Unified gas and supercritical fluid chromatography on 50 μm i.d. Columns

A unified approach to sequential gas and supercritical fluid Chromatography using 50 μm i.d. open tubular columns is described. Sample introduction is performed by means of a rotary injection valve. In order that linear velocities can be optimized independently, a second rotary valve in the chromatographic oven is used to direct the flow of column eluate to the flame ionization detector through either fused silica tubing in GC, or a frit restrictor in SFC. Applications of sequential GC-SFC on a 50 μm i.d. open tubular column are demonstrated, and comparisons made between sequential GC-SFC on 50 and 100 μm i.d. columns.     

Microfabrication of three-dimensional bioelectronic architectures

The functionality and structural diversity of biological macromolecules has motivated efforts to exploit proteins and DNA as templates for synthesis of electronic architectures. Although such materials offer promise for numerous applications in the fabrication of cellular interfaces, biosensors, and nanoelectronics, identification of techniques for positioning and ordering bioelectronic components into useful patterns capable of sophisticated function has presented a major challenge. Here, we describe the fabrication of electronic materials using biomolecular scaffolds that can be constructed with precisely defined topographies. In this approach, a tightly focused pulsed laser beam capable of promoting protein photo-cross-linking in specified femtoliter volume elements is scanned within a protein solution, creating biomolecular matrices that either remain in integral contact with a support surface or extend as free-standing structures through solution, tethered at their ends. Once fabricated, specific protein scaffolds can be selectively metallized via targeted deposition and growth of metal nanoparticles, yielding high-conductivity bioelectronic materials. This aqueous fabrication strategy opens new opportunities for creating electronic materials in chemically sensitive environments and may offer a general approach for creating microscopically defined inorganic landscapes.     

The analysis of lubricating oil additives by supercritical fluid chromatography with packed and open tubular capillary columns

Lubricating oil additives have been analyzed by supercritical fluid chromatography on open tubular and packed capillary columns. Carbon dioxide and modified carbon dioxide were used as mobile phases and detection was accomplished by flame ionization and micro UV. Rapid and efficient analysis of the lubricating oil additives was demonstrated.     

Glucuronide conjugates of Soraprazan (BY359), a new potassium-competitive acid blocker (P-CAB) for the treatment of acid-related diseases

Glucuronide conjugates of Soraprazan (BY359), a potent novel anti-secretory drug (currently in Phase II clinical trials), were not directly accessible synthetically. This was due to the relative instability of Soraprazan under the harsh Lewis acid conditions employed in popular glucuronidation methodologies and a lack of reactivity under alternative, Koenigs-Knorr, coupling conditions. We have now devised a successful synthesis using the novel N-acetylated Soraprazan to access the required glucuronide metabolites on gram scale. Coupling of this novel aglycone with methyl 1-O-trichloroacetimidoyl-2,3,5-tri-O-isobutyryl-α-d-glucopyran-uronate in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave the protected glucuronide intermediates. A one-pot two-step deprotection involving hydrolysis of the ester functionalities and removal of the N-acetyl group with alkaline hydrazine delivered the title compounds in satisfactory yield.     

Proof of the Fukui conjecture via resolution of singularities and related methods. II $$^{\star}$$

The present article is a direct continuation of the first part of this series. We reduce a proof of the Fukui conjecture (concerning the additivity problem of the zero-point vibrational energies of hydrocarbons) to that of a proposition related to the theory of algebraic curves, so that we can focus on the key mechanism of the additivity phenomena. Namely, by establishing what is called the Basic Piecewise Monotone Theorem (BPMT), we reduce a proof of the Fukui conjecture to that of a proposition, called the Local Analyticity Proposition, Version 1 (LAP1), which admits a proof via resolution of singularities. By LAP1, the essential part of the mechanism of the asymptotic linearity phenomena is extracted and is elucidated by using tools from the mathematical theory of algebraic curves, whose language is of vital importance in analyzing the crux of the additivity mechanism. Dedicated to the memory of Prof. Kenichi Fukui (1918–1998).     

