Stellan Hjertén's contribution to the development of monolithic stationary phases

This overview is presented to celebrate the birthday of one of the luminaries of the separation science and my friend - Stellan Hjertén. He made significant contributions to a variety of areas in separation science such as electrophoresis, LC, and CEC to name just a few. Since the scope of his work was enormous, this review will focus only on a single aspect of his scientific activities, the design and applications of monolithic materials. During the years starting from 1989, Stellan Hjertén published many excellent papers concerning the preparation of acrylamide chemistry-based monoliths and their use in both micro-HPLC and CEC. The following text details his works in the field.     

The contribution of gas chromatography to the resynthesis of the post-Byzantine artist’s technique

Gas chromatographic analysis of ethyl chloroformate derivatives of samples taken from the paint layers of post-Byzantine panel paintings permitted the successful characterisation of the different binding media used in them. This paper describes an analytical study of various post-Byzantine binding media such as egg yolk and egg/oil emulsion, using gas chromatography. The characterisation of these icons’ binding media is an important task, as it contributes to our understanding of and the reconstruction of the post-Byzantine artists’ palette. It also enables us to investigate the validity of our assumptions about the influences of Venetian style on Greek icon painting techniques from the sixteenth to the early nineteenth century, which up to now have been based on information in artists’ handbooks. The methodology involves two experimental steps: (1) hydrolysis of the proteins and triglycerides in the binding media to obtain free amino acids and fatty acids, and (2) the formation of ethyl chloroformate derivatives via derivatization with ethyl chloroformate (ECF). This methodology is of considerable interest, since it permits the identifcation of the nature of the proteinaceous binders used in these works through the simultaneous derivatization and determination of amino acids and fatty acids. Advantages of this methodology include the small quantity of sample required and the minimum preparation time involved. The proteinaceous media can be determined based on the ratios of seven stable amino acids, while the type of emulsions and drying oils used can be determined from the fatty acid ratio. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Is the dynamical polarization a significant part of the contribution of the triples to the correlation energy?

One may call dynamical polarization of doubly excited configurations the energy lowering of these configurations under the response of the other electrons to the so-created fluctuation of the electric field. This contribution of triply excited configurations may be identified and calculated through a computation that only requires a computation time proportional to the sixth power of the number of molecular orbitals (MOs), instead of the seventh power for the total contribution of the triples. Its amplitude depends on the choice of the MOs and becomes important when localized MOs are used.     

Some questions on the exchange contribution to the effective potential of the Kohn–Sham theory

The current success of Density Functional Theory applications hinges upon the availability of explicitly density-dependent functionals to self-consistently solve a set of one-electron equations, the Kohn–Sham (KS) equations, which determine the occupied orbitals and its associated electronic density. In KS theory, a local exchange potential is proposed as part of an effective potential. This potential is compared to the exchange operator of the Hartree–Fock theory, which is of a non-local nature. The present paper discusses the variational framework of the KS equations, and the equivalence between both exchange potentials within a correlation-free theory. The common difficulties of current local exchange functionals to correctly simulate the non-locality of the exchange energy density in chemical systems are also analyzed and explained through an exactly solvable model. We give then numerical arguments and conclude by analyzing the performance of various commonly used approximations to exchange functionals.     

Csaba Horváth's contribution to the theory and practice of capillary electrochromatography

This overview has been written as a tribute to a luminary of chromatography--Csaba Gyula Horváth, who passed away earlier this year. Since the scope of his work was enormous, the following pages focus only on one single aspect of his scientific activities, capillary electrochromatography. He was a visionary, recognizing the great potential of this method and devoted a large part of his efforts to studies of problems related to CEC, covering a huge variety of issues embracing the theoretical foundation, instrumentation, and column technology. During the period of time from 1996 to 2004, Csaba Horváth published almost 30 excellent papers concerning capillary electrochromatography, which are reviewed in this article.     

The nuclear magnetic shielding constants of formamide: the contribution of the non-tightly bound water molecules of the “first hydration shell”

The magnetic shielding constants of the nuclei of formamide are calculated for the isolated molecule, the molecule surrounded by its “first hydration shell” obtained from a Monte Carlo treatment, and the molecule surrounded only by the four water molecules engaged in the short solute—solvent hydrogen bonds. The results show that the six “remote” waters produce important chemical shift variations which in the case of the NH protons, are qualitatively determining. They are due mainly to a variation of the polarization of the wavefunction of the solute.     

