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.

Synthesis, Structure and Photoluminescence of a New Cd(Ⅱ) Coordination Polymer Based on 4-(Carboxymethoxy)-benzoic Acid and 1,10-Phenanthroline Derivative

A new ID coordination polymer, [Cda（L1）2（L2）2].H2O （1, H2L1 = 4-（carboxy- methoxy）benzoic acid and L2 = 2-（4-fluorophenyl）-I H-imidazo[4,5-f][1,10]phenanthroline）, has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985（5）, b = 10.768（5）, c = 12.512（5） A, a = 68.959（5）, β = 80.354（5）, γ = 79.663（5）°, V= 1227.4（10） A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F（000） = 630, μ（MoKa） = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd（II） atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.

Crystal Structure, Thermal Behavior and Luminescence of a New Copper Coordination Polymer Constructed with 4-(Carboxymethoxy)-benzoic Acid

A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.

A Green Synthesis of 2-Ethylanthraquinone by Dehydration of 2-(4'-ethylbenzoyl) benzoic Acid over Solid Acid Catalysts

The dehydration of 2-（4＇-ethylbenzoyl） benzoic acid （BE acid） to 2-ethylanthraquinone （2-EAQ） was investigated over solid acid catalysts. The results showed that H-beta zeolite catalyst modified by dilute HNO3 solution exhibited an excellent performance. In our study, the conversion of BE acid can reach 96.7%, and the selectivity to 2-EAQ is up to 99.6%.

Crystal Structures of Urokinase-type Plasminogen Activator in Complex with 4-(Aminomethyl) Benzoic Acid and 4-(Aminomethyl-phenyl)-methanol

Urokinase-type plasminogen activator （uPA） is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors： 4- （aminomethyl）-benzoic acid （AMBA） and 4-（aminomethyl-phenyl）-methanol （AMPM）, both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA （Ki = 2.68 mM） than AMPM （Ki = 13.99 mM）. The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.

Synthesis and Crystal Structure of 2-[(4-Methoxy- 6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl] Benzoic Acid Methyl Ester

The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.

Metal-organic frameworks derived from divalent metals and 4-(1H-1, 2, 4-triazol-1-yl)benzoic acid

Two inorganic-organic coordination polymers, [Cd(TBA)2]·3H2O (1) and [Cu(TBA)2]·2H2O (2) have been synthesized by reaction of the metal ions of Cd(II) and Cu(II) with the ligand HTBA [HTBA = 4- (1H-1, 2, 4-triazol-1-yl)benzoic acid] under solvothermal condition. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction (XRPD), and thermo gravimetric analysis (TGA). The structural analyses reveal the two independent polymers exhibit different structures. Complex 1 exhibits a 3D framework with 1D channels, and complex 2 shows a 2-fold interpenetrating 3D diamond net.

A New Nickel(Ⅱ) Coordination Compound Constructed by Pyridyl-triazole and Oxybis(Benzoic Acid): Synthesis,Crystal Structure and the Effect on the Thermal Decomposition of Ammonium Perchlorate

A new energetic complex, Ni（3,4＇-Hbpt）2（Hoba）2（H20）2 （3,4＇-Hbpt = 3-（3-pyridyl）- 5-（4＇-pyridyl）-l-H-l,2,4-triazole and H2oba = 4,4＇-oxybis（benzoic acid））, has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P2j/c with a = 10.2357（9）, b = 24.594（2）, c = 10.4225（9）/k, β = 114.0110（10）°, V = 2396.7（4） A3, Dc = 1.460 g/cm3,μ = 0.482 mm-1, Mr = 1053.63, F（000） = 1088, Z = 2, the final R = 0.0358 and wR = 0.0973 with I 〉 2σ（I）. Both 3,4＇-Hbpt and H2oba ligands adopt monodentate modes linking one Ni（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate （AP） is explored by differential scanning calorimetry （DSC）, which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.

Syntheses and Characterizations of the Lanthanide Compounds with 4-(4-Pyridyl)benzoate and 2,6-Pyridinedicarboxylate as Ligands

Two new lanthanide coordination polymers, namely [Ln2（μ3-OH）（pydca）-（pyba）3（H2O）]n（Ln = Pr, 1; Eu, 2; Hpyba = 4-（4-pyridyl）benzoic acid; H2 pydca = 2,6-pyridinedicarboxylic acid）, have been hydrothermally synthesized and characterized by IR spectroscopy and X-ray single-crystal diffraction. The chains of 1 and 2 are constructed by tetrametallic units of [Ln4（OH）2（pyba）2], which are further linked by μ4-k1N, k1O, k2O′, k2O″-pydca and μ2-k1N, k1O, k1O′-pyba to form 2D frameworks. Luminescence measurement reveals that compound 2 exhibits strong reddish emission at room temperature.

