively understood. Aiming at contributing to the understanding of the molecular-level mechanisms governing the cation specific effects on the aqueous solubilities of biocompounds, experimental solubility measurements and classical molecular dynamics simulations were performed for aqueous solutions of three amino acids (alanine, valine, and isoleucine), in the presence of a series of inorganic salts. The evidence gathered suggests that the mechanism by which salting-in inducing cations operate in aqueous solutions of amino acids is different from that of anions, and allows for a novel and Consistent molecular description of the effect of the cation on the solubility based on specific interactions of the cations with the negatively charged moieties of the biomolecules.

The increasing need for large quantities of biologically active peptides for the market strongly raised the problem of the environmental sustainability of their synthesis. In this respect, we describe herein a solid phase procedure in water, using PEG peptide amide resins and NCAs under controlled conditions. This procedure afforded with reasonable yield and purity a short peptide amide, without the need of coupling reagents or protecting groups.