From 2011 to 2022: The development of pyrazole derivatives through the α,β-unsaturated carbonyl compounds

The synthesis of pyrazole derivative using α,β-unsaturated carbonyl compounds has attracted increasing attention of the synthetic organic chemist community. Interestingly, the simplicity of the synthetic method, high reactivity, and ease of incorporating diversity into the desired prototype have contributed a lot toward the exploration of α,β-unsaturated carbonyl compounds by various research groups. Due to the tremendous pharmacological significance of pyrazole derivatives, their synthesis has been one of the leading research frontiers in recent years. As prime examples, sildenafil, zometapin, Celebrex, and rimonabant have been successfully commercialized in the market to treat various life-challenging diseases. Considering the great profile of α,β-unsaturated carbonyl compound in the synthesis of biologically active pyrazole derivatives, this review incorporates contemporary literature (2011–2022) on the synthesis of pyrazole and its derivatives using α,β-unsaturated carbonyl compound as a starting precursor.     

The development of problems within the phlogiston theories, 1766–1791

This is the first of a pair of papers. It focuses on the development of the most notable phlogistic theories during the period 1766–1791, including the main experiments that their proponents proposed them to interpret. There was a rapid proliferation of late phlogistic theories, particularly from 1784, and the accounts of composition and important implications of the main theories are set out and their issues analysed. Each of them either reached impasses due to internal problems, or included features that made them unacceptable even to other phlogistians. The expositions and analyses of these theories are given in terms of details that were in the literature at the time or otherwise potentially understandable by the participants given contemporary practice. Some relevant methodological aspects of the history of science are discussed, and the secondary literature is briefly surveyed. The second paper deals with the contemporary development of the new chemistry, and with theory comparison and theory choice in the same period.     

Application of the avidin–biotin interaction to immobilize DNA in the development of electrochemical impedance genosensors

Impedance spectroscopy is a rapidly developing technique for the transduction of biosensing events at the surface of an electrode. The immobilization of biomaterial as DNA strands on the electrode surface alters the capacitance and the interfacial electron transfer resistance of the conductive electrodes. The impedimetric technique is an effective method of probing modifications to these interfacial properties, thus allowing the differentiation of hybridization events. In this work, an avidin bulk-modified graphite–epoxy biocomposite (Av-GEB) was employed to immobilize biotinylated oligonucleotides as well as double-stranded DNA onto the electrode surface. Impedance spectra were recorded to detect the change in the interfacial electron transfer resistance (R _et) of the redox marker ferrocyanide/ferricyanide at a polarization potential of +0.17 V. The sensitivity of the technique and the good reproducibility of the results obtained with it confirm the validity of this method based on a universal affinity biocomposite platform coupled with the impedimetric technique.     

The tightness contribution to the Brønsted alpha for hydride transfer between NAD+ analogues

It has been shown that the rate of symmetrical hydride transfer reaction varies with the hydride affinity of the (identical) donor and acceptor. In that case, Marcus theory of atom and group transfer predicts that the Br?nsted alpha depends on the location of the substituent, whether it is in the donor or the acceptor, and the tightness of the critical configuration, as well as the resemblance of the critical configuration to reactants or products. This prediction has now been confirmed for hydride transfer reactions between heterocyclic, nitrogen-containing cations, which can be regarded as analogues of the enzyme cofactor, nicotinamide adenine dinucleotide (NAD+). A series of reactions with substituents in the donor gives Br?nsted alpha of 0.67 +/- 0.03 and a tightness parameter, tau, of 0.64 +/- 0.06. With substituents in the acceptor alpha = 0.32 +/- 0.03 and tau = 0.68 +/- 0.08. The reactions are all spontaneous, with equilibrium constants between 0.4 and 3 x 10(4), and the two sets span about the same range of equilibrium constants. The two tau values are essentially identical with an average value of 0.66 +/- 0.05. These results can be semiquantitatively mimicked by rate constants calculated for a linear, triatomic model of the reaction. Variational transition state theory and a physically motivated but empirically calibrated potential function were used. The computed rate constants generate an alpha value of 0.56 if the hydride affinity of the acceptor is varied and an alpha of 0.44 if the hydride affinity of the donor is varied. The calculated kinetic isotope effects are similar to the measured values. A previous error in the Born charging term of the potential function has been corrected. Marcus theory can be successfully fitted to both the experimental and computed rate constants, and appears to be the most compact way to express and compare them. The success of the linear triatomic model in qualitatively reproducing these results encourages the continued use of this easily conceptualized model to think about group, ion, and atom transfer reactions.     

