Synthesis and Characterization of New Schiff Bases Formed by Condensation of 2,9-Phenathroline-1,10-dialdehyde with Sulfur-Containing Amines

Four new Schiff bases of 1,10-phenanthroline-2,9-dicarboxaldehyde with sulfur-containing amines such as 2-mercaptoaniline, S-alkyl/aryl dithiocarbazates and thiosemicarbazide have been synthesized and characterized by spectroscopic and X-ray crystallographic techniques. A comparative study of the methods of synthesis has been made using both traditional and microwave techniques. A significant reduction in reaction time has been observed when the microwave method was used. In some of the reactions, the yields also increased significantly.

QSPR Study on the Boiling Points of Some Oxygenand Sulfur-containing Organic Compounds

Structural and thermodynamic parameters of 56 oxygen-containing and 56 sulfur- containing organic compounds were computed at the B3LPY/6-311G＊＊ level using density functional theory （DFT） method. Furthermore,the dependent equations between the experimental data of boiling points （Tb） and theoretical parameters were proposed with SPSS12.0 for windows software,whose correlation coefficients R2 are 0.933 and 0.945. These dependent equations were validated by cross-validation method （q2 are 0.923 and 0.929,respectively）. VIF （variance inflation factors） and t-value methods were also used to verify the significance and self-correlationship of each variable. Results indicate that our dependent equation exhibits good prediction ability,and molecular polarizability （α） is the main factor affecting the Tb of oxygen- and sulfur-containing organic compounds. To our interest,obvious dependence could also be found among the oxygen- and sulfur-containing organic compounds＇ experimental data of boiling points （Tb） with R^2 of 0.857.

An Innovative Method for the Determination of Sulfur-containing Compounds by Vapor Molecular Absorption Spectrometry

Since the most sensitive resonance lines of nonmetallic elements are situated in vacuum ultraviolet region （below 190 nm）, they can not be directly determined with a common AAS instrument covering the spectral range from 190 to 700 nm. The molecular absorption spectrometry is often used for the determination of nonmetallic elements. Syty et al. used vapor molecular absorption spectrometry（VMAS） to determine the sulfur dioxide and sulfide, in which a hydrogen hollow cathode lamp was used as a continuum source to determine SO;at 210 nm and a deuterium arc

Study on structural characteristics and adsorption performance of ultrasonic treated Mn-containing sulfur transfer agent

To prepare manganese-containing spinel sulfur transfer agent with acid peptization, ultrasonic wave is used for the first time to modify the structure of sulfur transfer agent in this work. Mini fixed bed reactor was used to investigate the effect of ultrasonic power, time and temperature on the structure and oxidation adsorption performance of sulfur transfer agent and the adsorption kinetics and mechanism of SO2 were analyzed. SEM, TEM, XRD and N2 adsorption-desorption techniques were employed to characterize and analyse the function of sulfur transfer agent. The results indicated that manganese-containing spinel is a kind of promising sulfur transfer agent and exhibits higher sulfur capacity and desulfurization degree under the selected conditions of the ultrasonic wave power of 60%, and with the treatment period for 3 h at a temperature of 60 ℃.

DFT Study of Geometrical and Vibrational Features of Sulfur Containing Amino Acids in Hydrated Media： L-Cysteine and L-Methionine

Geometry optimization at the B3LYP/6-31＋＋G＊ level of theory has been undertaken on clusters containing L-Met （L-methionine） or L-Cys （L-cysteine） surrounded by eight water molecules. The comparison of the structural parameters of L-Met and L-Cys with X-ray experimental values is in good agreement within 4.8%. This result shows that the privileged positions of water molecules and the possible hydrogen bonding network formed around the backbone of both AAs （amino acids） are adequate. Subsequent calculations of the harmonic vibrational modes followed by a post-processing treatment enable us to assign the vibrational modes of L-Met and L-Cys surrounded explicitly by eight water molecules. The frequencies of the assigned modes are in good agreement with available IR （infra red） and Raman values within 5%.

