Effect of diisopropyl thiophosphoryl‐N‐oxydiethylene sulfenamide and some disulfidic compounds in the covulcanization of NR–EPDM blends

Synergistic combinations of diisopropyl thiophosphoryl‐N‐oxydiethylene sulfenamide (DIPTOS) with some disulfide accelerators or sulfur donors improve the physical properties of NR–EPDM blend vulcanizates. Various combinations of DIPTOS with dibenzothiazyl disulfide (MBTS), tetramethyl thiuram disulfide (TMTD), bis(N‐oxydiethylene) disulfide (ODDS) and bis(diisopropyl) thiophosphoryl disulfide (DIPDIS) were used in this study. DIPTOS when used alone produces NR vulcanizates with a moderate range of physical properties, whereas in conjunction with MBTS and DIPDIS it exhibits significant mutual activities. Morphological studies of the tensile‐fractured surfaces of the blend vulcanizates by scanning electron microscopy corroborate the physical data. Copyright © 2003 Society of Chemical Industry     

Prediction of the structures of proteins with the UNRES force field, including dynamic formation and breaking of disulfide bonds

The presence of disulfide bonds is essential for maintaining the structure and function of many proteins. The disulfide bonds are usually formed dynamically during folding. This process is not accounted for in present algorithms for protein-structure prediction, which either deduce the possible positions of disulfide bonds only after the structure is formed or assume fixed disulfide bonds during the course of simulated folding. In this work, the conformational space annealing (CSA) method and the UNRES united-residue force field were extended to treat dynamic formation of disulfide bonds. A harmonic potential is imposed on the distance between disulfide-bonded cysteine side-chain centroids to describe the energetics of bond distortion and an energy gain of 5.5 kcal/mol is added for disulfide-bond formation. Formation, breaking and rearrangement of disulfide bonds are included in the CSA search by introducing appropriate operations; the search can also be carried out with a fixed disulfide-bond arrangement. The algorithm was applied to four proteins: 1EI0 (alpha), 1NKL (alpha), 1L1I (beta-helix) and 1ED0 (alpha + beta). For 1EI0, a low-energy structure with correct fold was obtained both in the runs without and with disulfide bonds; however, it was obtained as the lowest in energy only with the native disulfide-bond arrangement. For the other proteins studied, structures with the correct fold were obtained as the lowest (1NKL and 1L1I) or low-energy structures (1ED0) only in runs with disulfide bonds, although the final disulfide-bond arrangement was non-native. The results demonstrate that, by including the possibility of formation of disulfide bonds, the predictive power of the UNRES force field is enhanced, even though the disulfide-bond potential introduced here rarely produces disulfide bonds in native positions. To the best of our knowledge, this is the first algorithm for energy-based prediction of the structure of disulfide-bonded proteins without any assumption as to the positions of native disulfides or human intervention. Directions for improving the potentials and the search method are suggested.     

滇韭挥发性成分分析

用同时蒸馏萃取装置提取挥发油并用气相色谱-质谱联用仪对滇韭挥发性成分进行了分离和鉴定,分离并鉴定出95个组分,占峰面积的71 50%,用面积归一化法测定了各种成分的质量分数,其主要挥发性成分为:w(三甲基磷化硫醚) =0 15%,w(丁基丙烯基硫醚) =0 03%,w(1, 2 二乙硫基乙烯) =0 38%,w(烯丙基甲基硫醚) =0 79%,w(二烯丙基硫醚) =0 11%,w(2 甲氧基茴香硫醚) =0 15%,w(甲基乙基二硫醚) =0 02%,w(二甲基二硫醚) =0 08%,w(二烯丙基二硫醚) =0 10%,w(二丙基二硫醚) =1 03%,w〔(甲硫基)二甲基二硫醚〕=0 17%,w(甲基1 丙烯基二硫醚) =0 32%,w(二2 羟基乙基二硫醚) =0 11%,w(二甲基三硫醚) =0 02%,w(甲基2 丙烯基三硫醚) =0 06%,w(二2 丙烯基三硫醚) =0 45%,w(二丙基三硫醚) =1 54%,w(二甲基四硫醚) =0 39%,w(4H 噻唑) =0 02%,w(4, 5 二甲基噻唑) =0 50%,w(4, 5 二甲基异噻唑) =0 06%,w(5 甲氧基噻唑) =0 24%,w(3, 4 二甲基异噻唑) =0 22%,w(3, 4 二甲基噻吩) =0 27%,w(4H 2 乙基噻吩) =0 02%,w(1, 3 二噻烷) =0 03%,w(1, 3, 5 三噻烷) =0 03%,w(1, 2 二硫戊环) =0 09%,w〔2, 4 二硫杂戊烷〕=0 98%,w(3, 5 二乙基1, 2, 4 三硫戊环) =0 55%,w(二甲基亚砜) =0 05%,w(3 甲硫基丁醛) =0 02%,w(2 甲基硫代乙酸) =0 37%,w     

