烷基结构对MoDDPs摩擦磨损性能的影响

制备了不同碳原子数的伯、仲烷基MoDDPs,并研究了其油溶性,测定了其加入到100SN基础油中的抗磨性、减摩性和极压性。比较了烷基碳链的长短及伯、仲烷基不同结构对MoDDPs摩擦磨损性能的影响。结果表明仲烷基MoDDPs的摩擦磨损性能优于伯烷基MoDDPs。

基于Py-GC/MS分析的二烷基二硫代磷酸锌的烷基结构研究

利用裂解气质联用(Py-GC/MS)技术研究二烷基二硫代磷酸锌(ZDDP)的烷基结构。通过分析500℃试样的裂解气质图谱,得出主要的裂解产物为硫醇和烯烃,这些产物与试样的烷基结构有直接联系,从而推断出对应的烷基结构及相对含量比例。实验结果表明:T202系列试样均含有正丁基、异辛基和正辛基,且相对含量n(正丁基)∶n(异辛基)∶n(正辛基)=1∶3∶2,T203和T204系列试样均含有异辛基和正辛基,n(异辛基)∶n(正辛基)=1∶1,T205系列试样均含有异辛基,异丙基和正辛基,n(异辛基)∶n(异丙基+正辛基)=1∶1,烷基种类与市场上ZDDP型号相一致。

烷基苯分子结构与分配系数间定量关系的研究

应用Benson基团加和法，对烷基苯分子结构与分配系数间的关系进行了研究。对部分烷基苯的正辛醇／水分配系数做了估算，估算结果表明烷基苯分配系数的对数值具有良好的基团加和性，预测值与测量值吻合很好。

锆离子改善十烷基磷酸组装膜结构及性能研究

利用烷基磷酸、金属锆离子和不锈钢电极表面的相互作用,通过表面自组装,在304不锈钢电极表面分别修饰了单层和双层烷基磷酸自组装膜,采用接触角和极化曲线对修饰电极进行测量.实验表明,双层烷基磷酸修饰膜具有更佳的耐腐蚀性能.

HPLC法测定奥美沙坦酯2个氯代基因毒杂质的含量

是为了建立HPLC 法测定奥美沙坦酯原料药中3和氯代基遗传毒杂质的含量。方法 色谱柱为苯基键合硅烷硅胶为填充剂(Kromail Eternity 5-Pheny Hexyl 250×4.6mm,5μm),用磷酸二氢钾溶液(将2.04克的磷酸二氢钾溶于水中,稀释到1000ml,用磷酸将 pH调整到3.2)作为移动相,用乙腈作为移动相 B,用直线梯度法将其从样品中分离出来;该方法的探测波长为215 nm;流量1.0ml/分钟,温度40℃,10μ L进样。结果 结果表明,在0.17μ g/ml—8.5μ g/ml范围之内,3个样品的峰面积与其含量有很好的相关性(r=0.9999),平均加标为98.9%;结果表明,在0.17μ g/ml—8.5μ g/ml范围之内,杂质4与其峰面积之间有很好的相关性(r=0.9999),平均回收率为103.3%;杂质5质量浓度在0.17μg/ml~8.5μg/ml内与峰面积呈良好的线性关系(r=0.9998),平均回收率为97.7%。结论 本方法可用于同时测定奥美沙坦酯原料药中3和氯代基遗传毒杂质的含量,且专属性强,耐用性好。

奥美沙坦酯中4-氯甲基-5-甲基-1,3-二氧杂环戊烯-2-酮和4,5-二氯甲基-1,3-二氧杂环戊烯-2-酮的HPLC法测定

目的:建立高效液相色谱法(HPLC)测定奥美沙坦酯中氯代烷基结构类潜在基因毒性杂质[4-氯甲基-5-甲基-1,3-二氧杂环戊烯-2-酮(杂质1)和4,5二氯甲基-1,3-二氧杂环戊烯-2-酮(杂质2)]。方法:采用色谱柱为Kromasil Eternity 5-Phenyl Hexyl柱(4.6 mm×250 mm,5μm);检测波长:215 nm,流动相A:乙腈:2.04 g·L^(-1)磷酸二氢钾溶液(用1.73 g·L^(-1)磷酸溶液调节pH值至3.4)(20∶80);流动相B:2.04 g·L^(-1)磷酸二氢钾溶液(用1.73 g·L^(-1)磷酸溶液调节p H值至3.4):乙腈(20∶80),进行梯度洗脱,流速为1.0 m L·min^(-1),柱温40℃,进样量10μL。结果:杂质1和杂质2与主峰分离良好,在浓度为0.106 6~0.710 4μg·m L^(-1)和0.123 5~0.617 4μg·m L^(-1)范围内杂质1和杂质2的线性关系良好(相关系数分别为1.000 0和0.997 1);杂质1和杂质2的平均回收率分别为98.09%和114.85%,RSD(n=9)分别为7%和7%。通过上述色谱条件进行验证,杂质1和杂质2检测限的相对浓度分别可达0.000 3%和0.000 4%,适用于杂质1和杂质2的测定。同时3批奥美沙坦酯成品中,杂质1和杂质2未检出,表明这两种杂质经过奥美沙坦酯的合成、精制和干燥处理后未传递到成品中。结论:经方法学验证,本法准确性好、灵敏度高,适用于奥美沙坦酯中的杂质1和杂质2的定量控制。

