Background:Cholangiocarcinoma(CCA)is a cancer type that builds in the bile ducts that carry digestive fluid,bile.These ducts connect the liver to the gallbladder and the small intestine.The disease is often diagnosed ...Background:Cholangiocarcinoma(CCA)is a cancer type that builds in the bile ducts that carry digestive fluid,bile.These ducts connect the liver to the gallbladder and the small intestine.The disease is often diagnosed at an advanced stage,resulting in a low 5-year survival rate.This study aims to evaluate the concentrations of serum thiol/disulfide in CCA patients and healthy volunteers and investigate the association between oxidative activity and clinical and pathological characteristics in CCA patients.By examining the relationship between reduced thiol/disulfide measures and tumorigenesis of the disease,we can potentially identify an unfavourable prognosis in CCA patients.Methods:To assess the status of thiol/disulfide in the blood of Cholangiocarcinoma patients using a novel automated homeostasis assay,we recruited 55 individuals for this study(CCA patients,n=27;healthy volunteers,n=28).We measured the levels of serum total thiol(TT)(–SH+–S-S–),native thiol(NT)(–SH),and disulfide(DD)(–S-S–)in both the CCA group and the control group.Additionally,we calculated the ratio of thiol/disulfide(–SH/–S-S–).Results:We explored the relationship between oxidative activity and clinical and pathological characteristics in CCA patients.The study found no significant differences in age and sex between CCA patients and controls.NT and TT levels were higher in the control group compared to the CCA group.However,the disulfide level did not significantly differ between the two groups.Pearson's correlation matrix analysis revealed positive correlations between TT and NT levels and negative correlations between NT/TT%,DD level,and DD/TT%.Conclusion:Our findings suggest a statistical difference in serum thiol/disulfide parameters.As a marker of total oxidant status,thiol and disulfide levels have decreased in patients with CCA.However,no correlation was found between the tumour markers CEA and CA19-9 and thiol levels.A decrease in blood thiol and disulfide concentrations or the ratio of thiol to disulfide may indicate an increase in oxidative stress and decreased antioxidant capacity.As an indication of the prognosis of cholangiocarcinoma disease in the early period,it may be used to determine the effectiveness of medical interventions.The NT/TT%,disulfide/native thiol percentage,and DD/TT%ratios did not significantly change between the groups.Therefore,measuring serum thiol levels could be a helpful marker for assessing prognosis in the early stages of CCA.Nevertheless,further studies must validate these results and investigate the underlying mechanisms.展开更多
In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modific...In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.展开更多
Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organ...Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organoselenium whose GPx mimetic property has been suggested to rely on the oxidation of non-protein or protein thiols critical to the activities of some sulfhydryl enzymes.This study,therefore investigated the GPx mimic/antioxidant property of DPDS as well as the role of thiols of two key sulfhydryl enzymes,cerebral Na^(+)/K^(+)-ATPase(sodium pump)and hepatic delta-aminolevulinic acid dehydratase(δ-ALAD)in the GPx mimicry of DPDS.Albino Wistar rats were euthanized,and the liver and brain were removed and used to assay for the effect of DPDS on lipid peroxidation induced by two prooxidants[Fe2^(+)(10μM)and H2O2,(1 mM)]as well as the activities of the sulfhydryl enzymes.The results revealed that DPDS profoundly(P<0.05)counteracted Fe2^(+)and H2O2-induced lipid peroxidation in the rats’hepatic and cerebral tissues.Furthermore,the results of assay systems for lipid peroxidation and sodium pump revealed that DPDS inhibited Na^(+)/K^(+)-ATPase and lipid peroxidation in the brain tissue homogenates in the same reaction system.A similar result was obtained in the assay system for lipid peroxidation and hepaticδ-ALAD as DPDS simultaneously inhibited the enzyme’s activity and lipid peroxidation.This suggests that the GPx mimetic property of DPDS may be linked to the enzymes’loss of activity,which further validates the suggestions that the enzymes’inhibition,as well as the antioxidant action of DPDS,rely on the oxidation of critical thiols of the enzymes.However,the GPx mimicry of DPDS should be investigated in the presence of thiol-blocking or oxidizing agents in biological systems in order to further ascertain the role of protein thiols.展开更多
