cis,trans-4-戊基环己基甲酸的合成及异构体转位

采用Ni5249P为催化剂，在水相碱性条件下，反应温度为175℃，反应压力为9MPa，加氢合成4-戊基环己基甲酸[m（civ）：m（trans-）=75：253。在200-220℃进行异构体转位，可以使4-戊基环己基甲酸产物中m（cir）：m（trans-）=2：98，trans-4-戊基环己基甲酸收率为95％。

毛细管气相色谱法测定乳脂中的cis-9,trans-11-共轭亚油酸

建立了测定乳脂中cis-9,trans-11-共轭亚油酸(CLA)的毛细管气相色谱方法。样品经正己烷-异丙醇提取、甲醇-甲醇钠甲酯化后,进行气相色谱分析;采用程序升温,以保留时间定性,外标法定量。采用该方法测得共轭亚油酸的回收率为100.26%,相对标准偏差(RSD)为1.9%(n=6),检测限为1 mg/L。该方法样品用量少,前处理简单,建立的实验条件准确可靠,不仅可以用来测定cis-9,trans-11-CLA的含量,而且对于乳制品中所含的其他脂肪酸的分析测定也具有指导意义。

一种直接在Trans-树中挖掘频繁模式的新算法

Frequent pattern mining plays an essential role in many important data mining tasks. FP-growth is a veryefficient algorithm for frequent pattern mining. However, it still suffers from creating conditional FP-tree separatelyand recursively during the mining process. In this paper, we propose a new algorithm, called Least-Item-First Pat-tern Growth (LIFPG), for mining frequent patterns. LIFPG mines frequent patterns directly in Trans-tree withoutusing any additional data structures. The key idea is that least items are always considered first when the current pat-tern growth. By this way, conditional sub-tree can be created directly in Trans-tree by adjusting node-links and re-counting counts of some nodes. Experiments show that, in comparison with FP-Growth, our algorithm is about fourtimes faster and saves half of memory; it also has good time and space scalability with the number of transactions,and has an excellent performance in dense dataset mining as well.

2-苯基/环己基环十二酮的还原选择性及trans-1,2-二取代环十二烷的构象分析

通过研究2-苯基/环己基环十二酮在不同还原剂和温度下的还原反应证实了2-取代环十二酮的还原反应具有cis-选择性.在此基础上,通过2-取代环十二酮的Na BH4还原反应、1,2-环氧环十二烷的开环反应及cis-2-苯基环十二醇的Mitsunobu反应和水解反应制备了一系列trans-1,2-二取代环十二烷;采用1H NMR、13C NMR、X射线衍射和量子化学计算等方法对其优势构象进行了分析.结果表明,trans-1,2-二取代环十二烷的优势构象为[3333]方形构象,1个取代基位于边碳外向位(Side-exo),另1个位于角碳反向位(Corneranti).cis-2,12-二取代环十二酮的Li Al H4还原产物的X射线衍射分析结果表明,生成的1,2,3-三取代环十二烷保持了环十二烷的[3333]方形构象,2个取代基位于边碳外向位,羟基位于角碳顺向位(Corner-syn),取代基呈现出cis-cis关系.

Determination of trans-4-hydroxy-2-alkenals in thermally treated soybean oil by SPE-HPLC