Synthesis and Characterization of Tris(cyclopentylcyclopentadienyl)lanthanide Complexes (C_5H_9C_5H_4)_3NdBrLi(THF)_3 and (C_5H_9C_5H_4)_3SmTHF

(C5H9C5H4)(3)NdBrLi(THF)(4)(1)(C5H9=cyclopentyl) was obtained from the reaction of NdCl3 with C5H9C5H4Na and LiBr (Nd:Na:Li=1:2:1 molar ratio) in THE X-ray crystallography showed that the ten-coordinated neodymium atom is bonded to three cyclopentylcyclopentadienyl(eta(5)) rings and a single bromine atom bridging a lithium which is bonded to three THF molecules. Complex 1 is triclinic, P1 space group with unit dimensions of a= 12.048(2), b= 13.498(3), c= 13.831(3)Angstrom, a = 104.16(3), beta = 104.07(3), gamma =95.96(3)degrees, V=2083.3(7)Angstrom(3), Z=2, D-c=1.35Mg/m(3) and F(000)=874. (C5H9C5H4)(3)SmTHF (2) was synthesized by reaction of anhydrous SmCl3 with C5H9C5H4Na at a molar ratio of 1:3. The structure was determined by X-ray crystallography. The ten-coordinated samarium atom is bonded to three cycloperrtylcyclopentadienyl rings and one oxygen of THF molecule to form a pseudo-tetrahedron. Complex 2 is orthorhombic, Fdd2 space group with unit cell dimensions of a =28.175(5)Angstrom, b =46.24(2) Angstrom, c =9.167(4) Angstrom(3), V=11943(8)Angstrom(3), Z= 16, D-c = 1.38Mg/m(3) and F(000)=5136.

An alternate aqueous phase synthesis of the Pt3Co/C catalyst towards efficient oxygen reduction reaction

Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is highly demanded.Herein we initially report an alternate aqueous phase one-pot synthesis of such catalysts(containing nominally ca.20 wt.%Pt)based on dimethylamine borane(DMAB)reduction.The as-obtained electrocatalyst(denoted as Pt3Co/C-DMAB)is compared with the ones obtained by NaBH4 and N2H4·H2O reduction(denoted as Pt3Co/C-NaBH4 and Pt3Co/C-N2H4·H2O,respectively)as well as a commercial Pt/C,in terms of the structure and electrocatalytic property.It turns out that Pt3Co/C-DMAB exhibits the highest ORR performance among all the tested samples in an O2-saturated 0.1 mol/L HClO4,with the mass activity(specific activity)ca.4(6)times as large as that for Pt/C.After 10000 cycles of the accelerated degradation test,the half-wave potential for ORR on Pt3Co/C-DMAB decreases only by 4 mV,in contrast to 24 mV for that on Pt/C.Pt3Co/C-NaBH4 or Pt3Co/C-N2H4·H2O shows a specific activity comparable to that for Pt3Co/C-DMAB,but a mass activity similar to that for Pt/C.ICP-AES,TEM,XRD and XPS characterizations indicate that Pt3Co nanoparticles are well-dispersed and alloyed with a mean particle size of ca.3.4±0.4 nm,contributing to the prominent electrocatalytic performance of Pt3Co/C-DMAB.This simple aqueous synthetic route may provide an alternate opportunity for developing efficient practical electrocatalysts for ORR.