Thiols play vital roles in cellular metabolism knowledge of which may be important in the design of future anticancer drugs. Previous work on the composition of the thiols present in human cancer cell lines has shown ...Thiols play vital roles in cellular metabolism knowledge of which may be important in the design of future anticancer drugs. Previous work on the composition of the thiols present in human cancer cell lines has shown the presence of an unknown low molecular weight species, deemed to be a “Conthiol”, which could be important in this respect. This was prepared and isolated from a human prostate cancer cell line (LNCaP) in the form of an adduct of 2-mercuri-4-nitrophenol;it accounts for 56.5% of the total cellular thiols present in this cell line. Initial LC-MS analysis of this adduct had indicated that the possible molecular weight of the thiol was in the region of 467 daltons. In further analytical studies to identify the thiol, attempts were made to release it from the adduct by passage through a Thiopropyl Sepharose6B column. LC-MS analysis of the column eluate revealed two components yielding negative ion fragments of 427 m/z and 449 m/z. Only the former component contained thiol, indicating that a breakdown and/or possible rearrangement of the Conthiol had occurred. Further investigations of the column thiol eluate using ICP-MS analysis showed that the sulfur content agreed with the spectrophotometric analysis result (Ellman assay) and that the molecule did not contain phosphate. Amino acid analyses of the eluate were negative. In an attempt to prevent the breakdown of the thiol released by the Thiopropyl Sepharose 6B column, the adduct was treated with 5% v/v bromine water prior to applying to the column. In this instance the thiol containing eluate obtained from the column was treated with an equimolar quantity of mercuric chloride forming a fresh adduct, RS-Hg-SR. LC-MS analysis of this mercurial adduct detected a negative ion fragment of 782 m/z which on further ionization gave a ladder like pattern showing loss of mass units of 58 in each rung. This would seem to suggest the presence of a repeat polymer like structure containing 5 monomers, which, plus the thiol atom, gives a possible formula weight of 322;probably revealing only a part of the unknown Conthiol molecule whose properties and formula weight do not correlate with any known cellular thiol. Further analysis of the thiol released from the adduct on the Thiopropyl Sepharose 6B column by Infra-red (FTIR) provided little information except to confirm the presence of the thiol group and C=O stretch bands together with the possibility of a lactam ring at 1651 and 1634 cm·s<sup>-</sup><sup>1</sup>.展开更多
The thiol components of the nonhistone proteins prepared from isolated nuclei from rat liver, regenerating liver and hepatoma 223 cells have been investigated after reaction with radio labelled N-ethylmaleimide and 5-...The thiol components of the nonhistone proteins prepared from isolated nuclei from rat liver, regenerating liver and hepatoma 223 cells have been investigated after reaction with radio labelled N-ethylmaleimide and 5-5’-dithiobis-(2-nitrobenzoic acid) (DTNB). The labelled adducts formed were examined by isoelectric focusing analysis in polyacrylamide gel and the distribution of the radiolabels within sliced portions of the gels determined. In the case of the 14C labelled NEM adduct the label was found to be spread amongst numerous protein components within the gel however, in the case of the 35S labelled DTNB adducts, only a small proportion of the label was found in the protein material which was retained in the acidic isoelectric point (pI) region of the gel. The bulk of the 35S labelled adduct (56% - 60%) was found to have migrated into the anode solution (10 mM phosphoric acid). This could be adsorbed onto a hydrophobic resin (XAD2) resin and eluted with methanol. Gel filtration chromatographic analysis of this adduct material on BioGel P2, (exclusion limit 1500 daltons) showed low molecular weight components to be present. Slightly different patterns were obtained for these nuclei, each containing several 35S components with molecular weights greater than the Ellman reagent itself. These 35S labelled thiol components did not contain any protein, peptide or amino acid components indicating strongly that a novel species of thiols could be present in these nuclei bound within the non-histone protein matrices.展开更多
The low molecular weight thiols present in the deproteinized extract of a prostate cancer cell line (LNCaP-FGC) were analysed after derivatization with the Ellman reagent (ESSE). The mixed disulphides formed (RSSE) we...The low molecular weight thiols present in the deproteinized extract of a prostate cancer cell line (LNCaP-FGC) were analysed after derivatization with the Ellman reagent (ESSE). The mixed disulphides formed (RSSE) were fractionated, characterized and quantified by liquid chromatography on a C-18 column using UV detection. This revealed the presence, in femtomoles per cell, of glutathione (8.30 ± 0.73), cysteine (2.71 ± 0.04) and cysteinylglycine (0.83 ± 0.10), accounting for the bulk of the thiol present. Further analysis of the cell extracts using a novel and sensitive mass spectrometry technique allowed the detection of low level of an additional derivative which was identified as cysteinylglycerate using NMRspectroscopy.展开更多
Objective: The aim of this study was to evaluate thiol-disulphide homeostasis in patients with Multiple Sclerosis (MS) during attack and remission. Design and Methods: A total of 82 patients admitted to our clinic wer...Objective: The aim of this study was to evaluate thiol-disulphide homeostasis in patients with Multiple Sclerosis (MS) during attack and remission. Design and Methods: A total of 82 patients admitted to our clinic were divided into 2 groups according to whether they are having an attack or not. Peripheral blood samples were taken from all patients and their native thiol, disulphide and total thiol concentrations were measured by a newly developed automated method. In addition, their disulphide/native thiol, disulphide/total thiol and native thiol/total thiol ratios were calculated. Results: The average disulphide values, disulphide/native thiol and disulphide/total thiol ratios of the patients with MS who were having an attack were found to be significantly higher compared to those in remission (p = 0.001, p = 0.001, p = 0.001, respectively). Conclusion: Our results have shown that thiol-disulphide balance was shifted to the oxidative area during the relapse. These homeostasis parameters, which can be easily measured by this newly developed method at low costs, may be important in terms of showing the disease activity and presenting the underlying mechanisms of the disease.展开更多
