Effect of Temperature on the Reaction of 2-(N-acetylamine)-3-(3,5-di-<i>tert</i>-butyl-4-hydroxyphenyl)-propionic Acid with Oxygen in an Alkaline Condition

Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.

Pig Liver Esterase-catalyzed Hydrolysis of Three Diesters of meso-Bicyclic Dicarboxylic Acid and Three Tetraesters of Tetrahydrofuran -2,3,4,5-tetracarboxylic Acid

Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective hydrolysis catalyzed by pig liver esterase(PLE). The results of the PLEcatalyzed hydrolysis were discussed.

Δ4-3-oxosteroid-5β-reductase deficiency: Responses to oral bile acid therapy and long-term outcomes

BACKGROUND Disorders of primary bile acid synthesis may be life-threatening if undiagnosed,or not treated with primary bile acid replacement therapy. To date, there are few reports on the management and follow-up of patients with Δ4-3-oxosteroid 5β-reductase(AKR1 D1) deficiency. We hypothesized that a retrospective analysis of the responses to oral bile acid replacement therapy with chenodeoxycholic acid(CDCA) in patients with this bile acid synthesis disorder will increase our understanding of the disease progression and permit evaluation of this treatment regimen as an alternative to the Food and Drug Administration(FDA) approved drug cholic acid, which is currently unavailable in China.AIM To evaluate the therapeutic responses of patients with AKR1 D1 deficiency to oral bile acid therapy, specifically CDCA.METHODS Twelve patients with AKR1 D1 deficiency, confirmed by fast atom bombardment ionization-mass spectrometry analysis of urine and by gene sequencing for mutations in AKR1 D1, were treated with differing doses of CDCA or ursodeoxycholic acid(UDCA). The clinical and biochemical responses to therapy were monitored over a period ranging 0.5-6.4 years. Dose adjustment, to optimize the therapeutic dose, was based on changes in serum biochemistry parameters,notably liver function tests, and suppression of the urinary levels of atypical hepatotoxic 3-oxo-Δ4-bile acids measured by mass spectrometry.RESULTS Physical examination, serum biochemistry parameters, and sonographic findings improved in all 12 patients during bile acid therapy, except one who underwent liver transplantation. Urine bile acid analysis confirmed a significant reduction in atypical hepatotoxic 3-oxo-Δ4 bile acids concomitant with clinical and biochemical improvements in those patients treated with CDCA. UDCA was ineffective in down-regulating endogenous bile acid synthesis as evidenced from the inability to suppress the urinary excretion of atypical 3-oxo-Δ4-bile acids. The dose of CDCA required for optimal clinical and biochemical responses varied from 5.5-10 mg/kg per day among patients based on maximum suppression of the atypical bile acids and improvement in serum biochemistry parameters, and careful titration of the dose was necessary to avoid side effects from CDCA.CONCLUSION The primary bile acid CDCA is effective in treating AKR1 D1 deficiency but the therapeutic dose requires individualized optimization. UDCA is not recommended for long-term management.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Helical Coordination Polymer with a 3-Fold Interpenetration Structure Based on 5-(Hydroxymethyl)isophthalic Acid

5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold interpenetration structure, namely [Zn1/2（HIA）1/2（DPEE）1/2]n （1）, was hydrothermally synthesized at 160 ℃, using H2HIA ligands to assemble with DPEE ligands and Zn2＋ ions. Complex 1 crystalizes in orthorhombic system, space group Pnna, with a = 8.2118（5）, b = 17.1698（7）, c =14.9922（7） ？, V = 2113.82（18） ？3, μ = 1.194 mm-1, Z = 4 and S = 0.967. Moreover, some physical characteristics of complex 1, such as powder X-ray diffraction （PXRD）, thermogravimetry analyses （TGA） and photoluminescent properties, were also investigated.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

Syntheses, Structures and Properties of Three Novel La(Ⅲ)/Co(Ⅱ) Coordination Polymers Based on 5-(3-(Tetrazo-5-yl)phenyl)isophthalic Acid

Three novel complexes, namely {[La(tapipa)(4,4′-bibp)·(H2O)2]·H2O}n(1),{[La-(tapipa)(H2O)4(OH)]·3 H2O}n(2),[Co(tapipa)(1,4-bbib)]n(3)(tapipa = 5-(3-(tetrazo-5-yl)phenyl)isophthalic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and 1,4-bbib = 1,4-bis(benzimidazo-1-ly)benzene) have been synthesized under solvothermal conditions and characterized by PXRD, IR,TGA, and so on. Complex 1 presents a 2 D layer structure, which is finally packed into a 3 D supramolecular structure by means of hydrogen bonds;complexes 2 and 3 exhibit 1 D chains and 2 D wavy-type structures, respectively, which are expanded into 3 D supramolecular structures through hydrogen bonds and π-π interactions. Furthermore, the luminescence properties of complex 1 and the variable-temperature magnetic susceptibilities of 3 were investigated. Complex 1 has highly selective sensing for Fe^3+ and Cr2O7^2- ions.