Effect of the intermolecular disulfide bond on the conformation and stability of glial cell line-derived neurotrophic factor

Glial cell line-derived neurotrophic factor (GDNF) is a memberof the TGF-ß superfamily of proteins. It exists asa covalent dimer in solution, with the 15 kDa monomers linkedby an interchain disulfide bond through the Cys101 residues.Sedimentation equilibrium and velocity experiments demonstratedthat, after removal of the interchain disulfide bond, GDNF remainsas a non-covalent dimer and is stable at pH 7.0. To investigatethe effect of the intermolecular disulfide on the structureand stability of GDNF, we compared the solution structures ofthe wild-type protein and a cysteine-101 to alanine (C101A)mutant using Fourier transform infrared (FTIR), FT-Raman andcircular dichroism (CD) spectroscopy and sedimentation analysis.The elimination of the intermolecular disulfide bond causesonly minor changes (     

Synthesis and thermal characteristics of poly(thioarylene)s by thermal polymerization

Thermal polymerization of bis[4-(4-bromophenylthio)phenyl] disulfide (I), bis[4-(4-bromophenyloxy)phenyl] disulfide (II) and bis[(4-(4-bromophenylsulfony)phenyloxy)phenyl] disulfide (III) was carried out at 250°C in diphenyl ether. The resulting poly(thioarylene)s show high crystallinity and high thermal stability. The blends and copolymers of poly(thioarylene) were also prepared, whose thermal properties were investigated by DSC measurements.     

水相合成双-[γ-（三乙氧基硅）丙基]-二硫化物

以γ-氯丙基三乙氧基硅烷(简称γ2)、硫氢化钠、硫为原料,通过加入缓冲剂控制反应体系的pH以抑制γ2的水解,同时运用相转移催化技术,在水相中合成了双-[γ-(三乙氧基硅)丙基]二硫化物(简称Si-75)。主要考察了n(NaHS)∶n(S)、n(γ2)∶n(Na2Sx)、n(Na2CO3)∶n(NaHS)、反应温度、相转移催化剂用量等对合成工艺的影响,最终制得的Si-75外观呈浅黄色,产率为95.4%,w(S)=13.5%。     

Cure synergism in XNBR vulcanization in presence of thiophosphoryl disulfides and amine disulfide/thiazole accelerators

The study deals with the vulcanization of carboxylated nitrile butadiene rubber (XNBR) having synergistic combinations of accelerators comprising thiophosphoryl disulfide as one of the components. Other constituent accelerators employed in the present investigation are 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazyl disulfide (MBTS), bis(N-oxydiethylene)disulfide (ODDS), N-oxydiethylene 2-benzothiazole sulfenamide (OBTS), etc. The binary combinations of thiophosphoryl disulfides with OBTS exhibited the highest mutual activity in the respective areas, so far as the physical properties are concerned. Structural characterization of different thiophosphoryl disulfide-accelerated XNBR vulcanizates, including those formed from the synergistic combinations with OBTS, were studied using a methyl iodide probe. It was found that the amount of sulfidic crosslinks arising from the reaction between  COOH groups of XNBR and thiophosphoryl disulfides, actually controls the network structure as wellas the physical properties of the vulcanizates. © 1996 John Wiley & Sons, Inc.     

Structure-function analysis of the soluble glycoprotein, sGP, of Ebola virus

In addition to the transmembrane protein, GP(1,2), the Ebola virus glycoprotein gene encodes the soluble glycoproteins sGP and Delta-peptide. Two more soluble proteins, GP(1) and GP(1,2DeltaTM), are generated from GP(1,2) as a result of disulfide-bond instability and proteolytic cleavage, respectively, and are shed from the surface of infected cells. The sGP glycoprotein is secreted as a disulfide-linked homodimer, but there have been conflicting reports on whether it is arranged in a parallel or antiparallel orientation. Off-line HPLC-MALDI-TOF MS (MS/MS) was used to identify the arrangement of all disulfide bonds and simultaneously determine site-specific information regarding N-glycosylation. Our data prove that sGP is a parallel homodimer that contains C53-C53' and C306-C306' disulfide bonds, and although there are six predicted N-linked carbohydrate sites, only five are consistently glycosylated. The disulfide bond arrangement was confirmed by using cysteine to glycine mutations at amino acid positions 53 and 306. The mutants had a reduced ability to rescue the barrier function of TNF-alpha-treated endothelial cells--a function previously reported for sGP. This indicates that these disulfide bonds are critical for the proposed anti-inflammatory function of sGP.     