Self-assembled monolayers of octadecanethiol (ODT) on gold have been studied by electrochemical impedance spectroscopy (EIS). The fractional coverage has been examined as a function of immersion time of Au in ODT depo...Self-assembled monolayers of octadecanethiol (ODT) on gold have been studied by electrochemical impedance spectroscopy (EIS). The fractional coverage has been examined as a function of immersion time of Au in ODT deposition solution. The fractional coverage exhibits two distinct adsorption steps: an initial rapid step followed by a slow one. The fractional coverage of ODT monolayer increases sharply from zero to more than 99% of its maximum within the first minute. However, it takes a day for the fractional coverage to approach its final value.展开更多
Introduction Polymers containing thiol and sulphoxide which have active—SH and—SO groups respectively, have wide application to biological, pharmaceutical, industrial and other chemical field and—SH and—SO groups ...Introduction Polymers containing thiol and sulphoxide which have active—SH and—SO groups respectively, have wide application to biological, pharmaceutical, industrial and other chemical field and—SH and—SO groups are easy to form complexes with metals, so they have aroused an increasing interest of many authors. A large number of functional resins and corresponding metal complexes have been synthesized.展开更多
A cDNA library was constructed with 1.5×10~6 pfu from rice immature seeds,fromwhich a cDNA clone for rice thiol proteinase inhibitor,oryzacystatin(OC),was isolated byscreening with synthesized oligodeoxynucleotid...A cDNA library was constructed with 1.5×10~6 pfu from rice immature seeds,fromwhich a cDNA clone for rice thiol proteinase inhibitor,oryzacystatin(OC),was isolated byscreening with synthesized oligodeoxynucleotide probe,which contained a 309bp open read-ing frame,84bp 5′-end noncoding region and a poly(A)signal AATAAA at the 3′-end fol-lowed by 31Nt poly(A).Then the coding region of OC was amplified and inserted into thedownstream of λP_RP_L promoter for thermal-inducible expression in E.coli.Shifting the cul-ture temperature from 30℃ to 42℃ led to a high level expression of OC,which exhibited adistinct band of 12.0 kDa and accounted for at least 10% of the total soluble proteins fromSDS-PAGE.The papain-inhibitory activity of the expressed OC was further confirmed.展开更多
We introduce 1-Dodecanethiol(DT)to poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester based polymer solar cells as a processing additive.When the amount of DT is 1vol%,the device performance is be...We introduce 1-Dodecanethiol(DT)to poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester based polymer solar cells as a processing additive.When the amount of DT is 1vol%,the device performance is best.A final power conversion efficiency of 3.1%is achieved,which is an improvement of more than 40%compared to the reference solar cell without DT.To investigate the causes of improvement of the PCE,UV-vis spectroscopy,external quantum efficiency(EQE)is measured and an AFM is used.The enhanced photovoltaic performances are discussed in terms of optical properties and the film morphology.展开更多
The redox state of cellular thiols is widely studied because it was recently linked to many different diseases and pathologies. In this work we quantified the concentrations of protein disulfides (PSSP) and thiol-prot...The redox state of cellular thiols is widely studied because it was recently linked to many different diseases and pathologies. In this work we quantified the concentrations of protein disulfides (PSSP) and thiol-protein mixed disulfides (XSSP) in rat tissues (liver, kidney and heart) and cells (Raw 264.7) by an improved method of XSSP and PSSP determination after oxidative stress induced by diamide. Under native and denaturing conditions, a thiol block by N-ethymaleimide was introduced to avoid thiol exchange reaction activations by protein SH groups (PSH) (PSH + XSSP ←→ PSSP + XSH) and alterations of original XSSP/PSSP levels. Low molecular weight thiols (XSH) and PSH were respectively measured by HPLC on supernatants and on corresponding pellets by DTNB (Ellman’s reagent) after dithiothreitol reduction. PSSP concentrations of liver, heart and kidney were respectively 0.304, 0.605 and 0.785 μmoles/g and after diamide exposure they were significantly augmented of about 65%-70% in liver and heart, but not in the kidney. Normal XSSP, that were -20 times lower than normal PSSP were induced by diamide in liver and heart of about 40 times, but not in kidney. Thermodynamic criteria regarding the pKa values of thiols engaged as PSSP and GSSP were used to interpret dethiolation mechanisms via thiol exchange reactions.展开更多
