Non-innocent ligands in bioinorganic chemistry—An overview

This review touches the most common instances where non-innocent (“suspect”) behaviour of redox-active ligands, either substrates or supporting components, is observed in a biochemical context. These ligands include the O₂/O₂^?/O₂^2?, NO⁺/NO/NO^?, o-quinone/o-semiquinone/catecholate and tyrosyl/tyrosinate redox systems, the tetrapyrrole (porphyrinic) ligands, the pterins and flavins, and the dithiolene/ene-dithiolate ligands in molybdo- and tungstopterin. These non-innocent ligands are discussed in their interaction with biological iron, copper, manganese, molybdenum or tungsten centers.     

Photocatalysis of β-blockers – An overview

Photocatalysis is one of the most effective advanced oxidation processes to remove residual pharmaceuticals from the aquatic environment. β-Blockers are the group of pharmaceuticals commonly found in the environment and are showing potential risk to the aquatic and terrestrial organisms. This paper provides an overview of different photocatalytic procedures found in the literature for the abatement of β-blockers.     

Sulphur and peroxide vulcanisation of rubber compounds — overview

Vulcanisation is a process of transforming a plastic rubber compound into a highly elastic product by forming a three-dimensional cross-linked network structure in the rubber matrix. Many systems have been developed to vulcanise rubber compounds, among which sulphur and peroxide curing systems remain the most desirable. The application of sulphur systems leads to the forming of sulphidic cross-links between elastomer chains, while carbon–carbon bonds are formed in peroxidecuring. Both vulcanisation systems provide certain benefits to the cross-linked rubber articles, but also some disadvantages. The present work seeks to provide an overview on both vulcanisation systems; their composition, possibilities of their application, reaction mechanisms, structure of the cross-links formed and the main feature of the final cross-linked materials — vulcanisates.     

Photochemistry of thioxanthones—III. Spectroscopic and flash photolysis study on hydroxy and methoxy derivatives

The spectroscopic properties of 9 oil soluble hydroxy and methoxy thioxanthone derivatives have been examined in various solvents and the data compared to their photopolymerization efficiency and flash photolysis behaviour in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, most of the compounds exhibit low fluorescence and high phosphorescence quantum yields except 1-substituted derivatives where intra-molecular hydrogen bonding is involved. These observations are consistent with the high photoreactivity of the molecules occurring via the lowest excited triplet state. Photopolymerization rates of n-butyl methacrylate, using N-diethylmethylamine as co-initiator, correlate to some extent with the absorption maxima and extinction coefficients of the thioxanthones. Transient formation on micro-second flash photolysis is associated with the ketyl radical formed by the lowest excited triplet state of the thioxanthones abstracting a hydrogen atom from the solvent. In the presence of a tertiary amine, a new longer wavelength transient absorption is produced and is assigned to a radical-anion formed by the lowest excited triplet state of the thioxanthones abstracting an electron from the amine. A correlation was observed between the transient absorption due to the radical-anion and the ionisation potential of various amines. Flash photolysis studies in acid and base media confirmed the identity of the radical and radical-ion species. Intra-molecular hydrogen bonding in the α-position to the carbonyl group deactivates both the lowest excited singlet and triplet states of thioxanthone but has little effect on polymerization efficiency. The latter is associated with competition of the carbonyl group with the amine co-initiator for hydrogen bonding and consequent electron abstraction to give an active radical-anion. This is confirmed using micro-second flash photolysis.     

Porous ceramic membranes for catalytic reactors — overview and new ideas

The membrane reactor (MR) concept, combining in the same unit a conversion effect (catalyst) and a separation effect (membrane), already showed various potential benefits (increased reaction rate, selectivity and yield) for a range of reactions involving the membrane as extractor, distributor or contactor. Due to the generally severe conditions of heterogeneous catalysis, most MR applications use inorganic membranes, which can be dense or porous, inert or catalytically active. After a rapid overview of the working concepts of MRs, the main types of porous ceramic membranes, which have been developed for MR applications, are reported and discussed (characteristics and limitations). Starting from these general basis, our objective is to put recent developments into focus, with a special emphasis on porous composite infiltrated membranes and related synthesis methods. Some new ideas currently explored in our group, such as the ‘chemical valve membrane’ concept and the interest of nanophase materials for oxygen transport, will be also developed. An attempt in addressing the future developments of porous membranes for MRs will be finally proposed.     

