Comparative analysis of blue‐shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes

Methyl radical complexes H₃C…HCN and H₃C…HNC have been investigated at the UMP2(full)/aug‐cc‐pVTZ level to elucidate the nature of hydrogen bonds. To better understand the intermolecular H‐bond interactions, topological analysis of electron density at bond critical points (BCP) is executed using Bader's atoms‐in‐molecules (AIM) theory. Natural bond orbital (NBO) analysis has also been performed to study the orbital interactions and change of hybridization. Theoretical calculations show that there is no essential difference between the blue‐shift H‐bond and the conventional one. In H₃C…HNC complex, rehybridization is responsible for shortening of the N? H bond. The hyperconjugative interaction between the single electron of the methyl radical and N? H antibonding orbital is up to 7.0 kcal/mol, exceeding 3.0 kcal/mol, the upper limit of hyperconjugative n(Y)→σ*(X–H) interaction to form the blue‐shifted H‐bond according to Alabugin's theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Role of the special pair in the charge-separating event in photosynthesis

We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis.     

Allylic Peroxidations with Bis(2‐pyridylimino)isoindolato‐Cobalt and ‐Iron Complexes

Several novel substituted bis(2‐pyridylimino)isoindolato (BPI) cobalt(II) and iron(II) complexes [M(BPI)(OAc)(H₂O)] (M = Co: 1 ‐ 6, Fe: 7) have been synthesized by reaction of bis(2‐pyridylimino)isoindole derivatives with the corresponding metal(II) acetates. Reaction of 1‐6 with 1.5 ‐ 2 molar equivalents of t‐BuOOH gave the corresponding alkylperoxocobalt(III) complexes [Co(BPI)(OAc)(OOtBu)] (10 ‐ 15). Using an aqueous solution of t‐BuOOH (70 %), cyclohexene was selectively catalytically oxidized to the dialkylperoxide cyclohex‐2‐ene‐1‐t‐butylperoxide.     

Characteristics of Subtractive Anodic Stripping Voltammetry of Lead,Cadmium and Thallium at Silver‐Gold Alloy Electrodes

Silver‐gold alloy electrodes have been studied for the purpose of the quantitative determination of heavy metals by subtractive anodic stripping voltammetry, (SASV). The results have been compared with those obtained with the silver and gold electrodes. The 50/50 a/o Ag/Au alloy electrode is the most suitable for quantifying thallium in the presence of lead and cadmium. The separation of its peak from those of lead and cadmium is 200 mV, which is about twice the separation obtained on the pure metal electrodes and is also better than on mercury. The silver electrode is suitable for the simultaneous determination of thallium, lead and cadmium. The peaks of lead and cadmium overlap on the 50/50 alloy. Pure silver or pure gold can be used for simultaneous quantification of these two metals. The use of gold for quantifying lead and cadmium is more limited because the peak potential of cadmium is shifted in the negative direction as its concentration increases and at [Cd²⁺]>200 nM, the two peaks merge. SASV enables correction for background currents and is of utmost importance for obtaining well‐defined peaks. The peaks of lead, cadmium and thallium appear over a relatively narrow potential range (ca. 200 mV) on all the electrodes presented in this work. For this reason, the quantifying of a peak is based on the derivative at the inflection point of only one of its branches (ascending or descending). All SASV measurements were carried out without removal of oxygen.     

Studies on the Synthesis and Properties of Temperature Responsive and Biodegradable Hydrogels

Novel linear poly(NIPA‐co‐CL) copolymers have been synthesized by radical copolymerization of N‐isopropylacrylamide (NIPA) and 2‐methylene‐1,3‐dioxepane (MDO). The structure of copolymers was confirmed by ¹H NMR and IR spectroscopy. Cross‐linked poly(NIPA‐co‐CL) hydrogels have also been prepared in toluene using N,N′‐methylenebisacrylamide as cross‐linking agent. The hydrogels thus obtained exhibit good temperature response and are biodegradable in the presence of proteinase K.

Temperature influence on the enzymatic degradation by proteinase K of poly(NIPA‐co‐CL) hydrogel (G‐60).     