a-Crystallin is the major structural protein of eye lens of vertebrates. In human lens, the ratio of aA-crystallin to aB-crystallin was found to be 3:1. aA-Crystallin contains two cysteine residues at positions 131 an...a-Crystallin is the major structural protein of eye lens of vertebrates. In human lens, the ratio of aA-crystallin to aB-crystallin was found to be 3:1. aA-Crystallin contains two cysteine residues at positions 131 and 142, which are at the junction between the a-crystallin domain and the C-terminal tail. We used the accessibility of the thiol groups by Ellman’s reagent (DTNB) as a tool to gain information about the various structural perturbations of hinge region of a-crystallin and during the binding with substrates. In the native condition, the cys-142 though reacted quite fast was not fully exposed. Several reagents were used to see the accessibility of cys-131. Rate constant for cys-131 was increased gradually with increase in the concentration of reagents. The bindings of substrates are affected by the accessibility of thiol indicating that the substrates bind to the hinge region of a-crystallin. By blocking of cys-142, it was observed that the accessibility of one thiol depends on the other thiol, and they are not independent. The hinge region of a-crystallin is very important as substrate binding site and from this study we have got various structural information about that region.展开更多
AIM To determine dynamic thiol/disulphide homeostasis in celiac disease and to examine the associate with celiac autoantibodies and gluten-free diet.METHODS Seventy three patients with celiac disease and 73 healthy vo...AIM To determine dynamic thiol/disulphide homeostasis in celiac disease and to examine the associate with celiac autoantibodies and gluten-free diet.METHODS Seventy three patients with celiac disease and 73 healthy volunteers were enrolled in the study. In both groups, thiol/disulphide homeostasis was examined with a new colorimetric method recently developed by Erel and Neselioglu. RESULTS In patients with celiac disease, native thiol(P = 0.027) and total thiol(P = 0.031) levels were lower, while disulphide(P < 0.001) level, disulphide/native thiol(P < 0.001) and disulphide/total thiol(P < 0.001) ratios were higher compared to the control group. In patients who do not comply with a gluten-free diet, disulphide/native thiol ratio was found higher compared to the patients who comply with the diet(P < 0.001). In patients withany autoantibody-positive, disulphide/native thiol ratio was observed higher compared to the patients with autoantibody-negative(P < 0.05). It is found that there is a negative correlation between celiac autoantibodies, and native thiol, total thiol levels and native thiol/total thiol ratio, while a positive correlation is observed between disulphide, disulphide/native thiol and disulphide/total thiol levels.CONCLUSION This study is first in the literature which found that the patients with celiac disease the dynamic thiol/disulphide balance shifts through disulphide form compared to the control group.展开更多
Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquiox...Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.展开更多
Objective: To determine serum thiol/disulfide homeostasis in panic disorder (PD). Methods: Serum native thiol, total thiol, and disulfide levels were measured in the patients with 40 PD patients and 40 healthy subject...Objective: To determine serum thiol/disulfide homeostasis in panic disorder (PD). Methods: Serum native thiol, total thiol, and disulfide levels were measured in the patients with 40 PD patients and 40 healthy subjects. Serum native thiol, total thiol, and disulfide levels were measured with a novel colorimetric, automated method. The thiol-disulfide ratio was also calculated. Results: The native thiol (p Conclusion: This is the first study in the literature to evaluate thiol-disulfide homeostasis in patients with PD. Our results suggest that the disulfide/thiol ratio is significantly greater in panic disorder patients.展开更多
In this work is described the synthesis of a multifunctional thiolated squalene. Thiol-ene coupling reactions were employed to functionalize the six double bonds of squalene, using thiolacetic acid. Hydrolysis of the ...In this work is described the synthesis of a multifunctional thiolated squalene. Thiol-ene coupling reactions were employed to functionalize the six double bonds of squalene, using thiolacetic acid. Hydrolysis of the resulting thioacetates, rendered the corresponding hexathiolated squalene SQ6SH. This compound was further photopolymerized separately with triallyl cyanurate, pentaerythritol triacrylate and diethyleneglycol divinyl ether. Real Time FTIR kinetics revealed that homopolymerization of the ene monomers took place in addition to the thiol-ene photopolymerization. Flexible films were obtained when SQ6SH was photopolymerized in bulk with the above mentioned unsaturated monomers.展开更多