An overview on synthetic entries to tetrahydro-β-carbolines

The tetrahydro-β-carboline (THBC) nucleus is a predominant feature of a vast array of naturally occurring alkaloids. Most of these alkaloids have been found to exhibit significant biological activities, which promote to develop a plethora of synthetic methods for the construction of THBCs. In this review, we focus on the recent developments and studies related to the synthesis of THBCs including total syntheses of related alkaloids mainly over the period of 2000–2017. In addition, a brief account of some significant THBC alkaloids with their sources and bioactivities is also presented in tabular format.     

Emulsification and Demulsification — An Historical Overview

The origins of the fields of emulsification and demulsification and early studies are reviewed with particular emphasis on the last fifty years. Trends and causes of the current revival in interest are indicated.     

Photochemistry of thioxanthones—I. Spectroscopic and flash photolysis study on oil soluble structures

The spectroscopic properties of six oil soluble thioxanthone structures have been examined in various solvents and the data compared to their photopolymerisation efficiency, photochemical stability and flash photolysis behaviour in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, all the compounds exhibit low fluorescence and high phosphorescence quantum yields but the ratio is solvent dependent. These observations are consistent with the high photoreactivity of the molecules occurring via the lowest excited triplet state. Photopolymerisation rates of n-butyl methacrylate with N-methyldiethylamine correlate with the absorption maxima and extinction coefficients of the thioxanthones and also the degree of quenching of their fluorescence by the tertiary amine, indicating the importance of electron transfer. Transient formation on microsecond flash photolysis is associated with the ketyl radical formed by the lowest excited triplet state abstracting a hydrogen atom from the solvent and this is confirmed by a strong quenching effect by molecular oxygen. In the presence of the tertiary amine, ketyl radical formation is generally suppressed but a new absorption band appears at longer wavelengths; it is tentatively assigned to the radical anion. Feasible mechanisms are discussed on the basis of the results.     

Photochemistry of thioxanthones—IV. Spectroscopic and flash photolysis study on novel n-propoxy and methyl,n-propoxy derivatives

The spectroscopic properties of seven oil soluble n-propoxy and methyl, n-propoxy substituted thioxanthone structures have been examined in various solvents and the data compared to their photopolymerization efficiencies, photochemical stabilities and flash photolysis behaviours in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, all the compounds exhibit low fluorescence and high phosphorescence quantum yields but the ratio is solvent dependent. These observations are consistent with the high photoreactivity of the molecules operating in the lowest excited triplet state which is nπ* in character. Photopolymerization rates of n-butyl methacrylate with N-diethylmethylamine co-initiator correlate with the absorption maxima and extinction coefficients of the thioxanthones and also the degree of quenching of their fluorescence by the amine, indicating the importance of electron transfer. In the absence of a tertiary amine, transient formation on micro-second flash photolysis in 2-propanol is associated with the ketyl radical formed by the lowest excited triplet state abstracting a hydrogen atom from the solvent. In the presence of a tertiary amine, both ketyl radical and radical anion (at longer wavelengths) are observed, the latter being formed via abstraction of an electron from the amine. This is confirmed by a flash photolysis study using amines of various ionization potentials where a correlation is observed with radical anion absorbance. A pH study confirms the identity of the transient species. Activation of the thioxanthone molecule in the 3 and 4 positions with a methyl group enhances initiator activity whereas substitution in the t-position deactivates the molecule through intra-molecular hydrogen atom abstraction.     

Quo vadis,chemometrics?