Synthesis,Characterization and Crystal Structure of the Dimeric Organotin Compound:{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2)

The title compound,{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2),has been synthesized by the reaction of(tetrahydro-pyrrodithiolocarbamoylthio)acetic acid with the di-n-bubyltin oxide in1∶1molar ratio.The complex has been characterized by elemental analysis,IR and NMR.The crystal structure of it has been determined by X-ray single crystal diffraction.And the results showed that the crystal belongs to triclinic system with space group P1and some crystal parameters:a=1.2202(9)nm,b=1.3158(10)nm,c=1.3804(10)nm,α=111.215(9)°,β=99.357(9)°,γ=96.075(10)°,V=2.006(2)nm 3,Z=1,F(000)=908,μ=1.489mm^(-1),D c=1.474g·cm^(-3),R_(1)=0.0375,wR_(2)=0.0839.The complex has a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn_(2)O_(2)unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom which has a distorted octahedron.Each of the endo-cyclic tin atoms exhibits a distorted trigonal bipyramid coordination geometry with an additional weak coordination carboxylate oxygen.Four carboxylate ligands are divided into two types.And two of them are bidentate and connecting to each of exo-cyclic tin atoms by using both oxygen atoms,whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom only.CCDC:220513.

Syntheses and Crystal Structures of 4,4′Diformyl-diphenoxyethane and 4,4′4′′-Triformyl-triphenoxytriethylamine

Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.

CRYSTAL STRUCTURE OF RhCl(dppm)_2·H_2O

C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares to final R = 0. 037 and Rw = 0. 036 for 3432 (F> 6. 0σ(F) ) observed reflections. The structure of the title compound contains RhCl-(dppm)2 and non-coordinated H2O molecules. The rhodium atom is coordinated by one chlorine atom and four phosphorus atoms of two DPPM ligands forming a tetragonal pyramidal configuration.

Synthesis and Characterization of Linked Clusters Capped by Alkylidyne

The lsolobal displacement reaction between the dianion {M(CO)3[(h5-C5H4) C(O)C6H4C(O)(h5-C5H4)](CO)3M}2- and two molecules of [(m3-C)CO2Et]Co3(CO)9 gave rise to the formation of terephthaloyl(biscyclopentadienyl)-bridged double cluster complexes [(h5-C5H4)C(O)C6H4C(O)(h5-C5H4)]{[(m3-C)CO2Et]Co2M(CO)8}2 (M = Mo 1, M = W, 2). In the reaction, single cluster complexes[(m3-C)CO2Et]-Co2M(CO)8[h5-C5H4C(O)C6H4CO2CH3] ( M = Mo 3, M = W, 4) were yielded as by-products. All the cluster complexes were characterized by C/H analysis, IR and 1H NMR spectroscopy, and the structure of 3 has been determined by single-crystal X-ray diffraction method. Crystal data: Mr = 750.19, monoclinic, space group P21/c, a = 22.652(5), b = 8.954 (2), c = 14.530(3) ? b = 104.00(3), V = 2859.6(10) 懦, Z = 4, Dc = 1.743 mg/m? F(000) = 1488, m = 1.644 mm-1, the final R = 0.0555 and wR = 0.1353 for 5519 observations with I > 2s(I).

Synthesis and Crystal Structure of N-(5-Phenylseleno)pentyl Succinimide

N-(5-phenylseleno)pentyl succinimide 1, C15H19NO2Se (Mr = 324.27), was prepared by treating Br(CH2)5SePh with potassium succinimide. Its crystal structure has been determined by X-ray single-crystal diffraction. The crystal of 1 belongs to monoclinic system, space group P21/c with the crystal cell parameters: a = 18.018(6), b = 5.980(2), c = 14.682(5) ? = 109.977(6)? V = 1486.7(9) 3, Z = 4, Dc = 1.449 g/cm3, (MoK? = 2.523 mm-1, F(000) = 664,the final R = 0.0302 and wR = 0.0666 for 2623 independent observed reflections with I > 2(I). Structure analyses revealed that there exist strong nonclassical hydrogen bonds (CH…O).

Structural Analysis of Hydroxamate Reagents by X-Ray Diffraction

Axis House manufactures and supplies alkyl hydroxamate reagent of various carbon chain lengths for application in flotation of oxide copper and other minerals. As a part of reagent performance improvement, the structural factors of hydroxamate are examined by various analytical tools in particular with X-ray diffraction of single crystals. In a recent publication, the structures of n-octyl hydroxamic acid and its corresponding potassium salt are presented with findings of hydroxamic functional group geometric preference, H-bonding, keto-enol tautomerisation, acid-salt aggregation and alignment of carbon chain. In this paper, an example of branched alkyl hydroxamate3,5,5-trimethyl hexyl hydroxamate. hydroxamate is presented and compared with the result of linear alkyl

Study on the effect of methyl bromide and metham sodium fumigation on the soil protozoan community in a greenhouse environment

