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.

UPLC-MS/MS法测定槲寄生抗肿瘤成分1,7-bis(4-hydroxyphenyl)-1,4-heptadien-3-one的含量

目的建立超高效液相色谱-串联质谱法(UPLC/MS/MS)测定槲寄生中具有抗肿瘤活性的新化合物1,7-bis(4-hydroxyphenyl)-1,4-heptadien-3-one(BHPHD)的含量,并通过多因素方差分析比较产地与寄主对药材抗肿瘤成分含量的影响。方法以Thermo Hypersil GOLD C18(50 mm×2.1 mm,1.9μm)为分离色谱柱,乙腈-体积分数0.1%甲酸水溶液为流动相,流速0.2 m L·min-1,梯度洗脱,质谱检测器,电喷雾正离子,多反应监测模式,监测离子对m/z 295.09→106.99。结果BHPHD在质量浓度为0.050~2.5 mg·L-1内线性关系良好,精密度、重复性、稳定性试验的RSD均≤3.5%,平均加样回收率(n=9)为97.2%(RSD=1.6%)。结论该方法可满足定量要求。多因素方差分析表明槲寄生中BHPHD的含量受产地影响较大(P<0.01),受寄主影响不大。

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.

Effects of ω-3 fatty acids on toll-like receptor 4 and nuclear factor-κB p56 in lungs of rats with severe acute pancreatitis

AIM To determine the effects of ω-3 fatty acids(ω-3FA) on the toll-like receptor 4(TLR4)/nuclear factor κB p56(NF-κBp56) signal pathway in the lungs of rats with severe acute pancreatitis(SAP).METHODS A total of 56 Sprague-Dawley rats were randomly divided into 4 groups: control group, SAP-saline group, SAP-soybean oil group and SAP-ω-3FA group. SAP was induced by the retrograde infusion of sodium taurocholate into the pancreatic duct. The expression of TLR4 and NF-κBp56 in the lungs was evaluated by immunohistochemistry and Western blot analysis. The levels of inflammatory cytokines interleukin-6 and tumor necrosis factor-alpha in the lungs were measured by enzyme-linked immunosorbent assay. RESULTS The expression of TLR4 and NF-κBp56 in lungs and of inflammatory cytokines in serum significantly increased in the SAP group compared with the control group(P < 0.05), but was significantly decreased in the ω-3FA group compared with the soybean oil group at 12 and 24 h(P < 0.05).CONCLUSION During the initial stage of SAP, ω-3FA can efficiently lower the inflammatory response and reduce lung injury by triggering the TLR4/NF-κBp56 signal pathway.

1D Lanthanide Coordination Polymers Based on 3-(Pyridin-4-yl)benzoic Acid: Syntheses, Structures and Luminescent Properties

ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln（3,4-pybz）3（HzO）2. H2O]n （Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-（pyridin-4-yl）benzoic acid） have been synthesized by hydrothermal reactions of lanthanide oxide and 3-（pyridine-4-yl） benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoelinic system, space group P1^-. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-（carboxylate）2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.

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.

Synthesis of Gingerenone C and 5-Hydroxy-1-(4′-hydroxy-3-methoxyphenyl)-7-(4′′-hydroxyphenyl)-3-heptanone

The two diarylheptanoids (E)-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl) hept-4-en-3-one 1 (Gingerenone C) and (±)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4- hydroxyphenyl)-3-heptanone 2 were synthesized from vanillin 3 and 4-hydroxybenzaldehyde 9.

A Study on Side Reactions of Hydroxyethylation of 3-Nitro-4- chlorobenzenesulfinic Acid with Ethylene Oxide

The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-（β-hydroxyethylsulfonyl）chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-（β- hydroxyethylsulfonyl）chlorobenzene, there presented three kinds of side reactions： 1. Condensation and elimination of HCI to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.

Synthesis and Crystal Structure of 4-(4,6-dimethoxyl -pyrimidin-2-yl)-3-thiourea Carboxylic Acid Methyl Ester

The title compound 4-（4,6-dimethoxylpyrimidin-2-yl）-3-thiourea carboxylic acid methyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at the room temperature. The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis＇ Crystallographic data： C9H12N4O4S, Mr = 272.29, monoclinic, space group C2/m with a = 1.6672（3）, b = 0.66383（12）, c = 1.1617（2） nm, β = 109.275（2）°, V = 1.2136（4） nm^3, Dc = 1.490 g/cm^3,μ = 0.281 mm^-1, F（000） = 568, Z = 4, R1 = 0.0341and wR2 = 0.1042.

A One-dimensional Cd(Ⅱ)Coordination Polymer Constructed from 1,4-Benzene-dicarboxylic Acid and 3-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)-1H-indole:Synthesis,Structure and Photoluminescence

A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.

Stereoselective Synthesis of 2-(4-Hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxane-6-aldehyde—The Key Intermediate of Sinaiticin

2-(4-Hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxane-6-aldehyde 8,the key intermediate of sinaiticin 10,was synthesized in 6 step from caffeic acid 4 and 4- hydroxybenzsaldehyde 1.the coupling reaction is the key step.

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.

Synthesis of 1,7-Bis(4-hydroxyphenyl)-3-hydroxy-1,3-heptadien-5-one

A facile synthesis of the analog of curcumin. 1,7-bis (4-hydroxyphenyl)-3-hydroxy-1.3-heptadien-5-one 1 was achieved. The key step was completed through the regioselective condensation of ketone 5 and acyl chloride 7.