Synthesis and properties of poly(4,4′-oxybis(benzene)disulfide)/graphite nanocomposites via in situ ring-opening polymerization of macrocyclic oligomers

An effective method for the preparation of poly(4,4′-oxybis(benzene)disulfide)/graphite nanosheet composites via in situ ring-opening polymerization of macrocyclic oligomers were reported. Completely exfoliated graphite nanosheets were prepared under the microwave irradiation followed by sonication in solution. The nanocomposites were fabricated via in situ melt ring-opening polymerization of macrocyclic oligomers in the presence of graphite nanosheets. The graphite nanosheets and resulted poly(arylene disulfide)/graphite nanocomposites were characterized with field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), tensile tester and electrical conductivity measurements. Compared with pure polymer, the electrical conductivity of the poly(arylene disulfide)/graphite nanocomposites were dramatically increased and had a value of about 10⁻³ S/cm for the nanocomposite containing 5 wt% graphite. The nanocomposites exhibit as both high performance polymeric material and electrically conductive material. Therefore, they show potential applications as high temperature conducting materials.     

Synthesis and properties of copolymer of 3‐thienylmethyl disulfide and benzyl disulfide for cathode material in lithium batteries

The copolymerization of 3‐thienylmethyl disulfide and benzyl disulfide has been investigated. Two monomers were synthesized in a novel facile way. Copolymer of them, especially poly (3‐thienylmethyl disulfide‐co‐benzyl disulfide), ratio 1 : 4, namely, TcB_1:4, was easily electrocopolymerized to form a stable and higher conductive structure at a lower potential on Pt, Au, or glass carbon electrode. TcB_1:4 and TcB_4:1, especially the former, exhibit better conductivities than those of pure poly 3‐thienylmethyl disulfide and poly benzyl disulfide. The copolymer has larger areas than that of monopolymer by cyclic voltammogram measurement. The copolymer shows a capability of supplying more power and energy than monopolymer itself. Copolymers could be used as cathode materials for lithium secondary batteries because their functional groups could not be destroyed before 80°C. In scanning electron micrography, the copolymers show larger compacter structure. The results of the copolymer systems show that they are potentials as cathode materials for lithium batteries. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhanced Thermostability of D-Psicose 3-Epimerase from Clostridium bolteae through Rational Design and Engineering of New Disulfide Bridges

D-psicose 3-epimerase (DPEase) catalyzes the isomerization of D-fructose to D-psicose (aka D-allulose, a low-calorie sweetener), but its industrial application has been restricted by the poor thermostability of the naturally available enzymes. Computational rational design of disulfide bridges was used to select potential sites in the protein structure of DPEase from Clostridium bolteae to engineer new disulfide bridges. Three mutants were engineered successfully with new disulfide bridges in different locations, increasing their optimum catalytic temperature from 55 to 65 °C, greatly improving their thermal stability and extending their half-lives (t_1/2) at 55 °C from 0.37 h to 4−4.5 h, thereby greatly enhancing their potential for industrial application. Molecular dynamics simulation and spatial configuration analysis revealed that introduction of a disulfide bridge modified the protein hydrogen–bond network, rigidified both the local and overall structures of the mutants and decreased the entropy of unfolded protein, thereby enhancing the thermostability of DPEase.     