Purpose: The triazole nucleus is an important part of the therapeutically interesting drug candidate as antimicrobial, analgesic, anticancer, anticonvulsant and anti-inflammatory agents. Methods: Therefore, in this st...Purpose: The triazole nucleus is an important part of the therapeutically interesting drug candidate as antimicrobial, analgesic, anticancer, anticonvulsant and anti-inflammatory agents. Methods: Therefore, in this study, twelve 4,5-disubstituted-1,2,4-triazole-3-thiols were synthesized by the reaction of substituted isothiocyanates and hydrazides using the common method of base catalysed intramolecular dehydrative cyclization of substituted thiosemicarbazides 3(a-f) and 4(a-f). The structures of these compounds were characterized by means of FT-IR, 1H-NMR, and elemental analysis data. All these compounds were screened for antibacterial, antioxidant, antitumor and cytotoxic activities. Results: Among these compounds: 5c, 5f and 6f were found active against gram positive cocci, the compounds 5a, 5b, 5d, 6a and 6f showed 85% free radical scavenging effect at 3 ppm when tested for antioxidant activity, 75% tumors inhibition was recorded using 5c, 5d and 6a and brine shrimps lethality assay declared 5a, 5b and 6d was 129.62 μg/ml, 161.577 μg/ml and 81.56 μg/ml respectively. Conclusion: Compounds carrying significant bioactivity can be further studied using animal models to establish their safety profile prior to initiating clinical trials.展开更多
文摘Background:Cholangiocarcinoma(CCA)is a cancer type that builds in the bile ducts that carry digestive fluid,bile.These ducts connect the liver to the gallbladder and the small intestine.The disease is often diagnosed at an advanced stage,resulting in a low 5-year survival rate.This study aims to evaluate the concentrations of serum thiol/disulfide in CCA patients and healthy volunteers and investigate the association between oxidative activity and clinical and pathological characteristics in CCA patients.By examining the relationship between reduced thiol/disulfide measures and tumorigenesis of the disease,we can potentially identify an unfavourable prognosis in CCA patients.Methods:To assess the status of thiol/disulfide in the blood of Cholangiocarcinoma patients using a novel automated homeostasis assay,we recruited 55 individuals for this study(CCA patients,n=27;healthy volunteers,n=28).We measured the levels of serum total thiol(TT)(–SH+–S-S–),native thiol(NT)(–SH),and disulfide(DD)(–S-S–)in both the CCA group and the control group.Additionally,we calculated the ratio of thiol/disulfide(–SH/–S-S–).Results:We explored the relationship between oxidative activity and clinical and pathological characteristics in CCA patients.The study found no significant differences in age and sex between CCA patients and controls.NT and TT levels were higher in the control group compared to the CCA group.However,the disulfide level did not significantly differ between the two groups.Pearson's correlation matrix analysis revealed positive correlations between TT and NT levels and negative correlations between NT/TT%,DD level,and DD/TT%.Conclusion:Our findings suggest a statistical difference in serum thiol/disulfide parameters.As a marker of total oxidant status,thiol and disulfide levels have decreased in patients with CCA.However,no correlation was found between the tumour markers CEA and CA19-9 and thiol levels.A decrease in blood thiol and disulfide concentrations or the ratio of thiol to disulfide may indicate an increase in oxidative stress and decreased antioxidant capacity.As an indication of the prognosis of cholangiocarcinoma disease in the early period,it may be used to determine the effectiveness of medical interventions.The NT/TT%,disulfide/native thiol percentage,and DD/TT%ratios did not significantly change between the groups.Therefore,measuring serum thiol levels could be a helpful marker for assessing prognosis in the early stages of CCA.Nevertheless,further studies must validate these results and investigate the underlying mechanisms.
基金the financial support from National Key Research & Development Program of China (2017B0602702)。
文摘In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.
文摘Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organoselenium whose GPx mimetic property has been suggested to rely on the oxidation of non-protein or protein thiols critical to the activities of some sulfhydryl enzymes.This study,therefore investigated the GPx mimic/antioxidant property of DPDS as well as the role of thiols of two key sulfhydryl enzymes,cerebral Na^(+)/K^(+)-ATPase(sodium pump)and hepatic delta-aminolevulinic acid dehydratase(δ-ALAD)in the GPx mimicry of DPDS.Albino Wistar rats were euthanized,and the liver and brain were removed and used to assay for the effect of DPDS on lipid peroxidation induced by two prooxidants[Fe2^(+)(10μM)and H2O2,(1 mM)]as well as the activities of the sulfhydryl enzymes.The results revealed that DPDS profoundly(P<0.05)counteracted Fe2^(+)and H2O2-induced lipid peroxidation in the rats’hepatic and cerebral tissues.Furthermore,the results of assay systems for lipid peroxidation and sodium pump revealed that DPDS inhibited Na^(+)/K^(+)-ATPase and lipid peroxidation in the brain tissue homogenates in the same reaction system.A similar result was obtained in the assay system for lipid peroxidation and hepaticδ-ALAD as DPDS simultaneously inhibited the enzyme’s activity and lipid peroxidation.This suggests that the GPx mimetic property of DPDS may be linked to the enzymes’loss of activity,which further validates the suggestions that the enzymes’inhibition,as well as the antioxidant action of DPDS,rely on the oxidation of critical thiols of the enzymes.However,the GPx mimicry of DPDS should be investigated in the presence of thiol-blocking or oxidizing agents in biological systems in order to further ascertain the role of protein thiols.