Trans-4-hydroxy-2-hexenal(4-HHE) and trans-4-hydroxy-2-nonenal(4-HNE) are secondary lipid peroxidation products in edible oils, which are cytotoxic and genotoxic. They could covalently bind with protein, phospholipids and DNA, further disrupting the normal function of liver, lung and brain.Derivation process was generally conducted during pretreatment before detection and quantification of 4-HHE and 4-HNE. However, the derivation procedures were time consuming and chemical degradation may occur during the process. Hence, this paper aims to establish a simple solid phase extractionhigh performance liquid chromatography(SPE-HPLC) method to determine the 4-HHE and 4-HNE contents in thermally treated soybean oil. C18 solid phase extraction was applied in the pretreatment process. Firstly, the reliability of the method was evaluated. Good linearity was observed in the range of 0.1–0.5 μg/m L and 0.5–10 μg/m L for 4-HHE and 4-HNE. The limit of detection(LOD) of 4-HHE and 4-HNE were 0.0486 and 0.0129 μg/m L, respectively. And the limit of quantitation(LOQ) of4-HHE and 4-HNE were 0.1458 and 0.0431 μg/m L, respectively. Recovery rate were in the range of89.11%–91.58% and 71.83%–79.40% for 4-HHE and 4-HNE, respectively. The method achieved the extraction, purification and detection of 4-HHE and 4-HNE simultaneously and had the advantages of simple operation, effectiveness, high precision, good repeatability. Then, the method was applied to monitor the concentrations of 4-HHE and 4-HNE in soybean oil heated at 180 °C for 40 h. The contents of 4-HHE and 4-HNE were 0–0.32 μg/g and 0–6.97 μg/g, respectively, which provided guidance for evaluating health risks of thermally treated soybean oil during heating.

Molecular Dynamic Simulation of Melting Points of Trans-1,4,5,8- tetranitro-1,4,5,8-tetraazadacalin （TNAD） with Some Propellants

Molecular dynamic simulation was employed to predict the melting points Tm of TNAD/HMX, TNAD/RDX, TNAD/DINA, and TNAD/DNP systems （tans-1,4,5,8- tetranitro-1,4,5,8-tetraazadacalin （TNAD）, dinitropiperazine （DNP）, cyclotetramethylenetetranitroamine （HMX）, cyclotrimethylenetrinitramine （RDX）, and N-nitrodihydroxyethylaminedinitrate （DINA））. Tm was determined from the inflexion point on the curve of mean specific volume vs. temperature. The result shows that the Tm values of TNAD/HMX, TNAD/RDX, and TNAD/DINA systems are 500, 536, and 488 K, respectively. The TNAD/DNP system has no obvious Tm value, which shows the system is insoluble. Using Tm, the solubility of the four systems was analyzed. The radial distribution functions of the four systems were analyzed and the main intermolecular forces between TNAD and other energetic components are short-range interactions. The better the solubility is, the stronger the intermoleenlar interaction is. In addition, the force field energy at different temperature was also analyzed to predict Tm of the four systems.

4-(trans-4”’-n-烷基环己烷甲氧基)-4'-氰基联苯的合成

从trans－4－n-烷基环己基甲醇和4-溴-4’-羟基联苯出发经磺酸酯化、醚化、氰代合成了三种4－（trans-4”－n-烷基环己烷甲氧基）－4’-氰基联苯液晶化合物，经IR、MS、元素分析确证了化学结构．

英语前缀trans-意象图式与语义分析

在英语词汇系统中,以trans-为前缀构成的单词数量多、意思差异大,学习者很难理解和记忆。但用意象图式理论对这类词汇进行图解分类发现,trans-构词有四种图式,包括:穿透图式、跨越图式、变化图式和"到另一侧"图式。从英语和汉语的视角分别对trans-构词做进一步的分类,提出了五类介词意象图式归类法和汉语五字意象图式归类法,使这类单词形成范畴,提高了记忆效率。

被修饰环糊精模版控制的trans-2-苯乙烯吡啶的分子内环化

环糊精(CDs)是由6,7或8吡喃葡萄糖与上下环绕的羟基组成的环状低聚糖,具有内疏水外亲水的结构特征。合成了一种酰化的γ-环糊精(CDs),并将酰化的环糊精衍生物与trans-2-苯乙烯吡啶分子包合,比较了固态、液态及凝胶态中包合物的光反应结果,发现修饰的环糊精对其分子内光环化产物的生成具有选择性,其中固态产物的选择性最好,可以得到产率较高的苯并[f]喹啉。

Effect of apoptosis on gastric adenocarcinoma cell line SGC-7901 induced by cis-9,trans-11-conjugated linoleic acid