Synthesis, Crystal Structure and Antifungal Activity of a New Zn(Ⅱ) Complex Based on 4-(5-(Pyridin-3-yl)-4H-1,2,4-triazol-3-yl) Benzoic Acid

A new complex[Zn(3,4-APT)2(H2 O)4]·8 H2 O(1,3,4-HAPT=4-(5-(pyridin-3-yl)-4 H-1,2,4-triazol-3-yl)benzoic acid)has been prepared and characterized by elemental analysis,X-ray single-crystal diffraction analysis,thermogravimetric analysis and infrared spectrum analysis.Theoretical calculation based on density functional theory(DFT)is also employed to explicate frontier orbitals of 3,4-HAPT.X-ray single-crystal diffraction analysis reveals that 1 belongs to the triclinic system,space group P1 with a=7.5123(3),b=8.6745(3),c=15.2074(6)Å,α=78.469(1),β=87.387(1),γ=65.448(1)°,V=882.42(6)Å,Z=1,D_(c)=1.528 g·cm^(–3),μ=0.780 mm^(–1),M_(r)=812.09,F(000)=424,the final R=0.0401 and wR=0.1136.Zn(II)ion is coordinated by two N atoms from two 3,4-HAPT as well as four O atoms from four coordinated water molecules,forming a 0D motif with distorted octahedral coordinated geometry.The adjacent 0 D units are linked into a 3 D supramolecular structure through hydrogen bonding interaction.In addition,complex 1 exhibits better antifungal activity against Colletotrichum gloeosporioides Penz than the ligand and metal salt by MIC,MBC tests and Kirby-Bauer disc diffusion method which exhibit potential application in the antifungal fields.

A Stable ‘Three-in-one’ Coordination Polymer

The title compound [Cu2（IB）2（HIB）2] 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-（1H-Imidazol-1-yl）benzoic acid （HIB）, and characte- rized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 24.513（8）, b = 18.948（5）, c = 17.248（6）, β = 119.81（2）o, V = 6951（4）3, Z = 8, C40H30Cu2N8O8, Mr = 877.80, Dc = 1.678 g/cm3, F（000） = 3584 and μ（MoKα） = 1.295 mm-1. The final R = 0.0542 and wR = 0.1335 for 5398 observed reflections with I 〉 2σ（I） and R = 0.0845 and wR = 0.1520 for all data. X-ray diffraction analysis reveals that the title complex is a unique ＇three-in-one＇ crystal of coordination network through strong hydrogen bonds and coordination covalent bonds. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurs below 300 ℃.

盐酸丁卡因有关物质的HPLC法测定

建立了HPLC法测定盐酸丁卡因中的有关物质对氨基苯甲酸和对丁胺基苯甲酸。采用C18色谱柱,0.01mol/L磷酸二氢钠溶液(含20mmol/L十二烷基磺酸钠,用磷酸调至pH3.0)-甲醇(25:75)为流动相,检测波长280nm。3批样品中未检出对氨基苯甲酸,对丁胺基苯甲酸含量均小于0.4%,杂质总量均小于1.0%。

盐酸丁卡因的合成工艺改进

以对氨基苯甲酸乙酯（苯佐卡因,EPABA）为原料,经过N-烷基化、水解、酯化三步反应得到盐酸丁卡因。采用FTIR、^1HNMR和HPLC对产物进行了表征。对N-烷基化过程、水解条件、酯化条件进行了优化。结果表明：盐酸丁卡因被成功合成。N-烷基化的最佳工艺条件为：反应温度60℃,n（三乙胺）∶n（EPABA）∶n（1-溴丁烷）=1.2∶1.0∶4.6,在此条件下合成对丁氨基苯甲酸乙酯（Ⅰ）,产品收率为75.62%;与现有工艺路线相比,在生成关键中间体Ⅰ时成功减少了双丁基化副产物的产生;水解反应的最佳合成条件为：n（Na OH）∶n（Ⅰ）=1.4∶1.0、反应温度为50℃、反应时间为8 h,在此条件下合成对丁氨基苯甲酸（Ⅱ）的收率为99.78%;当n[（β-氯乙基）二甲胺盐酸盐,Ⅲ]∶n（Ⅱ）=1.3∶1.0、反应温度为116℃、溶剂为甲基异丁基酮时,合成了盐酸丁卡因,收率为85.07%。