文摘Thiols play vital roles in cellular metabolism knowledge of which may be important in the design of future anticancer drugs. Previous work on the composition of the thiols present in human cancer cell lines has shown the presence of an unknown low molecular weight species, deemed to be a “Conthiol”, which could be important in this respect. This was prepared and isolated from a human prostate cancer cell line (LNCaP) in the form of an adduct of 2-mercuri-4-nitrophenol;it accounts for 56.5% of the total cellular thiols present in this cell line. Initial LC-MS analysis of this adduct had indicated that the possible molecular weight of the thiol was in the region of 467 daltons. In further analytical studies to identify the thiol, attempts were made to release it from the adduct by passage through a Thiopropyl Sepharose6B column. LC-MS analysis of the column eluate revealed two components yielding negative ion fragments of 427 m/z and 449 m/z. Only the former component contained thiol, indicating that a breakdown and/or possible rearrangement of the Conthiol had occurred. Further investigations of the column thiol eluate using ICP-MS analysis showed that the sulfur content agreed with the spectrophotometric analysis result (Ellman assay) and that the molecule did not contain phosphate. Amino acid analyses of the eluate were negative. In an attempt to prevent the breakdown of the thiol released by the Thiopropyl Sepharose 6B column, the adduct was treated with 5% v/v bromine water prior to applying to the column. In this instance the thiol containing eluate obtained from the column was treated with an equimolar quantity of mercuric chloride forming a fresh adduct, RS-Hg-SR. LC-MS analysis of this mercurial adduct detected a negative ion fragment of 782 m/z which on further ionization gave a ladder like pattern showing loss of mass units of 58 in each rung. This would seem to suggest the presence of a repeat polymer like structure containing 5 monomers, which, plus the thiol atom, gives a possible formula weight of 322;probably revealing only a part of the unknown Conthiol molecule whose properties and formula weight do not correlate with any known cellular thiol. Further analysis of the thiol released from the adduct on the Thiopropyl Sepharose 6B column by Infra-red (FTIR) provided little information except to confirm the presence of the thiol group and C=O stretch bands together with the possibility of a lactam ring at 1651 and 1634 cm·s<sup>-</sup><sup>1</sup>.
文摘The thiol components of the nonhistone proteins prepared from isolated nuclei from rat liver, regenerating liver and hepatoma 223 cells have been investigated after reaction with radio labelled N-ethylmaleimide and 5-5’-dithiobis-(2-nitrobenzoic acid) (DTNB). The labelled adducts formed were examined by isoelectric focusing analysis in polyacrylamide gel and the distribution of the radiolabels within sliced portions of the gels determined. In the case of the 14C labelled NEM adduct the label was found to be spread amongst numerous protein components within the gel however, in the case of the 35S labelled DTNB adducts, only a small proportion of the label was found in the protein material which was retained in the acidic isoelectric point (pI) region of the gel. The bulk of the 35S labelled adduct (56% - 60%) was found to have migrated into the anode solution (10 mM phosphoric acid). This could be adsorbed onto a hydrophobic resin (XAD2) resin and eluted with methanol. Gel filtration chromatographic analysis of this adduct material on BioGel P2, (exclusion limit 1500 daltons) showed low molecular weight components to be present. Slightly different patterns were obtained for these nuclei, each containing several 35S components with molecular weights greater than the Ellman reagent itself. These 35S labelled thiol components did not contain any protein, peptide or amino acid components indicating strongly that a novel species of thiols could be present in these nuclei bound within the non-histone protein matrices.
文摘The low molecular weight thiols present in the deproteinized extract of a prostate cancer cell line (LNCaP-FGC) were analysed after derivatization with the Ellman reagent (ESSE). The mixed disulphides formed (RSSE) were fractionated, characterized and quantified by liquid chromatography on a C-18 column using UV detection. This revealed the presence, in femtomoles per cell, of glutathione (8.30 ± 0.73), cysteine (2.71 ± 0.04) and cysteinylglycine (0.83 ± 0.10), accounting for the bulk of the thiol present. Further analysis of the cell extracts using a novel and sensitive mass spectrometry technique allowed the detection of low level of an additional derivative which was identified as cysteinylglycerate using NMRspectroscopy.