AIM: To determine the effect of apoptosis on gastric cancer cells (SGC-7901) induced by cis-9, trans-11-conjugated linoleic acid (c9, t11-CLA) and its possible mechanism in the inhibition of cancer cells growth.METHODS: Using cell culture, flow cytometery and immunocytochemical techniques, we examined the cell growth, frequency of apoptosis and distribution of cell cycle,expression of ki67, bcl-2, Fas, and c-myc of SGC-7901 cells which were treated with various c9, t11-CLA concentrations (25,50,100 and 200 μmol@L-1) of c9, t11-CLA for 24h and 48 h,with a negative control (0.1% ethanol).RESULTS: The growth of SGC-7901 cells was inhibited by c9,t11-CLA. Eight days after treatment with various concentrations of c9,t11-CLA, as mentioned above, the inhibition rates were 5.9 %, 20.2 %,75.6 % and 82.4 %, respectively. The frequency of apoptosis on SGC-7901 cells induced by different concentrations of c9, t11-CLA (except for 25 μmol@L-1, 24 h) was significantly greater than that in the negative control (P＜0.01). To further investigate the influence of the cell cycle progression, we found that apoptosis induced by c9, t11-CLA may be involved in blocking the cell cycle of SGC-7901 cells. Immunocytochemical staining demonstrated that SGC-7901 cells preincubated in media supplemented with different c9, t11-CLA concentrations for various time periods significantly decreased the expressions of ki67 (the expression rates were 18.70-3.20 %, at 24 h and 8.10-0.20 % at 48 h, respectively), bd-2 (4.30-0.15 % at 24 h and 8.05 %-0 at 48 h),and c-myc(4.85-2.20 % at 24 h and 4.75-0.30 % at 48 h) as compared with those in the controls (the expressions of ki67, bcl-2, and c-mycwere 15.1% at 24 h and 13.5 % at 48 h, 6.80 % at 24 h and 8.00 % at 48 h,5.50 % at 24 h and 5.30 % at 48 h, respectively) (P＜0.01),whereas the expressions of Fas were increased (0.60-2.75 %,24 h and 0.45-5.95 %, 48 h).CONCLUSION: The growth and proliferation of SGC-7901 cells are inhibited by cg, t11-CLA via blocking the cell cycle,pathways of bcl-2-associated mitochondria with reduced expression of bcl-2 and Fas-associated death domain protein (FADD) with enhanced expression of Fas. But expression of c-myc on SGC-7901 cells is lower than that in negative control, which needs to be studied further.

Solubility of trans-1,2-Cyclohexanediol in Some Solvents

The solubility of trans-1,2-cyclohexanediol in water, methyl acetate, acetic ester, propyl acetate, butyl acetate, methyl acrylate, ethyl acrylate, 2-pentanone and acetoacetic ester was measured at temperatures ranging from about 300 K to 330 K, using a modification of the experimental technique of laser monitoring observation system. The solubilities were calculated by λh method, in which new parameters were introduced to express the activity coefficients of trans-1,2-cyclohexanediol, and determined from the experimental data. The new parameters provide good calculated results. The experimental data were also correlated with a simple model, and results were compared with present λh model.

Solid-Liquid Equilibria of trans-1,2-Cyclohexanediol＋Butyl Acetate＋ Water Ternary System

Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure.It is shown that the solubilities of trans-1,2-cyclohexanediol in butyl acetate+water were affected greatly by the proportion of butyl acetate and water,and presented maximum value at given temperature.The UNIFAC model was used to correlate the experimental data.The average relative deviation(ARD)between experimental and calculated values is 3.03%.

