4-吡啶甲醛氨基硫代酸酯的合成及其光学性质

4-吡啶甲醛和S-肼基二硫代甲酸苄酯经醛胺缩合反应合成了一种新型的氨基硫代酸酯衍生物——4-吡啶甲醛氨基硫代酸酯(3),其结构经1H NMR,IR,MS,元素分析及X-射线单晶衍射表征。3属三斜晶系,Pī空间群,晶胞参数a=4.683,b=11.573,c=26.100,α=80.381°,β=88.074°,γ=89.40°,V=1 393.83,Z=4。运用UV-Vis并结合理论计算,初步研究了3的光学性能。3的λmax位于336 nm和403 nm。

含水四氢呋喃中二茂钛全氟辛基磺酸配合物催化锌粉还原二硫醚及其在合成硫代酸酯中的应用

以含水四氢呋喃作溶剂,室温下,在5.0 mol%二茂钛全氟辛基磺酸配合物催化下,锌粉可以有效地还原断裂S—S键,形成亲核性的硫负离子与酸酐(α-溴代羰基化合物)反应,高产率得到对应硫代酸酯(α-硫代羰基化合物).讨论了反应机理.

Efficient in-situ end-functionalization of polydienes by isothiocyanate via neodymium mediated coordinative chain transfer polymerization system

End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.

脱基硫代甲酸酯配合物的合成、晶体结构、光谱及三阶非线性光学性质研究

报道三种有推拉电子基团的肼基硫代酸酯衍生物配体(HL^(1～3)).此类配体与二价过渡金属离子配位时脱去一质子,形成D-M-D和A-M-A(D=给体,M=金属,A=受体)类型、含有共轭体系的中性配合物.本文集中研究了该类配体的镍、铜、钯、铂配合物的IR、磁化率、ESR谱,电子光谱和三阶非线性光学性质,通过光谱研究初步确定了它们均为平面正方形构型配合物,文中还报道了CuL_2~1晶体结构.晶体属P(?)空间群,a=0.7835(2),b=1.0530(2),c=1.1816(2)nm,a=100.61(3),β=92.38(3),γ=110.00(3)°,Z=1,最终的R因子为0.063.通过晶体结构测试,进一步确定铜配合物的结构为平面构型.

低价钛引起的芳基二硫醚与α,β-不饱和酯(腈)的反应

芳香族二硫醚在低价钛试剂作用下,S-S键还原断裂成芳硫负离子,再与α,β-不饱和酯(腈)发生Michael加成反应,得到β-硫代酸酯(腈)。

Hydrophobic intensification flotation:Comparison of collector containing two minerophilic groups with conventional collectors

The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and micro-flotation experiments.The results showed that S-[(2-hydroxyamino)-2-oxoethyl]-O-octyl-dithiocarbonate ester(HAOODE)exhibited stronger hydrophobization and better flotation performance to malachite(Cu2(OH)2CO3)than octyl-hydroxamic acid(OHA)and its combination with S-allyl-O-ethyl xanthate ester(AEXE).To understand the hydrophobic intensification mechanism of HAOODE to malachite,zeta potential,atomic force microscopy(AFM)and XPS measurements were carried out.The results recommended that malachite chemisorbed HAOODE to form Cu—HAOODE complexes in which the hydroxamate—(O,O)—Cu and—O—C(—S—Cu)—S—configurations co-existed.The co-adsorption of HAOODE’s hetero-difunctional groups was more stable than the single-functionalgroup adsorption of OHA and AEXE,which produced the“loop”structure and intensified the self-assembly alignment of HAOODE on malachite surfaces.In addition,the“h”shape steric orientation of the double hydrophobic groups in HAOODE facilitated stronger hydrophobization toward malachite than the“line”or“V”hydrophobic carbon chains of OHA or AEXE.Thus,HAOODE achieved the preferable flotation recovery of malachite particles in comparison with OHA and AEXE.