文摘Objective: The aim of this study was to evaluate thiol-disulphide homeostasis in patients with Multiple Sclerosis (MS) during attack and remission. Design and Methods: A total of 82 patients admitted to our clinic were divided into 2 groups according to whether they are having an attack or not. Peripheral blood samples were taken from all patients and their native thiol, disulphide and total thiol concentrations were measured by a newly developed automated method. In addition, their disulphide/native thiol, disulphide/total thiol and native thiol/total thiol ratios were calculated. Results: The average disulphide values, disulphide/native thiol and disulphide/total thiol ratios of the patients with MS who were having an attack were found to be significantly higher compared to those in remission (p = 0.001, p = 0.001, p = 0.001, respectively). Conclusion: Our results have shown that thiol-disulphide balance was shifted to the oxidative area during the relapse. These homeostasis parameters, which can be easily measured by this newly developed method at low costs, may be important in terms of showing the disease activity and presenting the underlying mechanisms of the disease.
基金the Natural Science Foundation of Hebei Province.
文摘Self-assembled monolayers of octadecanethiol (ODT) on gold have been studied by electrochemical impedance spectroscopy (EIS). The fractional coverage has been examined as a function of immersion time of Au in ODT deposition solution. The fractional coverage exhibits two distinct adsorption steps: an initial rapid step followed by a slow one. The fractional coverage of ODT monolayer increases sharply from zero to more than 99% of its maximum within the first minute. However, it takes a day for the fractional coverage to approach its final value.
基金Supported by the National Natural Science Foundation of China
文摘Introduction Polymers containing thiol and sulphoxide which have active—SH and—SO groups respectively, have wide application to biological, pharmaceutical, industrial and other chemical field and—SH and—SO groups are easy to form complexes with metals, so they have aroused an increasing interest of many authors. A large number of functional resins and corresponding metal complexes have been synthesized.
基金Supported by Prime Minister FouNdationthe High Techriology Research and Development Programme of ChinaRockefeller Foun-dation.
文摘A cDNA library was constructed with 1.5×10~6 pfu from rice immature seeds,fromwhich a cDNA clone for rice thiol proteinase inhibitor,oryzacystatin(OC),was isolated byscreening with synthesized oligodeoxynucleotide probe,which contained a 309bp open read-ing frame,84bp 5′-end noncoding region and a poly(A)signal AATAAA at the 3′-end fol-lowed by 31Nt poly(A).Then the coding region of OC was amplified and inserted into thedownstream of λP_RP_L promoter for thermal-inducible expression in E.coli.Shifting the cul-ture temperature from 30℃ to 42℃ led to a high level expression of OC,which exhibited adistinct band of 12.0 kDa and accounted for at least 10% of the total soluble proteins fromSDS-PAGE.The papain-inhibitory activity of the expressed OC was further confirmed.
基金Supported by the Natural Science Foundation of Hebei Province under Grant Nos F2010000306,F2012201089 and A2011201008Hebei Province Department of Education Fund(ZH 2011205)。
文摘We introduce 1-Dodecanethiol(DT)to poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester based polymer solar cells as a processing additive.When the amount of DT is 1vol%,the device performance is best.A final power conversion efficiency of 3.1%is achieved,which is an improvement of more than 40%compared to the reference solar cell without DT.To investigate the causes of improvement of the PCE,UV-vis spectroscopy,external quantum efficiency(EQE)is measured and an AFM is used.The enhanced photovoltaic performances are discussed in terms of optical properties and the film morphology.
文摘The redox state of cellular thiols is widely studied because it was recently linked to many different diseases and pathologies. In this work we quantified the concentrations of protein disulfides (PSSP) and thiol-protein mixed disulfides (XSSP) in rat tissues (liver, kidney and heart) and cells (Raw 264.7) by an improved method of XSSP and PSSP determination after oxidative stress induced by diamide. Under native and denaturing conditions, a thiol block by N-ethymaleimide was introduced to avoid thiol exchange reaction activations by protein SH groups (PSH) (PSH + XSSP ←→ PSSP + XSH) and alterations of original XSSP/PSSP levels. Low molecular weight thiols (XSH) and PSH were respectively measured by HPLC on supernatants and on corresponding pellets by DTNB (Ellman’s reagent) after dithiothreitol reduction. PSSP concentrations of liver, heart and kidney were respectively 0.304, 0.605 and 0.785 μmoles/g and after diamide exposure they were significantly augmented of about 65%-70% in liver and heart, but not in the kidney. Normal XSSP, that were -20 times lower than normal PSSP were induced by diamide in liver and heart of about 40 times, but not in kidney. Thermodynamic criteria regarding the pKa values of thiols engaged as PSSP and GSSP were used to interpret dethiolation mechanisms via thiol exchange reactions.
