New structurally diverse photoactive cadmium coordination polymers.

Four structurally diverse coordination polymers 1-4 (CP1-CP4) were designed and constructed from Cd(II) ions and various carboxyl ligands (H2oba, 4,4'-oxydibenzoic acid; H2bpa, (E)-4,4'-(ethene-1,2-diyl)dibenzoic acid; H2pbda, 4,4'-((1,3-phenylenebis(methylene))bis(oxy))dibenzoic acid) and the alkene containing ligand (CH3-bpeb, 4,4'-((1E,1'E)-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine). CP1-CP4 possess Cd2 binuclear secondary building units (SBUs). The geometry of the dicarboxylate ligands and the reaction conditions determined the final structure with a variety of motifs. CP1 possesses an interdigitated 2D structure, while CP2 consists of a 1D channel-like motif with isolated CH3-bpeb molecules embedded in the channels. The solid-state structure of CP3 consists of two unique layers interpenetrated to form a 2D + 2D → 2D polycatenated backbone, while a 1D channel-like motif filled by isolated CH3-bpeb molecules was observed for CP4. In all four coordination polymers pairs of CH3-bpeb molecules were bound or encapsulated by the Cd2 secondary building units at an appropriate distance and orientation for solid-state [2 + 2] photodimerization of one pair of CC bonds. Desolvation of CP3 with heat resulted in a decrease in solid-state fluorescence and a slowing of the rate of solid-state photodimerization.

Improving the Solubility and Bioavailability of Pemafibrate via a New Polymorph Form II.

Pemafibrate is a new generation of anti-hyperlipidemia drugs. However, its poor solubility in water (0.410 mg/mL at 25 °C) has limited its oral bioavailability. In this study, we aimed to improve the solubility and consequently the oral bioavailability of pemafibrate via a new polymorph. A new polymorph Form II was successfully obtained by controlling the crystallization temperature and characterized by multiple analysis methods. The thermodynamic properties of Form I and Form II are almost the same, the melting points of crystal Form I [differential scanning calorimetry (DSC) onset: 97.5 °C, melting entropy: -76 J/g] and crystal Form II (DSC onset: 96.6 °C, melting entropy: -80 J/g) are very close, and the crystallinity of both is very high. In pure water, Form II is about 1.9 times that of Form I in terms of the intrinsic dissolution rate (IDR) and powder solubility. In medium, the IDR characterization was performed in a pH 6.8 buffer. The solubility of this Form II in 0.1 M HCl (pH 1.0) and phosphate buffers (pH 6.8) was investigated, and the results showed that the solubility of Form II was 2.1 and 2.0 times that of Form I, respectively. The crystal structure of Form II shows that the hydrophilic carboxyl groups of the compound are arranged outside the unit cell, which may be the reason for the increased solubility. We also studied the pharmacokinetics of beagle dogs. The mean AUC0-24h of Form II is about 2.6 times that of Form I, indicating that the solubility and bioavailability of pemafibrate can indeed be improved by forming the new polymorph Form II. It may become an ideal solid form of active pharmaceutically ingredient suitable for pharmaceutical preparations, and it can be further studied in the later period.

Improving the solubility and bioavailability of anti-hepatitis B drug PEC via PEC-fumaric acid cocrystal.

PEC is a new generation of phosphamide ester anti-hepatitis B virus drug. It is a prodrug of tenofovir and can be rapidly metabolized to tenofovir. However, its poor solubility in water (0.219 mg mL-1 at 25 °C) has limited its oral bioavailability. In this study, we aimed to improve the solubility and consequently the oral bioavailability of PEC via a cocrystal. A cocrystal of PEC with fumaric acid (FUA) (PEC-FUA, 1 : 1) was successfully obtained and characterized. The crystal structure of this cocrystal was tested using a single crystal X-ray diffraction method. The intrinsic dissolution rate (IDR) characterization was performed in a pH 6.8 buffer. The solubility of this cocrystal in 0.1 M HCl (pH 1.0) and pH 6.8 phosphate buffers was investigated, and the results showed that the solubility of the cocrystal was 3.8 and 4.0 times that of free PEC, respectively. We also studied the pharmacokinetics of beagle dogs. The mean AUC0-24 h of the cocrystal is about 4.2 times that of free PEC, indicating that the solubility and bioavailability of PEC can indeed be improved by forming the cocrystal. It may become an ideal solid form of an active pharmaceutical ingredient suitable for pharmaceutical preparations, and it can be further studied later.

Coordination-Driven Stereospecific Control Strategy for Pure Cycloisomers in Solid-State Diene Photocycloaddition.