Synthesis of (S)-2-(3-Arylacrylamido)-3-{4-[2-(5-methyl-2-phenyl-oxazol-4-yl)ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.

3,5-二硝基水杨酸比色法测定还原糖含量的研究

比较了两种DNS试剂测定还原糖含量的影响因素。探讨了试剂添加量、显色时间、测定波长以及显色后存放时间对测量结果的影响。结果表明,DNS试剂的用量1.5ml,沸水浴显色时间5min,显色定容30min后,分别在540nm和550nm波长条件下测定,数据的准确性和稳定性较好。

3,5-二硝基水杨酸法测定葡萄酒中总糖含量的条件优化

根据3,5-二硝基水杨酸(3,5-dinitrosalicylic acid,DNS)与还原糖共热,可被还原成红棕色氨基化合物的原理,采用比色法测定葡萄酒样品经酸水解后总糖的含量。对水解条件、DNS法反应条件和葡萄酒基质影响等方面进行研究。最终确定葡萄酒样品的水解条件为:水解温度70.0℃,水解时间16.0min,HCl(浓盐酸1∶1稀释)添加量6.5mL,DNS比色法测定条件为:吸收波长540 nm,显色剂2mL,显色稳定时间30min内,线性范围0.1～2.0g·L-1,样液pH值7.0～13.0。结果表明DNS法操作简便、干扰少,精密度和重复性好(RSD<2.0%),加标回收率>98%,可以作为葡萄酒中总糖测定的方法。

响应面法对3,5-二硝基水杨酸比色法测定水果中还原糖含量条件的优化

采用3,5-二硝基水杨酸(DNS)比色法测定水果中还原糖的含量,在单因素试验的基础上,采用三因素三水平的响应面分析法(RSM)优化DNS法测定苹果还原糖的最佳条件,同时建立数学模型并验证其可靠性。回归方程失拟项不显著(P=0.133 7),预测值与实际值吻合(R^2=0.957 4);影响DNS法测定还原糖含量的因素主次顺序为:DNS用量﹥反应温度﹥显色时间;DNS法测定还原糖含量的最佳条件为:DNS用量4.0 m L,显色时间5.0 min,反应温度87.0℃,测得还原糖实际浓度为94.66 mg/L,与理论预测值基本相符。按照优化的最佳条件,以苹果、桃、葡萄、哈密瓜、脐橙、菠萝6种代表性水果为对象验证该方法的精密度、重复性和准确度,其标准偏差为0.1%~0.5%,相对标准偏差为2.0%~4.8%,加标回收率为90.6%~104.2%。该方法简便、快速,准确度高,重现性好,适合于苹果及其他水果中还原糖的测定。

3,5-二硝基水杨酸比色法测定麦冬多糖含量

采用3,5-二硝基水杨酸(DNS)比色法测定麦冬多糖含量。结果表明,麦冬多糖占麦冬总干重的40.4mg.g-1,RSD=2.48%(n=5),总糖供试液和单糖供试液的平均回收率分别是100.4%(RSD=0.17%)和101.1%(RSD=0.62%)。试验表明,DNS比色法测定多糖含量简单易行,且重现性好,可作为麦冬多糖含量的常规测定方法。

蒽酮-硫酸法和3,5-二硝基水杨酸法测定杜仲水提液多糖含量

采用蒽酮-硫酸法测定杜仲水提液中总糖含量,3,5-二硝基水杨酸法测定杜仲水提液中单糖含量,多糖含量为总糖与还原糖含量之差。该法简便、快速、准确、稳定,为其他材料水提液中多糖定量提供参考。

采用3,5-二硝基水杨酸比色法测定饲料总淀粉含量

采用3,5-二硝基水杨酸(DNS)比色法测定饲料样品中总淀粉含量。结果表明,该方法标准曲线在0.2～1.2mg范围内,线性关系良好,回归方程Y=0.7442X-0.0465,相关系数r=0.9998,平均加标回收率为96.8%～98.1%。实验表明,DNS比色法测定总淀粉含量简单易行,且重复性好,可作为饲料中总淀粉含量的常规测定方法。