Effects of Na2S2O3 and Glucose on the Compositions of Glycerolipids and Their Fatty Acids in Synechocystis sp. PCC 6803 Cells

Compositions of glycerolipids and fatty acid compositions of glycerolipids were compared among Synechocystis sp. PCC 6803 cells grown in the BG-11 medium containing different concentrations of glucose and Na2S2O3 in this study. It was found that Na2S2O3 can effectively increase the percentage of sulphoquinovosyl diacylglycerol (SQDG) and phosphatidylglycerol (PG) to total membrane lipids and the simultaneous application of glucose with Na2S2O3 can counteract the effect of Na2S2O3. In addition, Na2S2O3 can significantly increase the percentage of palmitic acid (C, 16:0) in fatty acid composition of monogalactosyl diacylglycerol (MGDG) and digalactosyl diacylglycerol (DGDG) and decrease the fatty acid unsaturation degree accordingly, and these effects can also be eliminated by glucose. These results indicate that Na2S2O3 can take as a reductant to make membrane lipids in a low unsaturated state, and the simultaneous application of glucose can decrease the reducing power of Na2S2O3. In addition, Na2S2O3 can take as a sulfur donor for the synthesis of SQDG.

Adsorption and flotation mechanism of a ketoxime-dithiocarbonate surfactant to chalcopyrite

The adsorption mechanism of O-isopropyl-S-[2-(hydroxyimino) propyl] dithiocarbonate ester(IPXPO) to chalcopyrite was investigated by using contact angle, in-situ atomic force microscopy(in-situ AFM), cyclic voltammetry(CV) and X-ray photoelectron spectroscopy(XPS). The results of contact angle and in-situ AFM demonstrated that IPXPO adsorbed on chalcopyrite increases surface hydrophobicity and roughness. It was found by CV experiments that a layer passive film was formed. The results of XPS spectra further revealed that the thiol S atom, oxime N atom, and O atom in the IPXPO molecule might react with copper atoms to form Cu-S, Cu-N, and Cu-O bonds, respectively. An artificial mixed minerals flotation test indicated that under the condition of pH=6.79 and IPXPO initial concentration 5×10^(-5)mol/L, the flotation recovery of chalcopyrite reached about 90%, while for pyrite only 25%, suggesting that IPXPO is an excellent collector for flotation separation and enrichment of chalcopyrite.

Evaluation of the effect of pyrrolidine dithiocarbamate in suppressing inflammation in mice with dextran sodium sulfate-induced colitis

AIM: To evaluate the effect of pyrrolidine dithio- carbamate (PDTC; an NF-κB inhibitor) administered at low (50 mg/kg) and high (100 mg/kg) doses in suppressing colitis in mice with dextran sodium sulfate (DSS)-induced colitis. METHODS: Mice were divided into a DSS-untreated group (normal group), DSS-treated control group, DSS+PDTC-treated groupⅠ(low-dose group), and DSS+PDTC-treated groupⅡ (high-dose group). In each group, the disease activity index score (DAI score), intestinal length, histological score, and the levels of activated NF-κB and inflammatory cytokines (IL-1β and TNF-α) in tissue were measured. RESULTS: The DSS+PDTC-treated groupⅡ exhibited suppression of shortening of intestinal length and reduction of DAI score. Activated NF-κB level and IL-1β and TNF-α levels were significantly lower in DSS+PDTC- treated groupⅡ. CONCLUSION: These findings suggest that PDTC is useful for the treatment of ulcerative colitis.

Floc flotation of jamesonite fines in aqueous suspensions induced by ammonium dibutyl dithiophosphate

The hydrophobic flocculation of jamesonite fines in aqueous suspensions induced by ammonium dibutyl dithiophosphate was investigated using laser particle size analysis, microscope analysis, electrophoretic light scattering and infrared spectroscopy.Single minerals of 4.607 μm for the 50% volumetric diameters were researched by varying several parameters, including p H,ammonium dibutyl dithiophosphate concentration, stirring strength and kerosene addition. It is found that the maximal floatability of jamesonite fines is induced by ammonium dibutyl dithiophosphate at p H 6, and the floc flotation increases with increasing ammonium dibutyl dithiophosphate concentration despite a simultaneous increase in the negative ζ potential of jamesonite, meaning that hydrophobic interaction between the particles increases much more strongly than electric double layer repulsion from the adsorption of ammonium dibutyl dithiophosphate. It is also found that the floc flotation is closely correlated with the size of flocs,which is strongly influenced by the stirring strength and enhanced by the addition of a small amount of kerosene. The results of FTIR spectra indicate that adsorption of ammonium dibutyl dithiophosphate onto jamesonite is chemical adsorption and the adsorption product is lead dibutyl dithiophosphate.

