Poly(vinyl alcohol)/poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) semi-interpenetrating polymer network hydrogels with rapid response to temperature changes

A series of thermosensitive and fast-response poly(vinyl alcohol) (PVA)/poly(N-isopropylacrylamide) (PNIPA) hydrogels were prepared by incorporating PVA into cross-linked PNIPA to form a semi-interpenetrating polymeric network (semi-IPN). Compared to the conventional PNIPA hydrogel, the semi-IPN hydrogels thus prepared exhibit significantly faster response rates and undergo full deswelling in 1 min (lose about 95% water within 1 min) when the temperature is raised above their lower critical solution temperature, and have larger equilibrium swelling ratios at room temperature. These improved properties are attributed to the incorporation of PVA, which forms water-releasing channels and results in increased hydrophilicity, into the PNIPA hydrogel networks.     

The preparation and characterization of novel cocylic(arylene disulfide) oligomers

A series of homo‐ and cocyclic(arylene disulfide) oligomers were synthesized under high dilution conditions by the catalytic oxidation of arylenedithiols with oxygen in the presence of a copper‐amine catalyst in DMAc. The aryl groups contained moieties such as sulfone, ether, and ketone. The free radical ring‐opening polymerization of these cyclic(arylene disulfide) oligomers led to the formation of linear poly(thio arylene)s. The homo‐ and cocyclic(arylene disulfide) oligomers were characterized by gradient high pressure liquid chromatography (HPLC), get permeation chromatography (GPC), ¹H‐NMR, and differential scanning calorimetry (DSC) methods. These cocyclic(arylene disulfide) oligomers except those containing sulfone moiety had lower melt flow temperature as low as 140 °C and therefore could readily undergo free radical ring‐opening polymerization under mild conditions. The glass transition temperatures of these cocyclics ranged from 72.3 to 190.0 °C, while the glass transition temperatures of the polydisulfides derived from these cocyclics ranged from 78.4 to 194.5 °C. In this article, a new method of preparing arylene dithiols 4,4′‐oxybis(benzenethiol) and diphenylmethane‐4,4′‐dithiol is reported. Copyright © 2003 John Wiley & Sons, Ltd.     

On the Importance of H-Bonding Interactions in Organic Ammonium Tetrathiotungstates

Four new organic ammonium tetrathiotungstates (N–Me–enH₂)[WS₄] (1), (N,N′-dm-1,3-pnH₂)[WS₄] (2), (1,4-bnH₂)[WS₄] (3), and (mipaH)₂[WS₄] (4), (N–Me–enH₂ = N-methylethylenediammonium, N,N′-dm-1,3-pnH₂ = N,N′-dimethyl-1,3-propanediammonium, 1,4-bnH₂ = 1,4-butanediammonium, and mipaH = monoisopropylammonium) were synthesized by the base promoted cation exchange reaction and characterized by elemental analysis, infrared, Raman, UV-Vis and ¹H NMR spectroscopy as well as single crystal X-ray crystallography. The structures of 1–4 consist of [WS₄]²⁻ tetrahedra which are linked to the organic ammonium cations via N–H⋯S hydrogen bonding. The strength and number of the S⋯H interactions affect the W–S bond lengths as evidenced by distinct short and long W–S bonds. The IR spectra exhibit splitting of the W–S vibrations, which can be attributed to the distortion of the [WS₄]²⁻ tetrahedron. From a comparative study of several known tetrathiotungstates it is observed that a difference of more than 0.033 ? between the longest and shortest W–S bonds in a tetrathiotungstate will result in the splitting of the asymmetric stretching vibration of the W–S bond.     

Determination of methylmercury fluxes across the air–water and air–soil interfaces by gas chromatography with electron capture detection

A method for the determination of methylmercury (MeHg) fluxes across the air–water and air–soil interfaces was developed using an in situ chamber. The MeHg in the air coming out of the chamber was captured by a column containing sulfhydryl cotton fiber adsorbent. MeHg was then desorbed from the column by using 2 mol L^–1 HCl. The MeHg in the effluent was extracted with benzene, and determined by gas chromatography with electron capture detection. Finally, the MeHg flux was calculated using the chamber. The method was applied to simulated experiments, and the results showed that the MeHg fluxes in the air–water system were higher than those in the air–soil–water system. The method was also successfully applied to the field measurements of an environment polluted by a chemical factory, and the results showed that the MeHg fluxes across the air–soil and air–water interfaces were 0.21–3.09 and 0.14–0.79 ng m^–2 h^–1, respectively. The method will be a useful tool in the environmental study of MeHg.     

