Synthesis of biodegradable amphiphilic AB‐type diblock copolymers of lactide and depsipeptide with pendant reactive groups

The syntheses of amphiphilic AB‐type diblock copolymers composed of hydrophobic polylactide segment and hydrophilic polydepsipeptide segment with amino or carboxyl groups were performed. The protected cyclodepsipeptides cyclo[Glc‐Lys(Z)] and cyclo[Glc‐Asp(OBzl)] (where Glc is glycolic acid, Lys is lysine, Asp is aspartic acid, Z is benzyloxycarbonyl, and OBzl is benzyl) were first polymerized in tetrahydrofuran (THF) with potassium ethoxide as an initiator to obtain the corresponding protected polydepsipeptides. After the terminal hydroxyl groups of the protected polydepsipeptides were converted into the potassium alcoholates with K/naphthalene, L ‐lactide was polymerized in the presence of the corresponding polymeric alcoholates as macroinitiators in THF to obtain poly[Glc‐Lys(Z)]‐block‐poly(L ‐lactide) and poly[Glc‐Asp(OBzl)]‐block‐poly(L ‐lactide). Subsequent deprotection of Z and OBzl groups gave the objective amphiphiles poly(Glc‐Lys)‐block‐poly(L ‐lactide) and poly(Glc‐Asp)‐block‐poly(L ‐lactide), respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1218–1225, 2002     

New approach to the first-order phase transition of Lennard-Jones fluids

The multicanonical Monte Carlo method is applied to a bulk Lennard-Jones fluid system to investigate the liquid-solid phase transition. We take the example of a system of 108 argon particles. The multicanonical weight factor we determined turned out to be reliable for the energy range between -7.0 and -4.0 kJ/mol, which corresponds to the temperature range between 60 and 250 K. The expectation values of the thermodynamic quantities obtained from the multicanonical production run by the reweighting techniques exhibit the characteristics of first-order phase transitions between liquid and solid states around 150 K. The present study reveals that the multicanonical algorithm is particularly suitable for analyzing the transition state of the first-order phase transition in detail.     

Vinyl polymerization. 364. Polymerization of methyl methacrylate initiated with benzaldehyde

Benzaldehyde (PhCHO) is found to be able to initiate the radical polymerization of methyl methacrylate (MMA). The rate of polymerization is expressed by the following equation: R_p = const[PhCHO]^0.5[MMA]^1.5. The overall activation energy is estimated to be 56.3 kJ mole^?1. The mechanism of polymerization is discussed.     

Accumulated detection of ethidium bromide using a UV-irradiated DNA film modified electrode and its application for electrochemical detection of an environmental pollutant

In this study, DNA was first fabricated on a glassy carbon electrode by UV-irradiation. Through this process, water-soluble DNA was converted into insoluble materials, and a stable DNA film formed on the electrode. Ethidium bromide (EtBr), a typical model substance for harmful chemicals having planer structure, was used as an electroactive intercalator. This allowed our group to investigate the electrochemical and accumulative behaviors of the intercalator in UV-irradiated DNA film on the electrode. The UV-irradiated, DNA film-modified electrode (UV-DNA-FE) made it possible to accumulate electroactive EtBr on the electrode and detect it after accumulation. The modified electrode was used to detect dibenzofuran (DBF) as an environmental pollutant. The measurements were successfully obtained by focusing on the variation of the electrode response of EtBr, based on the competitive reaction between EtBr and DBF for the intercalating sites of DNA. The results indicated the possibility of using UV-DNA film as a sensing mechanism.     

Encapsulation and/or release behavior of bovine serum albumin within and from polylactide-grafted dextran microspheres

Polylactide (PLA)-grafted dextran (Dex-graft-PLA) of various contents of sugar units was synthesized by anionic polymerization of L-lactide (L-LA) using the alkoxide of partially trimethylsilylated dextran (TMSDex) and subsequently removing the trimethylsilyl (TMS) groups. The copolymer showed different solubility from L-LA homopolymer with increasing the content of sugar units. We prepared bovine serum albumin (BSA)-loaded microspheres (MS)s according to a water-in-oil-in-water emulsion-solvent evaporation/extraction method using methylene chloride/DMSO as an organic cosolvent. MSs prepared from Dex-graft-PLA [MS(Dex-graft-PLA)s] exhibited higher loading efficiency of BSA than MSs prepared from PLLA [MS(PLLA)s]. The in vitro release rate of BSA from MS(Dex-graft-PLA) was faster than that from MS(PLLA). BSA released from MS(Dex-graft-PLA) maintained the secondary structure of native BSA to a great extent, compared with BSA released from MS(PLLA).     

