Chromatography in silico,basic concept in reversed-phase liquid chromatography

Basic phenomena in reversed-phase liquid chromatography have been quantitatively analyzed using a computational chemical calculation. Pyridine interacted with an ionized silica surface under neutral conditions. Alkyl-chain length affected the contact surface area with an analyte. Steric hindrance was demonstrated using a model graphitic carbon phase and unsaturated alkenes. Quantitative structure–retention relationships in reversed-phase liquid chromatography were demonstrated for phenolic compounds and acidic and basic drugs. The correlations between predicted and measured retention factors were satisfactory. Dissociation constants were derived from the atom partial charge and used to predict retention factors of partially ionized compounds.     

Polymerization of propylene with TiCl3–AlEt2Cl–polymeric electron donor catalyst

Polymeric donors having ether or carbonyl groups were added to the TiCI₃–AlEt₂CI catalyst system as the third component, and the effects on the polymerization of propylene were investigated in comparison with the effect of the electron donors with low molecular weight. The polymeric donors were effective in making the catalyst more active, but the donors of low molecular weight depressed the catalyst activity. In the case of poly(propylene glycol dimethyl ether) (PPG-DME), PPG–DME with a number of propylene oxide units (n) of more than 6.7 was effective in enhancing the catalyst activity. These effects were considered to be due to the different reactivities between TiCI₃ and AlEt₂CI-polymeric donor complexes having various chain lengths.     

Membrane disordering induced by chloroform and carbon tetrachloride

We studied effects of chloroform and carbon tetrachloride on bilayer membranes of dimyristoyl-phosphatidylcholine (DMPC) and egg yolk phosphatidylcholine (Egg-PC) by birefringence, dynamic light scattering and fluorescence methods. It is shown that interference light due to the membrane birefringence considerably decreases by addition of the organohalogen compounds for both lipid membranes, indicating a significant decrease in membrane order. In addition, results of dynamic light scattering and turbidity measurements show a rupture of multilamellar DMPC vesicles induced by addition of chloroform at concentrations above 0.2 v/v%. No rupture of the vesicles is observed within the limit of solubility of carbon tetrachloride in water, but excessive addition of carbon tetrachloride (above 0.2 v/v%) induces the vesicle rupture. Chain orientational order was estimated from the interference light intensity at low concentrations of the organohalogen compounds without the occurrence of the vesicle rupture. The estimation shows a monotonic decrease in the chain order with increasing the concentration. The decreases in DMPC chain order by chloroform and by carbon tetrachloride are about 17% at 0.2 v/v% and 23% at 0.05 v/v%, respectively. The reduction in the chain order is correlated with an increase in the membrane fluidity observed by excimer fluorescence of pyrene incorporated to the membrane. Behavior of membrane disordering of Egg-PC is approximately similar with that of DMPC. This implies the strong interaction between the organohalogen compounds and the lipid chains, whether or not the bilayer has the vacancy resulted from unsaturated double bonds and different chains in length. The results of this work suggest that damages of biological membranes by chloroform and tetrachloride are not only induced by a direct attack on proteins but also by a significant membrane disorder.     

Purification and characterization of carbohydrate-binding peptides from Lotus tetragonolobus and Ulex europeus seed lectins using affinity chromatography.

Carbohydrate-binding peptides of several anti-H(O) leguminous lectins were obtained from endoproteinase Asp-N or Lys-C digests of L-fucose-binding Lotus tetragonolobus lectin (LTA) and Ulex europeus lectin I (UEA-I) and from that of a di-N-acetylchitobiose-binding Ulex europeus lectin II (UEA-II) by affinity chromatography on columns of Fuc-Gel (for LTA and UEA-I) and on a column of a mixture of several oligomers of N-acetyl-D-glucosamine (GlcNAc) coupled to Sepharose 4B (GlcNAc oligomer-Sepharose 4B) (for UEA-II). These peptides were retained on the Fuc-Gel or GlcNAc oligomer-Sepharose 4B column and were presumed to have an affinity for the columns. The amino acid sequences of the retarded peptides were determined using a protein sequencer.     

Asymmetric allylsilane-mediated carbocyclization: A highly enantiospecific synthesis of (1S, 2S)-(+)-2-methyl-3-cyclopenten-1-ol

An enantiospecific synthesis of the title compound is described which involves the TiCl₄-promoted cyclization of the chiral allylic silane having formyl group, which was obtained via the Claisen rearrangement of ($\text{R}$, $\text{E}$)-1-trimethylsilyl-1-buten-3-ol.     