苯佐那酯软胶囊在中国健康受试者中的药代动力学研究

目的:研究中国健康受试者口服苯佐那酯软胶囊后苯佐那酯及其代谢产物4-N-丁基氨基苯甲酸(BBA)的药代动力学特征。方法:36名健康受试者分为A、B、C 3组,A、C组分别单次口服苯佐那酯软胶囊100 mg(低)、400 mg(高),B组单次及多次口服苯佐那酯软胶囊200 mg(中)。通过HPLC-MS/MS法检测血浆中BBA的浓度,推算血浆中苯佐那酯的浓度,估算药代动力学参数。结果:A、B、C 3组受试者单次给药苯佐那酯软胶囊后,BBA的Tmax分别为(0.74±0.40)、(0.54±0.24)、(0.61±0.43) h,Cmax分别为(1 603±443)、(2 833±1131)、(6 549±2 009) ng·mL^-1,AUC0-10h分别为(2 395±1 062)、(3 403±1 228)、(9 104±4 134) ng·h·mL^-1,t1/2分别为(1.42±0.52)、(1.84±0.89)、(1.70±0.75) h;苯佐那酯的Tmax分别为(0.62±0.25)、(0.62±0.27)、(0.58±0.37) h,Cmax分别为(1 201± 449)、(1 838±700)、(3 554±1 775) ng·mL^-1,AUC0-10h分别为(1 314±589)、(1 751±656)、(3 452± 2 111) ng·h·mL^-1,t1/2分别为(1.57±1.17)、(1.80±1.05)、(1.68±1.04) h。B组受试者多次给药苯佐那酯软胶囊200 mg后,BBA的Cav为(604±220) ng·mL^-1,DF为(5.34±1.26),RCmax为(1.20±0.45),RAUC为(1.10±0.13);苯佐那酯的Cav为(356±126) ng·mL^-1,DF为(5.91±1.35),RCmax为(1.24±0.57),RAUC为(1.31±0.33)。结论:在100~400 mg的给药剂量范围内,苯佐那酯不具有线性药代动力学特征。多次给药苯佐那酯软胶囊200 mg后,BBA和苯佐那酯在体内会产生蓄积。

A novel synthesis of fluvoxamine maleate

Fluvoxamine maleate is an excellent antidepressive drug. In the literatures, it was synthesized by the use of 4-（trifluoromethyl） aniline or 4-（trifluoromethyl） benzonitrile as starting materials and 5-methoxy-4＇-（trifluoromethyl-phenyl） valerophenone as a key intermediate. However, the methods in literatures have some disadvantages, such as the use of expensive materials, heavy pollution of environment, long reaction time and low yield of the product （only 30-40% overall yield）. We herein report an environmentally friendly synthetic method of fluvoxamine maleate, which used 4-（trifluoromethyl） benzoic acid and tetrahydrofuran as starting materials and FeCI3 as catalyst for the coupling of acid chloride with Grignard reagent. The fluvoxamine maleate was synthesized in 46% overall yield, through the oximation, etheration and salification of the intermediate successively.This method has some advantages, such as the use of commercially available materials, low cost, short production period （12-14 h）, high yield and light pollution.

Hydrothermal Synthesis and Crystal Structure of a Copper Complex

The title compound [Cu（IB）2]n·n（H2O） 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-（1H-Imidazol-1-yl）benzoic acid（HIB）,and character-rized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic,space group C2/c with a = 14.349（7）,b = 5.977（3）,c = 21.368（9） ,β = 104.956（9）o,V = 1770.5（2）3,Z = 4,C20H16CuN4O5,Mr = 455.92,Dc = 1.710 g/cm3,F（000） = 932 and μ（MoKα） = 1.279 mm-1.The final R = 0.0337 and wR = 0.0888 for 1972 observed reflections with Ⅰ 〉 2σ（Ⅰ） and R = 0.0369 and wR = 0.0926 for all data.X-ray diffraction reveals that the IB ligand links the Cu（Ⅱ） atoms into a double stranded chain.The extensive supramolecular interactions lead to the formation of an infinite 2D structure.

Chemical constituents and anticoagulant activity from Delphinium brunonianum Royle

Delphinium brunonianum Royle belongs to Ranunculaceae family and has the effects of dispelling wind to relieve itching and cooling blood to detoxify.It was found that the extracts of D.brunonianum had good anticoagulant activity which was extracted with 70%ethanol in our previous researches.Then,16 compounds were isolated and identified from the extract of D.brunonianum,among which compounds 5,7-10,12,14,15-16 were isolated from this genus for the first time,and compounds 2-4 were isolated from this plant for the first time.And the coagulation activity assay showed that compounds 10,14 and 15 had good anticoagulant activity by activated partial thromboplastin time(APTT),thrombin time(TT)and prothrombin time(PT)in vitro.