Synthesis of novel thionocarbamate for copper-sulfur flotation separation and its adsorption mechanism

As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electronic structures of IPDTC. The results showed that IPDTC had higher energy of the highest occupied molecular orbital but lower electronegativity than O-isopropyl-N-ethyl thionocarbamate(Z-200). It was predicted that IPDTC had strong collection ability according to the reaction energy criteria. Flotation results demonstrated that the collecting ability of IPDTC to chalcopyrite and pyrite was stronger than that of Z-200. Then, the flotation mechanism was analyzed by measurements of surface tension, adsorption capacity, XPS, FTIR and zeta potential. These results indicated that IPDTC could reduce the solution surface tension. The adsorption capacity of IPDTC on chalcopyrite was higher than that on pyrite, consistent with the results of the flotation tests. FTIR, zeta potential and XPS results also demonstrated that IPDTC was strongly absorbed on the chalcopyrite surface by formation of Cu—S—C bonds, but showed a weak affinity on the pyrite surface.

CoFe_2O_4/CdS nanocomposite:Preparation,characterisation,and application in sonocatalytic degradation of organic dye pollutants

A magnetic CoFe2O4/Cd S nanocomposite was prepared via one-step hydrothermal decomposition of cadmium diethanoldithiocarbamate complex on the surface of CoFe2O4 nanoparticles at a low temperature of 200 ℃.The nanocomposite was characterised by X-ray diffraction（XRD）,Fourier transform infrared spectroscopy（FT-IR）,scanning electron microscopy,energy-dispersive X-ray spectroscopy（EDX）,UV-visible spectroscopy,transmission electron microscopy（TEM）,N2 gas sorption analysis,X-ray photoelectron spectroscopy（XPS）,and vibrating sample magnetometry.The FT-IR,XRD,EDX and XPS results confirmed the formation of the CoFe2O4/Cd S nanocomposite.Based on the TEM analysis,the CoFe2O4/Cd S nanocomposite constituted nearly uniform,sphere-like nanoparticles of ～20 nm in size.The optical absorption spectrum of the CoFe2O4/Cd S nanocomposite displayed a band gap of 2.21 e V,which made it a suitable candidate for application in sono/photocatalytic degradation of organic pollutants.Accordingly,the sonocatalytic activity of the CoFe2O4/Cd S nanocomposite was evaluated towards the H2O2-assisted degradation of methylene blue,rhodamine B,and methyl orange under ultrasonic irradiation.The nanocomposite displayed excellent sonocatalytic activity towards the degradation of all dyes examined—the dyes were completely decomposed within 5–9 min.Furthermore,a comparison study revealed that the CoFe2O4/Cd S nanocomposite is a more efficient sonocatalyst than pure Cd S;thus,adopting the nanocomposite approach is an excellent means to improve the sonoactivity of Cd S.Moreover,the magnetic properties displayed by the CoFe2O4/Cd S nanocomposite allow easy retrieval of the catalyst from the reaction mixture for subsequent uses.

Synthesis and Characterization of Trithiocarbonate-Organoclays Nanohybrids and Their Interaction with MCF-7 Cancer Cells

This work presents a new approach for the fabrication of organic/inorganic nanohybrids as anticancer drugs by an intercalation method using S,S-bis（α,α′-dimethyl-α″-acetic acid） （trithiocarbonate） as a modifier and two organoclays, such as reactive octadecylamine/MMT （montmorillonite） and non-reactive dimethyldidodecyl ammonium/MMT. The chemical and physical structures and the surface morphology of these covalently and non-covalently linked nanohybrids were investigated by FT-IR （Fourier translbrm infrared） spectroscopy, ^13C and ^29Si solid state NMR （nuclear magnetic resonance） spectroscopy, XRD （X-ray powder diffraction） and SEM （scanning electron microscopy） analyses, respectively. To evaluate the anticancer activities of the novel BATC/organoclay hybrids against MCF-7 breast cancer cells, a combination of different biochemical and biophysical testing techniques were used. Cell proliferation and cytotoxicity were detected in vitro using a real-time analysis. Cell death was confirmed by using apoptotic and necrotic analyses, the effects of which were detennined by the double staining and Annexin-V-FLUOS testing method. The results demonstrate that intercalated hybrid complexes containing a combination of various anticancer sites, such as free and complexed carboxyl, trithiocarbonate, amine and ammonium cations significantly induced cell death in breast cancer via their interactions with the DNA macromolecules of cancer cells by destroying the self-assemb｜ed structure of growing cells. Fabricated hybrid complexes may represent a new generation of effective and selective anticancer drug systems with a synthetic/natural origin for cancer chemotherapy.