Stepwise hydration and multibody deprotonation with steep negative temperature dependence in the benzene.+ -water system

We studied the stepwise hydration and solvent-mediated deprotonation of the benzene*+ cation (Bz*+) and found several unusual features. The solvent binding energies DeltaH on-1,n for the reactions Bz*+(H2O)n-1 + H2O --> Bz*+(H2O)n are nearly constant at 9 +/- 1 kcal mol-1 for n = 1 to 8. We observed a remarkable sudden decrease in the entropy of association accompanying the formation of Bz*+(H2O)7 and Bz*+(H2O)8, indicating strong orientational restraint in the hydration shells of these clusters consistent with the formation of cagelike structures. We observed the size-dependent deprotonation of Bz*+ in a cooperative multibody process, where n H2O molecules (n >/= 4) can remove a proton from Bz*+ to form protonated water clusters. We measured, for the first time, the temperature dependence of such a process and found a negative temperature coefficient of a magnitude unprecedented in any chemical reaction, of the form k = AT-67+/- 4, or in an Arrhenius form having an activation energy of -34 +/- 1 kcal mol-1. The temperature effect may be explained by Bz*+ and four H2O molecules needing to be assembled from gas-phase components to form the reactive species. Such large temperature effects may be therefore general in solvent cluster-mediated reactions.     

SCF-π-electron calculations using orthogonalised atomic orbitals

Modifications of the SCF-LCAO-π-MO method analysed in the previous paper are described in which provision is made for the incorporation of Variable Bond Order and Variable Electronegativity procedures. A comparison is made with the results of other π-electron calculations and values are reported for twenty hydrocarbon systems.     

Clays as selective catalysts in organic synthesis

Suitably modified smectite clays can be very selective catalysts for a wide range of organic reactions. While it has long been known that such materials can act as Bronsted and Lewis acids, it has been shown recently that they are also effective Diels-Alder catalysts. A selection of illustrative reactions is given which emphasises their wide range of use, their selectivity, and the ease of work-up after reaction. In each case, mechanistic information is presented, e.g., on the site of reaction (whether interlayer or surface), rate determining steps, etc. The regiochemical consequences of the restricted reaction space are stressed.Based on material presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Aggregation of iron colloids in estuaries: a heterogeneous kinetics study using continuous mixing of river and sea waters

The kinetics of iron colloid aggregation in estuaries have been simulated with a model estuary in which seawater is continuously pumped into a reservoir initially containing river water. Profiles of colloidal Fe concentration versus salinity produced in this apparatus closely resembled field data for actual estuaries. Synthetic Fe colloids prepared by peptising Fe(OH)₃ with humic acid and phosphate showed very similar kinetic behaviour. Aggregation rate was found to be almost independent of velocity shear rate, implying that most aggregations are induced by brownian interparticle collisions. A heterogeneous kinetic model is proposed to explain the kinetic behaviour of Fe colloids during seawater-induced aggregation. This model describes kinetic behaviour in terms of a log-normal distribution of rate constants characterised by a mean value k and a standard deviation γ. Experiments showed that k is linearly related to the rate constant for salinity increase during mixing. This coupling of salinity changes and aggregation rate leads to Fe-salinity profiles that are nearly independent of the rate of salinity change, but which are dependent on γ.     

Characterization of the oxidation products of styryl-substituted terthiophenes and sexithiophenes using electronic absorption spectroscopy and time-dependent DFT

The electronic absorption spectra of a series of alkoxy-styryl substituted terthiophenes, their corresponding sexithiophenes, and the oxidation products of both have been measured. The terthiophenes studied sigma-dimerize to sexithiophenes during the oxidation process and there is clear evidence of sexithiophene radical cations, dications, and pi-dimers in the electronic absorption spectra. The oxidation of concentrated solutions produces predominantly pi-dimer bands, as expected. The absorption spectrum of the styryl-functionalized sexithiophene dication without alkoxy substitution closely resembles that of unsubstituted sexithiophene, while alkoxy substitution induces changes in the wavelength of the dication band maximum and the overall band shape. Time-dependent density functional theory (TDDFT) calculations have shown that styryl-based molecular orbitals are important in the transitions of the neutral molecules as well as the charged species, the dication in particular. Kinetics analyses confirm the stabilization effect induced by the alkoxy substituents. The presence of a reversible pi-dimer equilibrium was verified by cyclic voltammetry. It is clear from the experimental observations and the theoretical calculations that both the styryl and alkoxy groups are influencing the electronic properties of this class of molecules.