Synthesis of derivatives of imidazo[4,5-b]pyridine:Novel sulfur contained side chains for macrolide antibiotics

Two series of novel derivatives of imidazo[4,5-b]pyridine were synthesized. These compounds could be used as side chains of semisynthesised ketolide antibiotics. The side chains have free amine group which can attached to ketolide core. Macrolides with this kind of side chains will show obvious activities against erythromycin-resistant strains. The structure of the side chains was confirmed by ^1H, ^13C NMR, MS, HMBC spectra. 2007 Ping Sheng Lei. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Sulfi de ore prospecting in carbon-containing stratum using comprehensive time-domain induced polarization and controlled-source audio-frequency magnetotellurics

Carbon-bearing stratum normally features low resistance and high polarization.If the lithostratigraphy of the exploration area contains large amounts of carbon,the induced polarization anomaly caused by metal sulfide ore bodies will be inundated by the high polarization of carbon-containing wall rock.In this work,we adopted time-domain induced polarization(TDIP)and controlled-source audio-frequency magnetotellurics(CSAMT)on deep prospecting of the carbon-bearing stratum of the Ar Horqin Banner,Inner Mongolia.The underground medium is divided into target geologic bodies according to the geological information within the known exploration line borehole,and the physical properties of various target geologic bodies are calculated using weighted averages to build a geologic-geophysical model that can fit the observation data.Consequently,we can determine the range and morphological characteristics of the electrical properties of the ore-bearing geologic bodies in the inversion results in the study area.Then we can use the characteristics summarized from the known exploration line to interpret unknown exploration line.Results indicated that,when the diff erence in physical properties between the ore body and interference wall rock is not clear,the geologic body can be classifi ed via the paragenetic(associated)assemblage relations of the underground medium.Geological interpretation is guided by the comprehensive physical properties of ore-bearing geologic bodies to avoid interferences.

Characterizations of Phosphorus-containing Flame-retardant Poly(Ethylene Terephthalate) Copolyester

Copolyesters of phosphorus - containing flame - retardant poly(Ethylene Terephthalate) (PET) have been prepared and characterized with the objection of producing an effective, environmentally friendly, nonfugitive alternatives to halogen flame retardant system for practical application. With means of NMR, DSC, DTA/TGA, SEM and LOI, structure, thermal property and flam-mability are investigated which reveal that the flame -retardant PET when copolymerized with 2 - carboxyethyl (phenylphosphinic) acid (CEPP) confers excellent fire retardancy with LOI 】 28, broader thermal degradation temperature and increased char formation.

Determination of sulfur anions by ion chromatography-postcolumn derivation and UV detection

A novel method for determination of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate in foodstuffs by ion chromatography separation with postcolumn derivation and UV detection has been developed. All species are separated at Dionex IonPac AG22A and AS22A with mobile phase of a mixture of 4.5 mmol/L sodium carbonate and 0.8 mmol/L sodium bicarbonate at a flow-rate of 1.0 mL/min. The postcolunm derivation solution was 0.24% iodine in 0.2% phosphate acid and the detection wavelength was set at 288 nm. The detection limits （LOD, signal-to-noise ratio of 3） of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate were 0.004, 0.006, 0.006, and 0.007 mg/L, respectively. Within-day relative standard deviations （RSD, n = 10） of formaldehyde sulfoxylate, sulflte, thiocyanate, and thiosulfate were 3.24%, 3.76%, 2.68%, and 2.07%, respectively. The recoveries of the four anions were in the range of 67.2-116.5%.

食用香料α-甲硫基甲基肉桂醛的制备

含硫香料化合物具有阈值低、特征性强的特点,对很多食物的特征香气具有重要的贡献。FEMA号为3717的α-甲硫基甲基肉桂醛是一个具有典型西兰花、青蚕豆香气的含硫香料化合物。受到制备方法的限制,该香料至今未能实现规模化生产,文献报道的产率只有约8%。以肉桂醛为原料,二甲亚砜和草酰氯为甲硫基甲基化试剂,开发了制备食用香料α-甲硫基甲基肉桂醛的新方法。用GC-MS监测反应中原料肉桂醛的残余量,考察了投料比、溶剂种类、反应温度等反应条件对产物产率的影响。结果表明:以二甲苯为溶剂,二甲亚砜和草酰氯先反应产生亲电性的甲基亚甲基硫钅翁盐的中间体,然后向反应体系中加入三乙胺、1,4-二氮杂双环[2.2.2]辛烷(DABCO)和肉桂醛,在回流条件下DABCO与肉桂醛共轭加成产生的亲核的烯醇负离子与甲基亚甲基硫钅翁盐离子反应,加成产物经过消除后得到α-甲硫基甲基肉桂醛,优化条件后产率可达52%。采用^(1)H NMR的NOE差谱方法,测定了产物α-甲硫基甲基肉桂醛的立体构型,确定了分子中的双键为反式构型。希望研究可为食用香料α-甲硫基甲基肉桂醛的规模化生产提供方法参考。