Thioether Analogues of Disulfide‐Bridged Cyclic Peptides Targeting Death Receptor 5: Conformational Analysis,Dimerisation and Consequences for Receptor Activation

Cyclic peptides containing redox‐stable thioether bridges might provide a useful alternative to disulfide‐bridged bioactive peptides. We report the effect of replacing the disulfide bridge with a lanthionine linkage in a 16‐mer cyclic peptide that binds to death receptor 5 (DR5, TRAIL‐R2). Upon covalent oligomerisation, the disulfide‐bridged peptide has previously shown similar behaviour to that of TNF‐related apoptosis inducing ligand (TRAIL), by selectively triggering the DR5 cell death pathway. The structural and biological properties of the DR5‐binding peptide and its desulfurised analogue were compared. Surface plasmon resonance (SPR) data suggest that these peptides bind DR5 with comparable affinities. The same holds true for dimeric versions of these peptides: the thioether is able to induce DR5‐mediated apoptosis of BJAB lymphoma and tumorigenic BJELR cells, albeit to a slightly lower extent compared to its disulfide homologue. NMR analysis revealed subtle variation in the conformations of the two peptides and suggests that the thioether peptide is slightly less folded than its disulfide homologue. These observations could account for the different capability of the two dimers to cluster DR5 receptors on the cell surface and to trigger apoptosis. Nevertheless, our results suggest that the thioether peptide is a potential candidate for evaluation in animal models.     

Oxidative folding of proteins

The oxidative folding of proteins is reviewed and illustrated with bovine pancreatic ribonuclease A (RNase A). The mutual effects of conformational folding and disulfide bond regeneration are emphasized, particularly the "locking in" of native disulfide bonds by stable tertiary structure in disulfide intermediates. Two types of structured metastable disulfide species are discerned, depending on the relative protection of their disulfide bonds and thiol groups. Four generic pathways for oxidative folding are identified and characterized.     

Synthesis and characterization of poly(methylene disulfide) and poly(ethylene disulfide) polymers in the presence of a phase transfer catalyst

Poly(methylene disulfide) and poly(ethylene disulfide) were synthesized from the polycondensation of methylene dichloride and ethylene dichloride monomers, respectively, in the presence of benzyltriethylammonium chloride as a phase transfer catalyst. The structures of the synthesized polysulfides were confirmed via the elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and X-ray diffraction techniques. Moreover, the thermal behaviors of synthesized poly(methylene disulfide) and poly(ethylene disulfide) were characterized using differential scanning calorimetry and thermogravimetric analysis methods. The synthesized poly(methylene disulfide) and poly(ethylene disulfide) have molecular weights of about 2262 and 2863 g/mol, respectively. In addition, the polymers have crystalline structures absorbed in the amorphous sections. However, the d-spacing of polymers’ crystalline parts was different. Moreover, poly(methylene disulfide) and poly(ethylene disulfide) have a two- and one-step degradation behavior, respectively.     

Poly[bis(2-aminophenyloxy)disulfide]: A polyaniline derivative containing disulfide bonds as a cathode material for lithium battery

A new conductive polyaniline derivative containing disulfide bonds, poly[bis(2-aminophenyloxy)disulfide] (PAPOD), has been proposed as a high energy-storage material. PAPOD has been synthesized using a moderate oxidant ferric chloride and characterized by elemental analysis, X-ray photoelectron spectroscopy (XPS), FT-IR, FT-Raman, and UV–vis spectroscopy. The cyclic voltammograms of this polymer show that the intramolecular self-catalysis occurs between the conductive main-chain polyaniline (doping/undoping processes of the π-conjugated system) and side-chain disulfide bonds (scission/reformation processes of the S–S bonds) in PAPOD. Because the redox reaction of conductive main-chain polyaniline occurs in the same potential range as that of the side-chain disulfide bonds of this polymer, the Li/PAPOD test cell displays a charge capacity of 230 mAh g⁻¹-cathode and an energy density of 460 mWh g⁻¹-cathode, which is about 2–3 times higher than those of inorganic intercalation compounds.     

Evaluation of redox-responsive disulfide cross-linked poly(hydroxyethyl methacrylate) hydrogels

Poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels were prepared with a disulfide containing cross-linker bis(2-methacryloxyethyl) disulfide (DSDMA) that exhibited enhanced release in the presence of glutathione (GSH), a biologically available reducing agent. Varying concentrations of the DSDMA cross-linker were incorporated into the prepolymer before the radical polymerization, enabling the cross-link density to be easily tuned. Dye release studies were performed using rhodamine B and rhodamine 6G dyes, and the UV response of the dyes released into the supernatant measured with the addition of GSH. Using ether-based cross-linkers as a control, the disulfide cross-linkers exhibited a substantial increase in release rates, confirming the responsive nature of the hydrogels to biological reducing agents. The polymers were also tested in a cell culture system for their ability to release the anti-fibroproliferative agent, mitomycin C (MMC). Polymers cross-linked with DSDMA delivered MMC over a slightly longer time period than control polymers prepared with a conventional ether cross-linker.     