The Effect of Sulfate Ion on the Isomerization of n-Butane to iso-Butane

The effect of sulfate ion (SO42-) loading on the properties of Pt/SO42- -ZrO2 and on the catalytic isomerization of n-butane to iso-butane was studied. The catalyst was prepared by impregnation of Zr(OH)4 with H2SO4 and platinum solution followed by calcination at 600℃. Ammonia TPD and FT-IR were used to confirm the distribution of acid sites and the structure of the sulfate species. Nitrogen physisorption and X-ray diffraction were used to confirm the physical structures of Pt/SO42--ZrO2. XRD pattern showed that the presence of sulfate ion stabilized the metastable tetragonal phase of zirconia and hindered the transition of amorphous phase to monoclinic phase of zirconia. Ammonia TPD profiles indicated the distributions of weak and medium acid sites observed on 0.1 N and 1.0 N sulfate in the loaded catalysts. The addition of 2.0 N and 4.0 N sulfate ion generated strong acid site and decreased the weak and medium acid sites. However, the XRD results and the specific surface area of the catalysts indicated that the excessive amount of sulfate ion collapsed the structure of the catalyst. The catalysts showed high activity and stability for isomerization of n-butane to iso-butane at 200℃under hydrogen atmosphere. The conversion of n-butane to iso-butane per specific surface area of the catalyst increased with the increasing amount of sulfate ion owing to the existence of the bidentate sulfate and/or polynucleic sulfate species ((ZrO)2SO2), which acts as an active site for the isomerization.     

The Application of the Trichloroacetimidate Method to the Synthesis of α-D-Gluco- and α-D-Galactopyranosides

Abstract

The trichloroacetimidate method has been applied to the construction of α-d-galacto- and α-d-glucopyranosides. The readily available β-trichloroacetimidates of 2,3,4,6-tetra-O-benzyl-d-galacto- and glucopyranose (1-β and 3-β, respectively) have been employed in glycosidations with several monosaccharides (either A, B, C or D) under varying experimental conditions. With the galactose derivative 1-β as a donor and each of the monosaccharides A-D as acceptors, the corresponding disaccharides 1A-1D, were obtained in high yield and with good α-stereoselectivity when employing diethyl ether as solvent and either trimethylsilyl- or tert-butyldimethylsilyl trifluoro-methane sulphonate as catalyst. Glycosidations with the glucose derivative 3-β, as donor, and with the monosaccharide acceptors A, B or D, gave the corresponding disaccharides 3A, 3B and 3D, in high yield but with somewhat lower α-diastereoselectivity than observed with the galactose derivative 1-β. The stereochemical outcome of the reactions is rationalised in terms of possible reaction mechanisms.     

401 — The development of bienzyme glucose electrodes

Amperometric glucose electrodes are constructed on the basis of glucose oxidase and peroxidase. The first two types of electrodes employ a Pt or glassy carbon electrode and a bienzyme membrane. In the third type of electrode peroxidase was adsorbed on the organic metal electrode and the electrode obtained was covered with a glucose oxidase membrane. In the first two types of devices the electron exchange between the peroxidase-active center and the electrode is carried out by potassium ferrocyanide.The electrodes possess a linear dependence of the stationary current on the glucose concentration in the range of 0.01–1 mM. The stationary current is attained in 2–4 min. The sensitivity of the first and second types of electrodes shows little dependence in the potential ranging from 0.1 to 0.3 V (vs. saturated Ag⋎AgCl) and from 0.3 to −0.1 V respectively. The lowest sensitivity of the electrode based on organic metal is displayed at 0.1 V; the potential increase (up to 0.2 V) orthe decrease (to −0.1 V) leads to negligible sensitivity rise.The electrodes (types I and II) retain their activity for more than 100 days, whereas the third type for 4–6 days only. These electrodes possess a high selectivity, showing no response to the ascorbic acid and other electrode-active compounds present in blood plasma.