基于超高效液相色谱-三重四极杆串联质谱法的黑蒜加工过程中特征成分变化规律

基于超高效液相色谱-三重四极杆串联质谱技术建立了黑蒜中10种风味前体物质和21种游离氨基酸同时测定的检测方法。将该方法应用于黑蒜加工过程中特征成分变化规律的研究,结果表明,在温度75℃、相对湿度85%条件下,黑蒜中的特征成分含量在加工过程中发生了较大改变。其中,γ-氨基丁酸、S-烯丙基-L-半胱氨酸、异蒜氨酸、谷氨酰胺、甲基蒜氨酸、蒜氨酸、色氨酸和γ-L-谷氨酰-S-烯丙基-L-半胱氨酸变化最为显著,是黑蒜加工过程中小分子代谢物变化的化学标志物。该方法灵敏度高、准确性好,可满足检测需求。

蜂窝状ZSM-5沸石协同低温等离子体净化含硫恶臭气体

采用蜂窝状ZSM-5沸石协同低温等离子体净化5种典型含硫恶臭气体,通过沸石硅铝比、锰改性、放电电压参数的优化探究最佳工艺参数与处理效果。结果表明:降低硅铝比、锰改性利于提升蜂窝状ZSM-5沸石对含硫恶臭气体的整体吸附效率,增大硅铝比、适当增加锰负载量、提高放电电压则利于提升蜂窝状ZSM-5沸石协同低温等离子体对含硫恶臭气体的去除效率,其提升机制可能与沸石比表面积、外表面积和Mn^(3+)负载催化有关。在硅铝比为70(摩尔比)、锰负载量为10%(质量分数)、7.5 kV的条件下,锰改性蜂窝状ZSM-5沸石协同低温等离子体对含硫恶臭气体的去除效率均大于95%,比输入能量仅为2.3 J/L。

Fe-Co/LDHs催化剂的制备及催化氧化含硫废碱液

本文基于催化空气氧化模拟含硫废碱液和真实石化企业含硫废碱液,以水铝钙石为载体,利用浸渍法制备Fe-Co复合氧化物非均相负载型催化剂(Fe-Co/LDHs),并优化催化剂制备条件和反应条件。当催化剂中n(Fe):n(Co)=9:1(摩尔比)、总金属负载率为25%、焙烧温度为600℃时,制备的催化剂效果最好;处理6000 mg/L的模拟含硫废碱液时,每升添加10 g催化剂,在75℃下曝气量为2.5 L/min时效果最佳,3 h脱硫率可达到96.7%;而处理相同浓度的实际含硫废水时,3 h脱硫率可达92.4%,且循环使用10次后催化效果无明显下降。结果表明Fe-Co/LDHs催化剂的催化活性优异且稳定,具有较好的应用前景。

Propene and CO oxidation on Pt/Ce-Zr-SO_4^(2-) diesel oxidation catalysts:Effect of sulfate on activity and stability

Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^（2-） with 10 wt%SO_4^（2-）,the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^（2-） support,and the increased number of Pt particles built up more Pt^（-）-（SO_4^（2-））^（-） couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^（2-） with good sulfur resistance.

气相色谱-场电离高分辨飞行时间质谱在柴油详细组成分析中的应用

气相色谱-场电离飞行时间质谱联用方法(GC-FI TOF MS)结合了气相色谱在线分离、场电离软电离技术和高分辨飞行时间质谱技术,采用该技术表征了不同柴油样品的详细组成。结果表明,与现有的ASTM D2425方法相比,样品无需预分离,可直接进样分析,且提供的样品信息更加丰富,能够同时得到柴油的烃类化合物和含硫、含氮化合物类型分布和碳数分布。