Two-component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates: The in situ cleavage of disulfides by triarlyphosphines

A two-component initiator system based on the in situ cleavage of phenyl disulfide by a triarylphosphine has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers. This development has potential use in composite applications such that the prepolymer can suitably wet the composite material before being converted to high-molecular-weight polymer. The initiator precursors (phenyl disulfide and triphenylphosphine) do not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. A mixture of cyclic BPA carbonate oligomers and one of the initiator components (phenyl disulfide), combined and heated at 300°C with a mixture of the cyclics and the other initiator component (triphenylphosphine), does produce a high-molecular-weight polymer (M_w = ∼ 70,000). The polymerization-initiating species is thought to be thiophenyltriphenylphosphonium thiophenoxide. The effects of concentration of the initiator components, reaction temperature, time, and so forth on polymerization were studied; in general, the degree of polymerization ranged from about 65 to 75%. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2251–2255, 1997     

Thiuram vulcanization of natural rubber in the presence of hydrofuramide and ethanolamines

Influence of hydrofuramide and ethanolamines on efficient vulcanization (EV), semi-EV, and conventional sulfur vulcanization accelerated by tetramethyl thiuram disulfide is reported. In the case of thiuram vulcanization, the amines increase the cure rate but reduce the crosslink density. The interaction of tetramethyl thiuram disulfide with amines has been studied. The amines interact with thiuram disulfide (TMTD) giving rise to the formation of gaseous products. Thermogravimetric analysis shows weight loss of about 50% in case of TMTD–ethanolamine system and 25% in case of TMTD–hydrofuramide system. Gas chromatographic studies of the gaseous products indicate that it consists mainly of H₂S. The other constituents in the gaseous product are CO₂ and a thiol. A possible reaction based on these observations to account for decrease in crosslink density in thiuram vulcanization caused by amines is reported.     

Reactions of organic disulfides and gold(i) complexes

Gold-thiolate/disulfide exchange reactions of (p-SC(6)H(4)Cl)(2) with Ph(3)PAu(SC(6)H(4)CH(3)), dppm(AuSC(6)H(4)CH(3))(2), and dppe(AuSC(6)H(4)CH(3)) (2) were investigated. The rate of reactivity of the gold-thiolate complexes with (p-SC(6)H(4)Cl)(2) is: dppm(AuSC(6)H(4)CH(3))(2)> dppe(AuSC(6)H(4)CH(3))(2)>Ph(2)PAu (SC(6)H(4)CH(3)). This order correlates with conductivity measurements and two ionic mechanisms have been evaluated. (1)H NMR experiments demonstrate that in the reaction of dppm(AuSC(6)H(4)CH(3))(2) with (p-SC(6)H(4)Cl)(2), the mixed disulfide, ClC(6)H(4)SSC(6)H(4)CH(3), forms first, followed by the formation of (p-SC(6)H(4)CH(3))(2). The rate law is first order in (pp-SC(6)H (4)Cl)(2) and partial order in dppm(AuSC(6)H(4)CH(3))(2). Results from electrochemical and chemical reactivity studies suggest that free thiolate is not involved in the gold-thiolate/disulfide exchange reaction. A more likely source of ions is the dissociation of a proton from the methylene backbone of the dppm ligand which has been shown to exchange with D(2)O. The implications of this are discussed in terms of a possible mechanism for the gold-thiolate/disulfide exchange reaction.     

Preparation and Characterization of Stimuli-Responsive Magnetic Nanoparticles

In this work, the main attention was focused on the synthesis of stimuli-responsive magnetic nanoparticles (SR-MNPs) and the influence of glutathione concentration on its cleavage efficiency. Magnetic nanoparticles (MNPs) were first modified with activated pyridyldithio. Then, MNPs modified with activated pyridyldithio (MNPs-PDT) were conjugated with 2, 4-diamino-6-mercaptopyrimidine (DMP) to form SR-MNPs via stimuli-responsive disulfide linkage. Fourier transform infrared spectra (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize MNPs-PDT. The disulfide linkage can be cleaved by reduced glutathione (GHS). The concentration of glutathione plays an important role in controlling the cleaved efficiency. The optimum concentration of GHS to release DMP is in the millimolar range. These results had provided an important insight into the design of new MNPs for biomedicine applications, such as drug delivery and bio-separation.