Theoretical investigation of electron transfer transition in tetracyanoethylene-contained organic complexes

In this work, the authors use complete active space self-consistent field method to investigate the photoinduced charge-separated states and the electron transfer transition in complexes ethylene-tetracyanoethylene and tetramethylethylene-tetracyanoethylene. Geometries of isolated tetracyanoethylene, ethylene, and tetramethylethylene have been optimized. The ground state and the low-lying excited states of ethylene and tetracyanoethylene have been optimized. The state energies in the gas phase have been obtained and compared with the experimentally observed values. The torsion barrier of tetracyanoethylene has been investigated through the state energy calculation at different conformations. Attention has been particularly paid to the charge-separated states and the electron transfer transition of complexes. The stacked conformations of the donor-acceptor complexes have been chosen for the optimization of the ground and low-lying excited states. Equilibrium solvation has been considered by means of conductor-like screening model both in water and in dichloromethane. It has been found that the donor and tetracyanoethylene remain neutral in complexes in ground state (1)A(1) and in lowest triplet state (3)B(1), but charge separation appears in excited singlet state (1)B(1). Through the correction of nonequilibrium solvation energy based on the spherical cavity approximation, pi-->pi* electron transfer transition energies have been obtained. Compared with the experimental measurements in dichloromethane, the theoretical results in the same solvent are found higher by about 0.5 eV.     

Three New Neolignans from the Aril of Myristica fragrans

Three new neolignans, named 1‐deoxycarinatone ( 1 ), isodihydrocarinatidin ( 2 ), and isolicarin A ( 3 ), together with the known neolignan (+)‐dehydrodiisoeugenol ( 4 ), were isolated from mace (the aril of Myristica fragrans Houtt .). Their structures were elucidated as 2‐[(1S)‐2‐(4‐hydroxy‐3‐methoxyphenyl)‐1‐methylethyl]‐6‐methoxy‐4‐(prop‐2‐enyl)phenol ( 1 ), 4‐[(2R,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐(prop‐2‐enyl)benzofuran‐2‐yl]‐2‐methoxyphenol ( 2 ), and 4‐{(2S,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐[(1E)‐prop‐1‐enyl]benzofuran‐2‐yl}‐2‐methoxyphenol ( 3 ) on the basis of spectroscopic data.     

Oxidative Methyl Esterification of Primary Alcohols with Iodine‐Mediated Poly[4‐(Diacetoxyiodo)Styrene]

An operationally simple oxidative methyl esterification of primary alcohols in good yields using an iodine‐mediated poly[4‐(diacetoxyiodo)styrene] in methanol at room temperature is described. The polymeric reagent can be regenerated and reused as an environmentally benign reagent.     

Synthesis of well‐designed polymers carrying saccharide moieties via RAFT miniemulsion polymerization

Two hydrophobic vinyl saccharide monomers based on D ‐glucose and D ‐fructose were polymerized by employing the reversible addition‐fragmentation transfer (RAFT) miniemulsion polymerization technique to prepare well‐designed glycopolymers. Three dithiobenzoate‐RAFT agents [S?C(Ph)S? R], 1‐phenylethyl dithiobenzoate (PED), 2‐phenylprop‐2‐yl dithiobenzoate (PPD), and 2‐cyanoprop‐2‐yl dithiobenzoate (CPD), were used to control the growth of polymer chains. The best results were obtained in the presence of the PPD‐RAFT agent and the formed polymers have polydispersity index's (PDI) lower than 1.15. Under adequate miniemulsion polymerization conditions, a glycopolymer with PDI of 1.1 and molecular weight of 5 × 10⁴ g/mol has been successfully synthesized in a short reaction time of 100 min. Furthermore, some block copolymers containing saccharide segment with butyl or methyl methacrylate were prepared. Copyright © 2007 John Wiley & Sons, Ltd.     

呋喃西林水溶液在光和热作用下的稳定性

The influence of both light and heat on the stability of nitrofurazone aqueous solution was studied. Results show that in either heating experiments or the exposure to light at high temperatures, the degradation rate obeyed zero-order kinetics. The total rate constant ktotal caused by both light and heat can be divided into two parts: ktotal =kdark klight, where kdark and klight are the degradation rate constants caused by heat and light, respectively. The klight can be expressed as klight=Alight*exp(-Ea,light/RT)*E, where E is the illuminance of light, and Alight and Ea,light both are experimental constants. The values of these kinetic parameters were determined based on the experiments in the dark and upon exposure to three different light sources. Results show that the values of Alight and Ea, light varied with the light source. To save time, labor, and drugs, exponential heating experiments were employed and compared with the isothermal experiments. Results indicated that kinetic parameters obtained by exponential heating experiments are comparable to those obtained by isothermal experiments either in the dark or upon exposure to light.