3,5-二硝基水杨酸(DNS)法测定D-半乳糖醛酸含量的条件探索

[目的]优化3,5-二硝基水杨酸（DNS）法用于测定D-半乳糖醛酸含量的条件。[方法]通过单因素实验研究了3,5-二硝基水杨酸（DNS）法测定D-半乳糖醛酸含量的测定条件。[结果]单因素试实结果表明,利用3,5-二硝基水杨酸法测定D-半乳糖醛酸含量的优化条件为：测定波长540 nm,DNS用量4.0 ml,反应温度100℃,反应时间5 min,最佳测定时间60 min内。此条件下回归方程y=1.0226x-0.2784,回归系数r=0.9997,平均回收率99.96%,D-半乳糖醛酸含量测定范围0.5-1.1 mg/ml,统计分析表明,该方程显著存在。[结论]多次实验验证,该方法测定D-半乳糖醛酸含量时操作简单、准确度高、重复性好。

3,5-二硝基水杨酸比色法测定废烟草中总糖

对3,5-二硝基水杨酸比色法测定总糖含量的条件进行了研究,结果表明:最佳比色波长为540 nm,显色剂的最佳用量为2.5 mL,沸水浴时间为5 min.对废烟草样品进行测定,试验表明:该方法在2-240μg.mL-1浓度范围内遵循比耳定律,呈线性关系(R=0.999 3),变异系数为0.46%,平均回收率为98.9%,该法的准确性和精密度均较好.与经典的斐林试剂法相比,具有操作简便、快速、测定成本低等特点.尤其适合于低浓度糖样的测定.

3,5-二硝基水杨酸比色法定糖的条件优化

目的优化3,5-二硝基水杨酸比色法定糖条件。方法单因素试验法。结果优化后的参数条件为波长495nm,VDA/V总为1.5/3.5,反应温度90℃,反应时间5-7min。结论改良后的3,5-二硝基水杨酸比色法测定还原糖的结果更高效、准确和稳定。

一维链状配位聚合物乙醇合二丁基锡-3,5-二硝基-2-氧苯甲酸酯的合成、结构和性质

利用二丁基氧化锡和3,5-二硝基水杨酸在苯-乙醇中反应合成了新配合物乙醇合二丁基锡3,5-二硝基-2-氧苯甲酸酯(n-C4H9)2Sn(2-O-3,5-(NO2)2C6H2COO)(C2H5OH)(1),通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1属单斜晶系,P21/c空间群,a=1.363 33(10)nm,b=1.861 90(14)nm,c=0.841 51(6)nm,β=93.311(1)°,Z=4,V=2.132 5(3)nm3,R1=0.033 6,wR2=0.090 0。该化合物为由羧基桥联配位和分子间氢键形成的新型一维链状有机锡配合物,锡原子具有六配位[SnC2O4]畸变八面体构型。化合物1对2种人癌细胞A549和CoLo205增殖均有强的抑制作用,对乙酰乙酸乙酯与醇的酯交换反应具有高选择性和良好的催化活性。

((3-(3-硅胶丙基)硫基)丙基)硫酸酯作为可回收催化剂用于合成4,4'-芳亚甲基-双(1H-吡唑-5-醇)(英文)

Sulfuric acid ([3-(3-silicapropyl)sulfanyl]propyl)ester is employed as a recyclable catalyst for the condensation reaction between aromatic aldehydes and 3-methyl-l-phenyl-5-pyrazolone. This condensation reaction was performed in ethanol under refluxing conditions giving 4,4'-alkylmethylene-bis(3-methyl-5-pyrazolones) in 74-90% yields. The heterogeneous catalyst was recycled and used in eleven runs for the reaction between benzaldehyde and 3-methyl-l-phenyl-5-pyrazolone without losing catalytic activity.

超分子8-羟基喹啉/3,5-二硝基水杨酸的合成、晶体结构及抑菌活性

以8-羟基喹啉和3,5-二硝基水杨酸合成了一种黄色的超分子化合物,用X-射线衍射法确定了其晶体结构,大量的分子内和分子间氢键使此超分子化合物结构得以稳定。抑菌活性测试发现此超分子化合物的抑菌活性明显高于8-羟基喹啉和3,5-二硝基水杨酸,其中对枯草芽孢杆菌的抑菌效果最好。