文摘a-Crystallin is the major structural protein of eye lens of vertebrates. In human lens, the ratio of aA-crystallin to aB-crystallin was found to be 3:1. aA-Crystallin contains two cysteine residues at positions 131 and 142, which are at the junction between the a-crystallin domain and the C-terminal tail. We used the accessibility of the thiol groups by Ellman’s reagent (DTNB) as a tool to gain information about the various structural perturbations of hinge region of a-crystallin and during the binding with substrates. In the native condition, the cys-142 though reacted quite fast was not fully exposed. Several reagents were used to see the accessibility of cys-131. Rate constant for cys-131 was increased gradually with increase in the concentration of reagents. The bindings of substrates are affected by the accessibility of thiol indicating that the substrates bind to the hinge region of a-crystallin. By blocking of cys-142, it was observed that the accessibility of one thiol depends on the other thiol, and they are not independent. The hinge region of a-crystallin is very important as substrate binding site and from this study we have got various structural information about that region.
文摘AIM To determine dynamic thiol/disulphide homeostasis in celiac disease and to examine the associate with celiac autoantibodies and gluten-free diet.METHODS Seventy three patients with celiac disease and 73 healthy volunteers were enrolled in the study. In both groups, thiol/disulphide homeostasis was examined with a new colorimetric method recently developed by Erel and Neselioglu. RESULTS In patients with celiac disease, native thiol(P = 0.027) and total thiol(P = 0.031) levels were lower, while disulphide(P < 0.001) level, disulphide/native thiol(P < 0.001) and disulphide/total thiol(P < 0.001) ratios were higher compared to the control group. In patients who do not comply with a gluten-free diet, disulphide/native thiol ratio was found higher compared to the patients who comply with the diet(P < 0.001). In patients withany autoantibody-positive, disulphide/native thiol ratio was observed higher compared to the patients with autoantibody-negative(P < 0.05). It is found that there is a negative correlation between celiac autoantibodies, and native thiol, total thiol levels and native thiol/total thiol ratio, while a positive correlation is observed between disulphide, disulphide/native thiol and disulphide/total thiol levels.CONCLUSION This study is first in the literature which found that the patients with celiac disease the dynamic thiol/disulphide balance shifts through disulphide form compared to the control group.
文摘Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.
文摘Objective: To determine serum thiol/disulfide homeostasis in panic disorder (PD). Methods: Serum native thiol, total thiol, and disulfide levels were measured in the patients with 40 PD patients and 40 healthy subjects. Serum native thiol, total thiol, and disulfide levels were measured with a novel colorimetric, automated method. The thiol-disulfide ratio was also calculated. Results: The native thiol (p Conclusion: This is the first study in the literature to evaluate thiol-disulfide homeostasis in patients with PD. Our results suggest that the disulfide/thiol ratio is significantly greater in panic disorder patients.
文摘In this work is described the synthesis of a multifunctional thiolated squalene. Thiol-ene coupling reactions were employed to functionalize the six double bonds of squalene, using thiolacetic acid. Hydrolysis of the resulting thioacetates, rendered the corresponding hexathiolated squalene SQ6SH. This compound was further photopolymerized separately with triallyl cyanurate, pentaerythritol triacrylate and diethyleneglycol divinyl ether. Real Time FTIR kinetics revealed that homopolymerization of the ene monomers took place in addition to the thiol-ene photopolymerization. Flexible films were obtained when SQ6SH was photopolymerized in bulk with the above mentioned unsaturated monomers.
文摘Purpose: The triazole nucleus is an important part of the therapeutically interesting drug candidate as antimicrobial, analgesic, anticancer, anticonvulsant and anti-inflammatory agents. Methods: Therefore, in this study, twelve 4,5-disubstituted-1,2,4-triazole-3-thiols were synthesized by the reaction of substituted isothiocyanates and hydrazides using the common method of base catalysed intramolecular dehydrative cyclization of substituted thiosemicarbazides 3(a-f) and 4(a-f). The structures of these compounds were characterized by means of FT-IR, 1H-NMR, and elemental analysis data. All these compounds were screened for antibacterial, antioxidant, antitumor and cytotoxic activities. Results: Among these compounds: 5c, 5f and 6f were found active against gram positive cocci, the compounds 5a, 5b, 5d, 6a and 6f showed 85% free radical scavenging effect at 3 ppm when tested for antioxidant activity, 75% tumors inhibition was recorded using 5c, 5d and 6a and brine shrimps lethality assay declared 5a, 5b and 6d was 129.62 μg/ml, 161.577 μg/ml and 81.56 μg/ml respectively. Conclusion: Compounds carrying significant bioactivity can be further studied using animal models to establish their safety profile prior to initiating clinical trials.