Conductance Study of 1 : 1 19-Crown-6 Complexes with Various Mono- and Bivalent Metal Ions in Water

Formation constants (ML) of 1 : 1 19-crown-6 (19C6) complexes with mono- (M+) and bivalent metal ions (M2+) were determined in water at 25 °C by conductometry. The KML value of 19C6 for M+ and M2+ decreases in the order Rb+ K+ > Tl+ > Na+ = Ag+ > Li+ Cs+ and Pb2+ > Ba2+ > Sr2+ > Cd2+ > Ca2+, respectively. The selectivity for the neighboring alkali metal ions in the periodic table is lower for 19C6 than for 18-crown-6 (18C6) except for the case of Rb+ and Cs+. The same is true for the alkaline earth metal ions. Generally, the KML values of 19C6 with M2+ are greater than those with M+. For Na+ and the ions which are smaller in size than Na+ (Li+, Ca2+, Cd2+), the KML value is larger for 19C6 than for 18C6, but the contrary holds for all the other ions of larger sizes than Na+. The limiting ionic molar conductivity (°) of the 19C6–K+ complex in water at 25 °C was determined to be 43. Although 19C6 is larger than 18C6, the 19C6–K+ complex is much more mobile in water than the 18C6–K+ complex.     

The high throughput analysis of N-methyl carbamate pesticides in fruits and vegetables by liquid chromatography electrospray ionization tandem mass spectrometry using a short column

We developed a new analysis method for the nine N-methyl carbamate pesticides in fruits and vegetables using ESI LC/MS/MS with direct sample injection into a short column. After extraction of the pesticides with ethyl acetate from sample, the extract is evaporated to dryness and redissolved in ultra pure water before injection into LC/MS/MS. The method needs no cleanup steps. The average recoveries from fruits and vegetables fortified at the level of 0.01 μg/g ranged from 56.0 to 119.1% with the coefficients of variation ranging from 0.2 to 7.6% for intra-day (n = 5 × 3 days) and from 0.8 to 18.4% for inter-day (n = 15). At the fortified level of 0.5 μg/g, the recoveries ranged from 67.7 to 119.3% with the coefficients of variation ranging from 0.5 to 7.8% for intra-day (n = 5 × 3 days) and from 0.9 to 14.8% for inter-day (n = 15). The method is considered to be satisfactory for the monitoring of the carbamate pesticide residues in fruits and vegetables, suggesting that the present method is applicable to other pesticide residues in foods.     

Synthesis and characterization of trimetallic complexes with a borazine core

Treatment of [Cp*Ru(dppe)]⁺ with B-triethynyl-N-trimethylborazine and piperidine produces the trimetallic complex [Cp*Ru(dppe)(CC)]₃B₃N₃Me₃, the structure of which has been confirmed by X-ray diffraction. Reaction of RuHCl(CO)(PPh₃)₃ with B-triethynyl-N-trimethylborazine produces the trimetallic complex [RuCl(CO)(PPh₃)₂(CH=CH)]₃B₃N₃Me₃.     

Syntheses of 3-acetoacetylaminobenzo[b]furan derivatives having cysteinyl leukotriene 2 receptor antagonistic activity

Novel 3-acetoacetylaminobenzo[b]furan derivatives having a modified triene system at the 3-position were synthesized starting with 3-aminobenzo[b]furans. The enol isomers, 3-[(3-hydroxybut-2-enonyl)amino]benzo[b]furans (), of the 3-acetoacetylaminobenzo[b]furans were obtained as stable isomers owing to formation of a hydrogen bonding between the enol hydroxyl group and the amidocarbonyl group. The planarity of the C-2 substituent through the C-3 side chain suggested the existence of a modified conjugational triene system in the enol compound. Cysteinyl leukotriene 1 and 2 receptor antagonistic activities for these compounds were evaluated. 2-(4-Cyanobenzoyl or ethoxycarbonyl)-3-[(2-cyano-3-hydroxybut-2-enonyl)amino]benzo[b]furans (, ) were moderately active.     

A novel quantum mechanical/molecular mechanical approach to the free energy calculation for isomerization of glycine in aqueous solution

The free energy change associated with the isomerization reaction of glycine in water solution has been studied by a hybrid quantum mechanical/molecular mechanical (QM/MM) approach combined with the theory of energy representation (QM/MM-ER) recently developed. The solvation free energies for both neutral and zwitterionic form of glycine have been determined by means of the QM/MM-ER simulation. The contributions of the electronic polarization and the fluctuation of the QM solute to the solvation free energy have been investigated. It has been found that the contribution of the density fluctuation of the zwitterionic solute is estimated as -4.2 kcal/mol in the total solvation free energy of -46.1 kcal/mol, while that of the neutral form is computed as -3.0 kcal/mol in the solvation free energy of -15.6 kcal/mol. The resultant free energy change associated with the isomerization of glycine in water has been obtained as -7.8 kcal/mol, in excellent agreement with the experimental data of -7.3 or -7.7 kcal/mol, implying the accuracy of the QM/MM-ER approach. The results have also been compared with those computed by other methodologies such as the polarizable continuum model and the classical molecular simulation. The efficiency and advantage of the QM/MM-ER method has been discussed.