Syntheses,Spectroscopic Properties and Crystal Structures of (2-Cl-C_6H_4CH_2)_3SnS_2CN(C_5H_(10)) and (2-Cl-C_6H_4CH_2)_3SnS_2CN(C_4H_9N)

Two tri(2-chlorobenzyl)tin(IV) complexes with dithiocarbamate ligands (2-Cl- C6H4CH2)3SnS2CN(C5H10) 1 and (2-Cl-C6H4CH2)3SnS2CN(C4H9N) 2 have been synthesized by the reaction of tri(2-chlorobenzyl)tin(IV) chloride with dithiocarbamates and characterized by elemental analysis, IR and 1H NMR. The crystal structures were determined by X-ray single-crystal diffraction. The crystal of complex 1 belongs to triclinic, space group P with a = 9.121(5), b = 10.788(6), c = 15.549(8) ? a = 77.812(6), b = 88.279(8), g = 72.023(6)o, Z = 2, V = 1421.5(13) ?, Dc = 1.532 g/cm3, ?= 1.344 mm-1, F(000) = 660, R = 0.0382 and wR = 0.0984; and that of complex 2 is of monoclinic, space group P21/n with a = 13.892(10), b = 2.1274(8), c = 2.0553(15) ? b = 107.145(11)o, Z = 4, V = 2726(3) ?, Dc = 1.600 g/cm3, ?= 1.403 mm-1, F(000) = 1320, R = 0.0361 and wR = 0.0826. Their structures show a distorted trigonal bipyramidal configuration with five- coordination for the central tin atoms.

Impact of Soil Texture and Organic Matter Content on Methyl Isothiocyanate Volatilization from Soil Columns

Metam sodium （MS; sodium N-methyl dithiocarbamate） has emerged as a promising soil fumigant in the US to replace methyl bromide （MeBr）. Metam potassium （MK; potassium N-methyl dithiocarbamate） and MS break down into the volatile gas methyl isothiocyanate （MITC） to control soil borne pests. Many studies have focused on MS, but MK has not been studied as thoroughly. The objective of this research was to determine the effect of increasing organic matter （OM） treatments and soil texture to minimize the off-gassing of MS and MK. Bench-scale soil column studies were performed to simulate organic matter treatments that may decrease the volatilization loss of MITC. Incorporation depth of OM simulated surface tillage （0-15 cm） practices. Soil was packed in steel columns and MS or MK was applied at a depth of 15 cm and MITC volatilization was measured using gas chromatography/mass spectroscopy. Volatilization of MITC behaved similarly for MS and MK with MITC movement impacted by soil texture. MITC volatilization was lower from a sandy clay loam than a sandy soil. Surface incorporation of OM did not significantly decrease MITC volatilization. These results suggest that soil texture is the dominant factor reducing MITC off-gassing and prolonging the time needed to control soil borne pests.

Discovery of novel dithiocarbamic acid ester HGWJ-11C with significant anticancer action

To find novel lead compound, seventy-four compound libraries were built through two rounds by a solution-phase CC on the basis of our developed method for the synthesis of dithiocarbamic acid ester. After evaluation for the antitumor activities of libraries, six compounds were selected to be synthesized and examined their antitumor activities. It was found that compound 13 （HGWJ-11 C） with novel structure exhibited significant antitumor activities and the scaffold of dithiocarbamic acid was very crucial for the antitumor activity. The compound 13 is worth studying deeply as a potent hit compound.