High rumen degradable starch decreased goat milk fat via trans-10,cis-12 conjugated linoleic acid-mediated downregulation of lipogenesis genes,particularly,INSIG1

Background:Starch is an important substance that supplies energy to ruminants.To provide sufficient energy for high-yielding dairy ruminants,they are typically fed starch-enriched diets.However,starch-enriched diets have been proven to increase the risk of milk fat depression(MFD)in dairy cows.The starch present in ruminant diets could be divided into rumen-degradable starch(RDS)and rumen escaped starch(RES)according to their different degradation sites(rumen or intestine).Goats and cows have different sensitivities to MFD.Data regarding the potential roles of RDS in milk fat synthesis in the mammary tissue of dairy goats and in regulating the occurrence of MFD are limited.Results:Eighteen Guanzhong dairy goats(day in milk=185±12 d)with similar parity,weight,and milk yield were selected and randomly assigned to one of three groups(n=6),which were fed an LRDS diet(Low RDS=20.52%),MRDS diet(Medium RDS=22.15%),or HRDS diet(High RDS=24.88%)for 5 weeks.Compared with that of the LRDS group,the milk fat contents in the MRDS and HRDS groups significantly decreased.The yields of short-,mediumand long-chain fatty acids decreased in the HRDS group.Furthermore,increased RDS significantly decreased ruminal B.fibrisolvens and Pseudobutyrivibrio abundances and increased the trans-10,cis-12 conjugated linoleic acid(CLA)and trans-10 C18:1 contents in the rumen fluid.A multiomics study revealed that the HRDS diet affected mammary lipid metabolism down-regulation of ACSS2,MVD,AGPS,SCD5,FADS2,CERCAM,SC5D,HSD17B7,HSD17B12,ATM,TP53RK,GDF1 and LOC102177400.Remarkably,the significant decrease of INSIG1,whose expression was depressed by trans-10,cis-12 CLA,could reduce the activity of SREBP and,consequently,downregulate the downstream gene expression of SREBF1.Conclusions:HRDS-induced goat MFD resulted from the downregulation of genes involved in lipogenesis,particularly,INSIG1.Specifically,even though the total starch content and the concentrate-to-fiber ratio were the same as those of the high-RDS diet,the low and medium RDS diets did not cause MFD in lactating goats.

Efficient Splitting of Trans-/Cis-Olefins Using an Anion-Pillared Ultramicroporous Metal-Organic Framework with Guest-Adaptive Pore Channels

Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–guest interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.

Isolation and Crystal Structure of Trans-2,2',4,4'-tetramethyl-6,6'-dinitro Azobenzene

Trans-2,2?,4,4?-tetramethyl-6,6?-dinitro azobenzene (C16H16N4O4, Mr = 328.32) was isolated from benzene extract of the leaves of Aconitum sungpanense Hand. Mazz. as a new compound, and characterized by spectral methods and X-ray diffraction analysis. It crystallizes in monoclinic system, space group P21/c with a = 8.544(1), b = 13.997(2), c = 7.161(1) ? ?= 112.97(1), V = 788.4(2) ?, Z = 4, Dc = 1.383 g/cm3, F(000) = 344 and ?MoKa) = 0.102 mm-1. The final R = 0.0395 and wR = 0.1140 for 1913 independent reflections with Rint = 0.0109 and 1329 observed reflections with I > 2s(I). The molecule is composed of two phenyl rings through trans N=N.

Adsorptive Thermodynamic Properties and Kinetics of trans-1,2-Cyclohexandiol onto AB-8 Resin

AB-8 resin was used as an adsorbent for the removal of trans-1,2-cyclohexandiol(CHD) from aqueous solutions.Batch experiments were carried out to investigate the effect of contact time and temperature on sorption efficiency.The adsorptive thermodynamic properties and kinetics of CHD from water onto AB-8 resin were studied.The Langmuir and Freundlich isotherm models were employed to discuss the adsorption behavior.Thermodynamic parameters such as G,H and S were calculated.The results indicate that the equilibrium data are perfectly represented by Langmuir isotherm model.Thermodynamic study reveals that it is an exothermic process in nature and mainly physical adsorption enhanced by chemisorption with a decrease of entropy process.The kinetics of CHD adsorption is well described by the pseudo second-order model.The adsorbed CHD can be eluted from AB-8 resin by 5% ethanol aqueous solution with 100% elution percentage.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Ultrafast Investigation of Excited-State Dynamics in Trans-4-methoxyazobenzene Studied by Femtosecond Transient Absorption Spectroscopy

The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.