Two 3D Metal-organic Frameworks with 4-Fold [2＋2]-type Interpenetrated hms Nets Based on a Flexible Tricarboxylic Acid

Two 3D 4-fold interpenetrated metal-organic frameworks, [Mn（L）（bpy）]n （1） and [Cu（HL）（bpy）]n （2）（H3L = 4,4＇,4＇＇-（benzene-1,3,5-triyl-tri（methyleneoxy）） tribenzoic acid, bpy = 4,4′-bipyridine）, were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 1 crystallizes in monoclinic, space group Cc with a = 26.794（2）, b = 11.6346（10）, c = 21.4614（18） ？, β = 91.570（2）°, V = 6687.9（10） A^3, Z = 8, Mr = 736.59, D = 1.463 g·cm^（-3）, μ = 0.458 mm^-1c, R（int） = 0.0524, F（000） = 3040, the final R = 0.0844 and wR = 0.2266 for 8092 observed reflections（I 〉 2σ（I））. 2 crystallizes in monoclinic, space group Cc with a = 27.609（12）, b = 11.126（10）, c = 21.490（9） ？, β = 92.131（2）°, V = 6597（5） A^3, Z = 8, Mr = 746.21, Dc = 1503 g·cm^（-3）, μ = 0.726 mm^-1, R（int） = 0.0542, F（000） = 3080, the final R =0.0681 and wR = 0.1831 for 6777 observed reflections（I 〉 2σ（I））. Two compounds are 3D [2＋2]-type 4-fold interpenetrated frameworks with（6^3）（6^9.8） hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the Cu^Ⅱ ions in 2.

Synthesis and Crystal Structure of a New Quinazolinone Compound 2,3-Dihydro-2-(2-hydroxyphenyl)-3-phenyl-quinazolin-4(1H)-one

A new quinazolinone compound 2,3-dihydro-2-(2-hydroxyphenyl)-3-phenyl- quinazolin-4(1H)-one 3 ([C20H16O2N2]?C2H5OH, Mr = 362.42) and compound 2-(2-hydroxy- benzylidene-amino)-N-phenyl-benzamide 2 (C20H16O2N2, Mr = 316.34) were prepared from a precursor of 2-amino-N-phenyl-benzamide 1 (C13H12ON2, Mr = 212.25). Compound 3 was characterized by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbca with a = 1.2889(11), b = 1.6170(14), c = 1.7729(15) nm, V = 3.695(6) nm3, Z = 8, F(000) = 1536, Mr = 362.42, Dc = 1.303 g/cm3, μ(MoKα) = 0.087 mm-1, R = 0.0447 and wR = 0.0879. The crystal structure analysis indicates that the title compound has a two-dimensional network structure formed by hydrogen bonds and electrostatic interactions.

Synthesis, Crystal Structure and Properties of a New Coordination Polymer Constructed with 3-(4-hydroxypyridinium-1-yl)phthalic Acid

A new nickel coordination polymer {[Ni（dpa）（bpe）（H2O）]2}n（1） has been hydro-thermally synthesized, and structurally characterized by UV spectroscopy, elemental analyses and single-crystal X-ray diffraction（H2dpa=3-（4-hydroxypyridinium-1-yl） phthalic acid, bpe=μ-1,2-di（4-pyridyl） ethylene）. It crystallizes in the triclinic system, space group P1 with a=8.779（2）, b=10.909（3）, c=12.739（3）, α=72.45（2）, β=75.13（2）, γ=86.47（2）°, V=1124.1（5） 3, Z=2, Mr=516.14, Dc=1.525 g/cm3, μ=0.912 mm-1, Rint=0.0532, F（000）=532, the final R=0.0523 and wR=0.1089 for 3949 observed reflections（I〉2σ（I））. The coordination around the Ni center is a distorted octahedron coordination geometry involving two protonated H2dpa ligands, two bpe ligands, and one coordinated H2O molecule. The dpa2- anion, as a bridging ligand, connects two Ni centers to form binuclear units, which are linked together by the bpe ligands to form two-dimensional layers, and the interlayer hydrogen bonding further extends the 2D sheet into a 3D supramolecular framework.

A 3-fold Interpenetrated lvt Cd(Ⅱ) Network Constructed from 4-[(3-pyridyl)methylamino]benzoate Acid

A new three-dimensional（3D） coordination polymer, [Cd（L）2H2O]n·5nH2O 1 with 4-[（3-pyridyl）methylamino]benzoate acid（HL）, has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a = 20.7937（16）, c = 13.515（2）, V = 5843.5（11） 3, C26H34CdN4O10, Mr = 674.97, Dc = 1.534 g/cm3, μ（MoKα） = 0.808 mm-1, F（000） = 2768, Z = 8, the final R = 0.0276 and wR = 0.0691 for 5323 observed reflections（I 〉 2σ（I））. The result of thermal analysis shows that 1 is stable under 290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.

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.

Synthesis of (2S,4S)-2-Substituted-3- (3-Sulfanylpropanoyl)-6- Oxohexahydropyrimidine-4-Carboxylic Acids as Potential Antihypertensive Drugs

Proceeding from natural amino acid L-asparagine and commercially available aldehydes a stereoselective synthesis was developed of (2S,4S)-2-alkyl(aryl)-3-(3-sulfanylpropanoyl)-6-oxohexahy- dropyrimidine-4-carboxylic acids, potential antihypertensive drugs, inhibitors of the angiotensin converting enzyme.

Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.