Totally synthetic steroid heterocycles. Part 7.. A facile approach to 16-oxa-D-homoestrogens

In search of biologically active modified steroids, novel 16-oxa-D-homoestrone and -D-homoestradiol 3-methyl ethers were synthesized from 16-oxa-3-methoxy- D -homoestra-1,3,5(10),8,14-pentaen-17a-one. The straightforward synthesis involved stereoselective two-step reduction of the 8,14-diene system. The B/C stereoisomers were also derived from the estrapentaene. The stereostructures of these heterocyclic estrogens were determined on the basis of their spectral data.     

Computational chemical analysis of the retention of acidic drugs on a pentyl-bonded silica gel in reversed-phase liquid chromatography

A fast method to obtain a quantitative structure-retention relationship is required in chromatography for the rapid optimization of chromatographic separation conditions. Chromatographic data of acidic drugs are analyzed by a computational chemical method to simulate chromatographic simulation. The direct interaction between a model phase and a drug is calculated as an energy value using the molecular mechanics calculation of CAChe. Computational chemistry using a model adsorbent is a new method for quantitative analysis of retention in reversed-phase liquid chromatography. The correlation coefficient is 0.878 (n = 19) between the retention factors of acidic drugs and interaction energy values of the final structure (DeltaFS) between an acidic drug and model pentyl-bonded phase.     

Study of the degradation of polyurethane—Part 5: Photo-decomposition of ethyl N-phenylcarbamate, methylene bis (ethyl N-phenylcarbamate) and polyurethane in solution

In order to elucidate the photo-decomposition mechanism of polyurethane based on polyester diol-diphenylmethane-p,p′-diisocyanate, the effects of triplet quenchers, piperylene and oxygen on the photo-decomposition of the polymer, methylene bis (ethyl N-phenylcarbamate) (MEPC) and ethyl N-phenylcarbamate (EPC) were examined in solution. Energy levels and lifetimes of the excited states of these compounds were also determined.Piperylene and oxygen did not affect the photo-decomposition of the samples examined. The results imply that the photo-decomposition of the polymer starts from the excited singlet state. The energy levels and lifetimes for the photo-decomposition of the polymer were as follows: the excited singlet state (S₁): 98·6 kcal/mol (3·2 nsec): the excited triplet state (T₁): 76·7 kcal/mole (2·9 sec).     

Metal ion-catalyzed Diels-Alder and hydride transfer reactions. Catalysis of metal ions in the electron-transfer step

Rates of Diels-Alder cycloaddition of anthracenes with p-benzoquinone and its derivatives as well as rates of hydride-transfer reactions from 10-methyl-9,10-dihydroacridine to the same series of p-benzoquinones are accelerated significantly in the presence of metal ions in acetonitrile. An extensive comparison of the catalytic effects of metal ions in electron transfer from one-electron reductants (cobalt tetraphenylporphyrin and decamethylferrocene) to p-benzoquinones with those in the Diels-Alder reactions of the quinones as well as the hydride-transfer reactions has revealed that the catalysis of metal ions in each case is ascribed to the 1:1 and 1:2 complexes formed between the corresponding semiquinone radical anions and metal ions. The transient absorption and ESR spectra of the semiquinone radical anion-metal ion complexes are detected directly in the electron-transfer reduction of p-benzoquinone derivatives in the presence of metal ions. The catalytic reactivities of a variety of metal ions in each reaction are well correlated with the energy splitting values of pi(g) levels because of the complex formation between O(2)(.-) and M(n+), which are derived from the g(zz) values of the ESR spectra of the O(2)(.-)-M(n+) complex.     

Chemiluminescence of NS radical produced by the reaction of active nitrogen with sulfur vapor and sulfur chloride

Kinetics of NS (B² Π → X²Π) emission produced by the reaction of active nitrogen with sulfur vapor or sulfur chloride (S₂Cl₂) has been studied as a function of the total pressure and of the concentrations of atomic nitrogen and sulfur. The B ²Π state of NS is selectively formed by the three-body recombination reaction of N ans S atoms, N(⁴S) + S(³P) + M →. NS(B ²Π) + M. The highest vibrational level of the B ²Π state observed is ν′ = 12, which gives a lower bound for the dissociation energy of 4.93 eV.