EFFECT OF CIS-9, TRANS-11-CONJUGATED LINOLEIC ACID ON CELL CYCLE OF MAMMARY ADENOCARCINOMA CELLS(MCF-7)

Objective: To determine the effect of cis-9, trans-1 1-conjugated linoleic acid on the cell cycle of mammary cancer cells (MCF-7) and the possible mechanism of the inhibitory effect of c9,t11-CLA. Methods: Using cell culture and immunocytochemical techniques, we examined the cell growth, DNA synthesis, expression of PCNA, cyclin A, B1, D1, p16ink4a and p21cip/waf1 of MCF-7 cells at various c9,t11-CLA concentrations (25μM, 50μM, 100μM and 200μM), at 24h and 48h. 96% ethand was used as negative control. Results: The cell growth and DNA synthesis of MCF-7 cells were inhibited by c9,t11-CLA. After treatment with various doses of c9,t11-CLA mentioned above for 8 days, the inhibition frequency was 27.18%, 35.43%, 91.05%, and 92.86%, respectively. Inhibitory effect of c9,t11-CLA on DNA synthesis (except for 25μM, 24h) was demonstrated by significantly less incorporation of 3H-TdR than the negative control (P<0.05 and P<0.01). To further investigate the influence of the cell cycle progression, we found that c9,t11-CLA may arrest the cell cycle of MCF-7 cells. Immunocytochemical staining demonstrated that incubation with different concentration of c9,t11-CLA at various times significantly decreased the expression of PCNA, Cyclin A, B1, D1 in MCF-7 cells compared to the negative control (P<0.01), whereas the expression of p16ink4a and p21cip/waf1, cyclin-dependent kinases inhibitors (CDKI), were increased. Conclusions: The cell growth and proliferation of MCF-7 cells is inhibited by c9,t11-CLA via blocking cell cycle, accompanying reduced expression of cyclin A, B1, D1 and enhanced expression of CDKI (p16ink4a and p21cip/waf1).

Partially replacing cornstarch in a high-concentrate diet with sucrose inhibited the ruminal trans-10 biohydrogenation pathway in vitro by changing populations of specific bacteria

Background： The positive influence of replacing dietary starch with sugar on milk fat production has been proposed to be partially attributed to the inhibition of the rumen trans-10 biohydrogenation pathway. However,whether and how sucrose inhibits the rumen trans-10 biohydrogenation pathway remains elusive.Results： A batch in vitro incubation system was used to evaluate effects of replacing cornstarch in a high-concentrate diet（forage to concentrate ratio = 40：60） with 0（control）, 3, 6 and 9 % of sucrose on rumen fermentation pattern, fatty acid（FA） biohydrogenation pathways and bacterial populations relating to trans-11 to trans-10 biohydrogenation pathways. Replacing dietary cornstarch with sucrose did not alter rumen p H or concentrations of total volatile fatty acids（VFA） in comparison with the control but significantly influenced the profiles of individual VFA. The molar proportions of butyrate and valerate were linearly increased, while that of acetate was quadratically decreased and those of propionate, isobutyrate and isovalerate were linearly decreased with increasing concentrations of sucrose in the diet. Furthermore, replacing cornstarch with sucrose led to a linear decrease in C18：1 trans-10, linear increases in the proportions of C18：1 trans-11, C18：2n-6 and the ratio of trans-11 to trans-10, and linear decreases in biohydrogenation of C18：2n-6 and C18：3n-3. The abundance of Butyrivibrio fibrisolvens, a butyrate and CLA cis-9,trans-11 producer, was increased with the increasing inclusion of sucrose in the diet, while the population of Megasphaera elsdenii, a CLA trans-10, cis-12 producer, was significantly decreased by all levels of sucrose replacements.Conclusions： These results indicate that replacing starch in a high-concentrate diet with sucrose increased butyrate production and inhibited the rumen trans-10 biohydrogenation pathway, which was at least partially due to increased abundance of Butyrivibrio fibrisolvens and decreased abundance of Megasphaera elsdenii.