HPLC-GC-AED法研究柴油中硫化物组成及分布

采用HPLC-GC-AED法研究科威特常三线柴油中硫化物组成及分布。用HPLC对油样进行预分离,切割出5个馏分并回收,再采用GC-AED技术检测各组分中的硫化物,确定其结构类型及分布。结果表明,科威特常三线柴油中硫化物的类型为不同碳数取代基的苯并噻吩类和二苯并噻吩类;烷基取代苯并噻吩类中,各硫化物含量随取代基碳数增多呈递增分布,而烷基二苯并噻吩类中,取代基碳数较少的硫化物C3DBT、C2DBT、C1DBT中硫的含量较高。含硫化合物主要分布在L1～L3馏分,其中L2中硫的含量最高,占总硫的44.4%。最难以加氢脱除的含硫化合物4-MDBT主要分布在L2馏分中,而4,6-DMDBT主要分布在L3馏分中。

FCC汽油硫化物在ZSM-5催化剂上的加氢脱硫路径

采用气相色谱-原子发射光谱(GC-AED)方法,考察了催化裂化(FCC)汽油中的硫化物和相应模型硫化物在ZSM-5催化剂上的催化转化性能。结果表明,FCC汽油硫化物总转化率为86.3%,其中,硫醚和四氢噻吩的转化率都达到100%,硫醇、噻吩、烷基噻吩和苯并噻吩的转化率分别为96.6%、78.8%、85.8%和81.4%。3-甲基噻吩在ZSM-5催化剂上的转化产物中含有噻吩、2-甲基噻吩、2,5-二甲基噻吩、2,4-二甲基噻吩和2,3-二甲基噻吩。烷基噻吩和苯并噻吩硫化物在ZSM-5催化剂上脱硫反应网络中,一方面含有直接加氢脱硫反应,另一方面含有包括歧化、异构化和裂解等反应的间接加氢脱硫反应。

油气田含硫废水化学混凝-臭氧氧化复合处理工艺

对油气田含硫废水来源、组成及危害进行分析,提出化学混凝-臭氧氧化复合处理的工艺技术。通过单因素和正交实验,对化学混凝及臭氧氧化处理的影响因素进行分析,得到了优化的工艺条件:①采用化学混凝处理时,混凝剂选用HNJFZ混凝剂(加量为3500mg/L),絮凝剂选用FASG絮凝剂(加量为15mg/L),体系的pH值为8～9;②采用臭氧氧化深度处理时,臭氧浓度为60mg/L,氧化时间为40min,pH值为10.0左右。采用上述复合处理工艺条件对含硫废水进行处理验证。验证结果显示,含硫废水的水色清澈,CODCr由6346mg/L降至98.5mg/L,S2-浓度由132mg/L降至0.897mg/L,去除率分别达到98.4%和99.3%,可满足污水综合排放标准(GB8978—1996)的要求。

芳香杂环含硫化合物C-S键断裂方式

主要总结分析了二苯并噻吩类含硫化合物及其加氢中间体中C-S键类型和断裂方式,同时对二苯并噻吩和4,6-二甲基二苯并噻吩在过渡金属硫化物和磷化物上的加氢脱硫(HDS)反应网络和动力学进行了综述。在这些含硫化合物的HDS反应网络中包含了多种C-S键,其断裂机理呈现多样性,决定了催化剂活性中心的多样性和复杂性。因此,每一种HDS催化剂都表现出独特的催化性能。该综述有助于理解HDS催化剂构效关系,为深度HDS催化剂的开发提供理论支持。

固相微萃取、液液萃取结合气相色谱-质谱法分析芝麻香型白酒中的含硫化合物

应用固相微萃取法、液液萃取法结合气相色谱-质谱联用分析手段对芝麻香型白酒中含硫化合物进行定性分析。通过配制模拟酒样对固相微萃取法、液液萃取法的前处理条件进行优化。在最优条件下对36个芝麻香型白酒酒样中的微量成分提取分析,固相微萃取法共检出178种挥发性成分,液液萃取法共检出239种挥发性成分。两种方法共检出14种含硫化合物,均采用标准品比对进行准确定性。首次在中国白酒中检测出硫代丁酸甲酯、糠基甲基硫醚、硫代呋喃甲酸甲酯、4-甲基二苯并噻吩、3-甲硫基丁醛、甲基硫代磺酸甲酯6种含硫化合物;此外,首次在芝麻香型白酒中检出苯并噻唑和苯并噻吩。