LC-mass spectrometry analysis of N- and C-terminal boundary sequences of polypeptide fragments by limited proteolysis

Limited proteolysis is an important and widely used method for analyzing the tertiary structure and determining the domain boundaries of proteins. Here we describe a novel method for determining the N- and C-terminal boundary amino acid sequences of products derived from limited proteolysis using semi-specific and/or non-specific enzymes, with mass spectrometry as the only analytical tool. The core of this method is founded on the recognition that cleavage of proteins with non-specific proteases is not random, but patterned. Based on this recognition, we have the ability to determine the sequence of each proteolytic fragment by extracting a common association between data sets containing multiple potential sequences derived from two or more different mass spectral molecular weight measurements. Proteolytic product sequences derived from specific and non-specific enzymes can be accurately determined without resorting to the conventional time-consuming and laborious methods of SDS-PAGE and N-terminal sequencing analysis. Because of the sensitivity of mass spectrometry, multiple transient proteolysis intermediates can also be identified and analyzed by this method, which allows the ability to monitor the progression of proteolysis and thereby gain insight into protein structures.     

The role of esterification on detection of protonated and deprotonated peptide ions in matrix assisted laser desorption/ionization (MALDI) mass spectrometry (MS)

Esterification was used to investigate how introduction of aliphatic chains within the peptide structure affects the MALDI response of ions analyzed in both polarity regimes. In binary mixtures containing equimolar amounts of a peptide with its correspondent alkyl ester, derivatization of the carboxylic groups has the tendency to increase MALDI detection of the modified protonated peptide ions. This positive effect on ion yield is more pronounced when longer alcohols are employed. In negative mode, the situation is antithetic and esterification produces a deleterious effect on the ion yield of the corresponding deprotonated species. From the data reported here we postulate that modifications of the acidic character of peptides prevent formation of anionic species under MALDI analysis. Furthermore, suppression of the formation pathway for anions alters the overall number of molecules which can undergo protonation. This results in an increased ion yield for the protonated esters.     

Analysis of cerebrospinal fluid from patients with psychiatric and neurological disorders by two-dimensional electrophoresis: identification of disease-associated polypeptides as fibrin fragments

Two-dimensional electrophoresis (2-DE) of cerebrospinal fluid (CSF) samples--from 347 patients with various psychiatric and neurological disorders--and subsequent silver staining revealed two additional polypeptides (Mr 40,000) in 49% of 111 schizophrenics, 46% of 43 schizoaffective patients, 36% of 41 patients with affective disorders, 43% of 28 patients with multiple sclerosis, but not in 25 patients without neurological symptomatology, nor in 9 patients with Lues, and in only 2 of 25 patients with AIDS. The two polypeptides, as detected by 2-DE, eluted after size exclusion chromatography in fractions containing proteins with Mr greater than 200,000. After 2-DE of CSF samples, enriched by gel chromatography, the polypeptides were immobilized by blotting onto glass-fiber membranes and subjected to N-terminal sequencing. Polypeptide A was identified as beta-chain remnant (beta 2), derived from plasmin cleavage of fibrin(ogen). After size exclusion chromatography, 2-DE, and Western blotting, polypeptide A and B, as well as several other spots, reacted with fibrinogen antibodies, suggesting that the polypeptides are subunits of a fibrin degradation complex.     

载镍ZSM-5沸石中钠的作用

本文通过对一组不同Na含量NiZSM-5沸石的酸性、吸附性及催化活性的测试表明于载镍ZSM-5体系中添加碱金属钠离子, 不仅调节沸石的碱酸功能, 而且增加甲苯的吸附性, 提高甲苯的转化率, 表现出助催化效应。     

Comparative study of C(2) epimerization of d-glucose and d-mannose catalyzed by water soluble organometallic complexes with nitrogen ligands

Epimerization of d-glucose and d-mannose, catalyzed by the water soluble complexes of Cu(II), Ni(II), Co(II) and Cd(II) with bisnitrogen ligands 4–7, and by Mo(VI) complexes prepared in situ from ammonium heptamolybdate (AHM) with ligands 4–9 is compared. All examined complexes exhibit lower catalytic activity than AHM: strong coordination of the ligands by both (N,O) heteroatoms to metal ions, presumably affords catalytically less active species. Some free ligands and their metal (II) complexes catalyze both C(2) epimerization and isomerization of aldoses to d-fructose.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number.