Assessing current trends in chemometric publications reveals that most projects utilize known methodologies and fall into the category “application.” There seems to be worrying little of true innovation unless one counts “fashions” assimilated from other fields. The field may have reached a crossroad: One path leads to chemometrics becoming a fully mature but stagnant tool for analytical chemists; the other path, that is, maintaining chemometrics as an active and widely recognized research field, requires opening new research areas for chemometricians. It is argued that hard modeling as opposed to the ubiquitous soft modeling may become such a new direction. Hard modeling would focus on investigating chemical mechanisms that give raise to measured data as opposed to empirically analyzing data.Furthermore, chemometricians in academia are responsible for preparing the next generation of chemometricians. Despite the need for chemometricians in the workforce, the number of young chemometricians is low and will remain low unless changes in chemistry curricula happen. This remains a challenge because there are fundamental issues that need to be overcome. Copyright © 2014 John Wiley & Sons, Ltd.     

Rapid monitoring of grapevine reserves using ATR–FT-IR and chemometrics

Predictions of grapevine yield and the management of sugar accumulation and secondary metabolite production during berry ripening may be improved by monitoring nitrogen and starch reserves in the perennial parts of the vine. The standard method for determining nitrogen concentration in plant tissue is by combustion analysis, while enzymatic hydrolysis followed by glucose quantification is commonly used for starch. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR–FT-IR) combined with chemometric modelling offers a rapid means for the determination of a range of analytes in powdered or ground samples. ATR–FT-IR offers significant advantages over combustion or enzymatic analysis of samples due to the simplicity of instrument operation, reproducibility and speed of data collection. In the present investigation, 1880 root and wood samples were collected from Shiraz, Semillon and Riesling vineyards in Australia and Germany. Nitrogen and starch concentrations were determined using standard analytical methods, and ATR–FT-IR spectra collected for each sample using a Bruker Alpha instrument. Samples were randomly assigned to either calibration or test data sets representing two thirds and one third of the samples respectively. Signal preprocessing included extended multiplicative scatter correction for water and carbon dioxide vapour, standard normal variate scaling with second derivative and variable selection prior to regression. Excellent predictive models for percent dry weight (DW) of nitrogen (range: 0.10–2.65% DW, median: 0.45% DW) and starch (range: 0.25–42.82% DW, median: 7.77% DW) using partial least squares (PLS) or support vector machine (SVM) analysis for linear and nonlinear regression respectively, were constructed and cross validated with low root mean square errors of prediction (RMSEP). Calibrations employing SVM-regression provided the optimum predictive models for nitrogen (R² = 0.98 and RMSEP = 0.07% DW) compared to PLS regression (R² = 0.97 and RMSEP = 0.08% DW). The best predictive models for starch was obtained using PLS regression (R² = 0.95 and RSMEP = 1.43% DW) compared to SVR (R² = 0.95; RMSEP = 1.56% DW). The RMSEP for both nitrogen and starch is below the reported seasonal flux for these analytes in Vitis vinifera. Nitrogen and starch concentrations in grapevine tissues can thus be accurately determined using ATR–FT-IR, providing a rapid method for monitoring vine reserve status under commercial grape production.     

Photochemistry of benzene and quinoxaline fused Δ-1,2,3-triazolines and their trapping products

The benzene and quinoxaline fused Δ²-1,2,3-triazolines 1a and 1b were synthesized in good yields using Knoevenagel condensation and intramolecular 1,3-dipolar cycloaddition as two of the key reactions. Photolysis (254 nm) of Δ²-1,2,3-triazoline 1a or 1b in acetonitrile led to the homolytic cleavage of nitrogen that generated diethyl diazomalonate 7, highly reactive intermediates aziridines 8a,b, and isoindoles B. The latter two species subsequently underwent rearrangement to give the nitrogen extrusion products 9a,b, and polymers. Furthermore, the reactive intermediates were trapped by dienophiles to give the corresponding cycloadducts. Subsequent rearrangement of the N-bridged cycloadducts gave N-substituted pyrrolo[3,4-b]quinoxalines 12b and 15b in 6% and 9% yields, respectively. Irradiation of 1a in the presence of fumaronitrile led to the isolation of cycloadduct 16a with retention of stereochemistry. Thermal reaction of 1b gave more nitrogen extruded product 9b (58-63% yield) than that by photolysis (5-23% yield), which implied that zwitterionic intermediate might be involved in the former.     