We examined soil fumigation effects on soil protozoan abundance and community structure in greenhouses and explored the capacity of protozoa to recover after disturbances. A randomized complete block design with five treatments and 4 replicates was set up in Qingzhou, Shandong Province, China. In addition to methyl bromide （MB） and untreated control （CK）, three alternative fumigation treatments were studied, including MB＋VIF （virtually impermeable films）, metham sodium （MS） and MS＋VIF. Tomato cultivars （Lyeopersicum eseulentum Mill）, cv. Maofen-802 were selected as test crops. Results of four fumigations were demonstrated through three-level ten-fold dilution methodology. Abundance of three groups of soil protozoa-flagellates, amoebae, and ciliates was measured from July 2002 to July 2003. Results indicated that two chemical fumigants and their combinations with physical material all significantly repressed soil protozoan abundance. MB was a stronger fumigant than MS, and use of VIF increased their repressive power. The most serious population reduction occurred in amoebae, thus, they also required the longest time to recover. MB and MS also changed the protozoan community structure. MB use decreased the percentage of amoebae but increased percentage of ciliates, while MS incrcased the percentagc of amoebae and decreased the percentage of flagellates in the protozoan community.

Structural properties of hydroxyl-substituted alkyl benzenesulfonates at the water/vapor and water/decane interfaces

Molecular dynamics simulations have been performed to investigate the structural properties of hydroxyl-substituted alkyl benzenesulfonate monolayers formed at the water/vapor and water/decane interfaces.We report a detailed study of the interfacial properties-liquid density profile,hydrogen bond structure,surfactant aggregate structure and order parameter-of the novel anionic surfactant,sodium 2-hydroxy-3-decyl-5-octylbenzenesulfonate(C10C8OHphSO3Na).Simulation results show that:with increasing number of surfactant molecules,the average number of intramolecular hydrogen bonds per surfactant molecule in the monolayer decreases,but the structures forming the intramolecular hydrogen bonds still play a dominant role;the hydrophobic part of the alkyl tail chain,especially the decyl substituent on the third carbon atom in the benzene ring,becomes straighter,and more ordered towards the external interface at higher surfactant coverage;two-dimensional radial distribution functions can describe the characteristic of surfactant aggregate structures and highlight the decane phase effect on the orientation of the hydrophobic part of the surfactant;the surfactant molecules readily form long-range hydrogen bonded structures.Our results are an important complement to experimental studies.We used the all-atom model by employing the GROMACS and ffAMBER programs in the simulations,which provides a new way to simulate the interfacial behavior of alkyl benzenesulfonate surfactants.

Layered double hydroxides with larger interlayer distance for enhanced pseudocapacitance

The interlayer space of the layered materials is not always the electrochemical active area for contributing to the pseudocapacitive process. To our knowledge, few efforts have been devoted to investigating the effect of interlayer distance of layered double hydroxides（LDHs） on pseudocapacitors. Here, we obtained the CoAl-LDH with different interlayer distance via the reaction in aqueous media hydrothermally. Electrochemical characterization reveals that the CoAl（DS^-（dodecyl sulfate））-LDHs with an interlayer distance of 2.58 nm can deliver higher specific capacitance of 1481.7 F g^-1 than CoAl（SO4^2-）-LDH（0.87 nm, 1252.7 F g^-1） and CoAl（CO3^2-）-LDH（0.76 nm, 1149.2 Fg^-1） at a discharge current density of 1 A g^-1. An asymmetric supercapacitor with the CoAl（DS^-）-LDHs‖activated carbon also shows a better electrochemical performance, including a high energy density of54.2 W h kg^-1 at a power density of 0.9 kW kg^-1 and a longterm stability, in comparison with CoAl（SO4^2-）-LDH and CoAl（CO3^2-）-LDH ‖activated carbon.

Unusual reaction of a tungsten alkylidyne complex with water.Formation,characterization,and crystal structures of oxo trimers

The reaction of the alkyl alkylidyne W（CH2CMe3）3（=CSiMe3） （1） with H20 in THF and with D20 in benzene-d6 gave two new trimeric oxo complexes： W3O3（μ=O）3（CH2CMe3）6（THF）3 （2） and [W303（μ=O）3（Ch2CMe3）6（D2O）3] 2benzene-d6 （3.2benzened6）, respectively, each containing two alkyl ligands per W atom. This is in contrast to the dimer W2o（β-O）（CH2CMe3）6, containing three alkyl ligands per W atom, from the previously reported reaction of the alkyl alkylidyne analog W（CH2CMe3）3- （=-CCMe3） with H2O. In the reaction of 1 with D20 in THF, an unstable intermediate W2O2（μ-O）（CD2SiMe3）2（CH2CMe3）4 （4-d4） was identified. Kinetic studies of the reactions of 1 with excess H2O and D2O in THF-ds, yielding 4 and 4-d4, respectively, give a kinetic isotope effect （KIE） of 3.46（3） at 298（1） K, suggesting that the disappearance of 1 is a rate-determining step.