Effects of compound 209 on colorectal cancer cell HT-29 in vivo and in vitro

Compound 209 is a newly synthesized dithiocarbamate derivative with antiproliferation activity in vitro, however, its antitumor effect in vivo and the underlying mechanisms have yet to be identified. We explored the antitumor effect of compound 209 and the possible mechanisms for its inhibition of the growth of HT-29 xenograff tumor and proliferation of HT-29 cells. Cell proliferation was evaluated with SRB assay in vitro. The results showed that compound 209 had significant antiproliferation activity on HT-29 cells. Furthermore, the xenograff HT-29 nude mouse model was used to study the antitumor effect of compound 209 in vivo. We found that compound 209 significantly inhibited tumor growth and did not cause loss of body weight or leukocytopenia. Analysis by flow cytometry indicated that compound 209 arrested HT-29 cell cycle in G~ phase. Western blotting analysis suggested that compound 209 increased the expression of p27, cyclin E, CDK2, cyclin D1 and CDK4. These results demonstrated the antitumor effect of compound 209 and its potential use as an anticancer drug.

Enhanced antitumor effect of TM208 in combination with 5-fluorouracil in H_(22) transplanted mice

4-Methylpiperazine-l-carbodithioc-acid-3-cyano-3,3-diphenylpropyl ester hydrochloride（TM208）,a newly synthesized dithiocarbamate derivative,exhibits antitumor effect in vivo with low toxicity.However,the antitumor effect of TM208 in combination with drugs in clinical use for cytotoxic chemotherapy has not been identified.In our study,the antitumor effects and toxicities of TM208 in combination with cisplatin（DDP）,cyclophosphamide（CTX） and 5-fluorouracil（5-Fu）,respectively,were evaluated in vivo using a transplanted solid-type hepatocarcinoma H_（22） mice model.The results suggested that 5-Fu（5 mg/kg/2d） potentiated the antitumor effect of TM208（100 mg/kg/d） with significantly higher tumor inhibition rates（P0.01） and a slight elevation of toxicity;however,DDP and CTX in combination with TM208 did not exhibit similar enhanced antitumor effect.For further investigation,we found that the TM208 and 5-Fu combination therapy led to G_2/M cell cycle arrest of tumor cells in vivo by downregulating the protein expression of cyclin Bl,cdc2,cdk7,and upregulating the expression of p21 and p53.The protein expression levels of cyclin Dl and cyclin E were also downregulated in tumor cells treated with TM208 and 5-Fu,while those of cdk4 and cdk2 remained unchanged.The change of mRNA expression level of cdc2 was consistent with that of its protein in each group,while the mRNA expression of cyclin B1 remained unchanged among each group.These results demonstrated the dosage regimen of TM208 for combination therapy and could serve as evidence for clinical use of TM208 as an antineoplastic drug.

IC5, a dithiocarbamate derivative, inhibits colon cancer cell proliferation in vitro and colitis-associated colorectal carcinogenesis in vivo

Colorectal cancer （CRC） is one of the leading causes of cancer-related deaths, and inflammatory bowel diseases and dysregulated cell proliferation play important roles in colorectal carcinogenesis. Therefore, inhibition of inflammatory signaling and cell proliferation is used as a major strategy for chemoprevention of CRC. In the present study, it was found that IC5, a dithiocarbamate derivative, could inhibit the proliferation of LoVo human colon cancer cells in a concentration-dependent manner, with an IC50 of 22 gM. The anti-proliferation effect of IC5 was accompanied by a significant cell cycle arrest in G2/M phase. Further study revealed that IC5 significantly inhibited NF-~B signaling in LoVo cells, suggesting that IC5 could inhibit inflammatory responses. We then evaluated the in vivo efficacy of IC5 to inhibit colitis-associated colorectal carcinogenesis using an azoxymethane （AOM）/dextran sodium sulfate （DSS） mouse model. AOM/DSS treatment resulted in a CRC incidence of 58.3%, while the incidences were decreased to 37.5% and 25% in mice orally administered with 50 and 100 mg/kg IC5, respectively. In addition, IC5 also reduced the plasma levels of alanine aminotransferase and asparatate aminotransferase. Taken together, these results suggested that IC5 could prevent colitis-associated colorectal carcinogenesis, and more attention should be paid to it as a cancer chemopreventive agent in further investigation.

Efficient synthesis of thiohydantoin derivatives from amino acid esters and isothiocyanates in alkaline Al_2O_3

Various amino acid esters were reacted with different isothiocyanates in alkaline Al2O3 at room temperature for 1 h affording thiohydantoins in moderate to excellent yields.