Solid State Photochemistry of Nitrobenzaldehydes

The photochemical reaction of nilrobenzaldehyde with indole and antipyrine was investigated in solid state.The structures of the new products were identified by means of IR,MS,'H NMR and elemental analysis,and the crystal structure of audition product 2c was determined by X-ray diffraction analysis.The mechanism of this reaction was also proposed.     

Metal–organic framework-based mixed-matrix membranes for gas separation: An overview

Mixed-matrix membranes (MMMs) have been studied widely in the field of gas separation due to their potential to overcome performance barriers found in traditional polymeric membranes. Most polymeric membranes exhibit a trade-off between permeation and selectivity, which has limited their development in many challenging separation applications. One solution to this issue utilizes the introduction of fillers into the polymer matrix to produce MMMs. Out of the many different fillers, metal–organic frameworks stand out as a promising candidate due to their highly tunable structure, molecular sieving effect, and superior compatibility with the polymer matrix. This review will provide an in-depth look into the basic mechanisms of MMMs for gas separation and different approaches to model the permeation of gases through the membrane. In addition, challenges facing the field and recent research trends for MMMs will be discussed as well as their many applications for different gas separations. Finally, some insight on the future direction for MMMs will be covered, focusing on many intriguing opportunities and challenges that must be further explored to advance this technology.     

Multiphase structure and physical properties of organic composites obtained by mechanochemical reaction between BEDT–TTF and iodine-derived acceptors. An overview

The results of the studies of the physical properties of organic composites obtained by direct solid–solid charge-transfer (CT) reaction between bis(ethylenedithio)tetrathiafulvalene (BEDT–TTF) and iodine or gold iodide are presented and discussed. It is shown that the analysis of experimental data of dc conductivity and thermoelectric power and the relation between morphology of composites and their electrical properties result in understanding the charge transport phenomena and allow to propose the model of electrical transport in these materials. The main factors that affect the electrical properties of composites are recognized and the ways of controlling these factors and tuning the electrical properties are proposed. To cite this article: A. Graja, M. Golub, C. R. Chimie 6 (2003).     

Determination of captopril in pharmaceutical preparation and biological fluids using two- and three-way chemometrics methods

Spectrophotometric method has been developed for the direct quantitative determination of captopril in pharmaceuticalpreparation and biological fluids(human plasma and urine)samples.The method was accomplished based on parallel factoranalysis(PARAFAC)and partial least squares(PLS).The study was carried out in the pH range from 2.0 to 12.8 and with aconcentration from 0.70 to 61.50 μg mL~(-1)of captopril.Multivariate calibration models such as PLS at various pH and PARAFACwere elaborated from ultraviolet spectra deconvolution and captopril determination.The best models for this system were obtainedwith PARAFAC and PLS at pH 2.0.The applications of the method for determination of real samples were evaluated by analysis ofcaptopril in pharmaceutical preparations and biological fluids with satisfactory results.The accuracy of the method,evaluatedthrough the RMSEP,was 0.5801 for captopril with best calibration curve by PARAFAC and 0.6168 for captopril with PLS at pH 2.0model.     

Biosurfactants—An Overview

The large structural and functional variety of bio-surfactants (BS), which are produced by microorganisms, leads to the use of several methods to study these amphiphilic molecules. This review seeks to consolidate information on various surface-active product extraction techniques, microbiological screening methodologies, and analytical terminologies utilized in this sector. The potential benefits and drawbacks of various approaches for studying cell biomass or microbial culture broth for the generation of surface-reactive chemicals are also discussed. Additionally, the most popular techniques for detection, structural characterization, and purification of a variety of BS are introduced. A number of straightforward techniques are described in detail, including dialysis, ion exchange, solvent extraction, ultrafiltration, lyophilization, and thin layer chromatography (TLC). In addition to more sophisticated techniques like nuclear magnetic resonance (NMR), fast atom bombardment mass spectroscopy (FAB-MS), gas chromatography-mass spectroscopy (GC-MS), high-pressure liquid chromatography (HPLC), and infrared (IR), proteolysis and sequencing of amino acid are also explained. In this field of study, it is quite necessary to combine several analytical techniques, and it often takes multiple iterations to purify, isolate, and characterize different surface-active substances. The numerous approaches that are essential for researching bio-surfactants are covered in this review.