To obtain a pure product without the isomer byproducts is a goal that many chemists are pursuing. As one kind of very important synthesis method, the photochemical reaction is simple and straightforward yet low-selective. In this work, a coordination interaction-based oriented synthesis strategy has been proposed to realize the precise stereochemical control of the isomeric cyclic compounds in the photocycloaddition reaction. Through fixing the reactants via coordination interactions, the arrangements and configurations of the reactants can be adjusted, thereby successfully producing all of the related photocycloaddition products without isomer byproducts for the first time. This work not only provides a new route to synthesize the pure cyclic compounds but also expands the application of the photocycloaddition reaction.

Familial aggregation and heritability of hypertension in Han population in Shanghai China: a case-control study.

BACKGROUND: To explore the familial aggregation and heritability of hypertension in Han in Shanghai China. METHODS: According to l:l matched pairs design, 342 patients of hypertension and 342 controls were selected and investigate their nuclear family members in the case-control study. The method of genetic epidemiology research was used to explore the familial aggregation and heritability of hypertension. RESULTS: The prevalence rate of hypertension of first-degree relatives was significantly higher (34.44%) than that of second- degree relatives (17.60%) and third-degree relatives (13.51%) in Han Population in Shanghai China. Separation ratio p was 0.217, and prevalence rate of case group relatives was higher than that of control group relatives. The results showed a phenomenon of familial aggregation in the distribution of hypertension. The heritability of first- degree relatives was 49.51%; that of second-degree relatives and third-degree relatives were respectively 23.42 and 21.41%. CONCLUSION: The distribution of essential hypertension has phenomenon of familial aggregation in Han Population in Shanghai China. The separation ratio of essential hypertension in this study shows that essential hypertension conform to the characteristics of multigene genetic disease. The heritability of first-degree relatives is bigger than that of second-degree relatives and third-degree relatives.

Synthesis, structures and properties of two metal-organic coordination polymers derived from manganese(ΙΙ), thiabendazole and polydentate carboxylic acids.

Two novel binuclear Mn(II) metal-organic coordination complexes [Mn2(TBZ)2(CDC)(C2O4)]n (1), {[Mn2(TBZ)2(BDC)(0.5)(BTC)(H2O)2]·ET}n (2), (where TBZ = thiabendazole, H2CDC = trans-1,4-cyclohexanedicarboxylic acid, H2C2O4 = oxalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid, ET = ethanol, H2BDC = 1,4-benzenedicarboxylate) have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, electrochemical analysis and single crystal X-ray diffraction. The X-ray structure analysis reveals that 1 is s two-dimensional layer and 2 is s one-dimensional chain. In complex 1, it reveals 2-D layers composed of multi-(bidentate) bridging ligands (CDC and C2O4), and in 2, the coordinated BTC ligands adopt a monodentate mode and with BDC ligands adopt alternately chelating Mn1 and Mn2 bridges into 1-D chains. The 3-D structures of the two complexes are stabilized by π-π stacking interactions and hydrogen bonds.

catena-Poly[[[2-(1,3-thia-zol-4-yl)-1H-benzimidazole]-manganese(II)]-µ-oxalato].

In the title compound, [Mn(C2O4)(C10H7N3S)] n , the Mn(II) cation is chelated by one 2-(1,3-thia-zol-4-yl)-1H-benzimidazole ligand and two oxalate anions in a distorted N2O4 octa-hedral geometry. Two independent oxalate anions are located on individual inversion centers and bridge the Mn(II) cations into a polymeric chain running along [101]. The thia-zole ring is approximately coplanar with the benzimidazole ring system [dihedral angle = 4.19 (9)°]. In the crystal, classical N-H⋯O hydrogen bonds and weak C-H⋯O hydrogen bonds link the polymeric chains into a three-dimensional supra-molecular architecture.

Aquachloridobis[2-(1,3-thia-zol-4-yl-κN)-1H-benzimidazole-κN(3)]nickel(II) nitrate.

In the title compound, [NiCl(C(10)H(7)N(3)S)(2)(H(2)O)]NO(3), the Ni(II) ion is coordinated by four N atoms from two chelating 2-(1,3-thia-zol-4-yl)-1H-benzimidazole ligands, one Cl atom and one water mol-ecule in a distorted octa-hedral geometry. In the crystal, O-H⋯O, N-H⋯O and N-H⋯Cl hydrogen bonds link the complex cations and nitrate anions into a three-dimensional network. π-π inter-actions between the thia-zole and imidazole rings and between the thia-zole and benzene rings are observed [centroid-centroid distances = 3.592 (3) and 3.735 (3) Å].

[Study on synthesis and fluorescence characterization of europium and terbium complexes of 1-(5-(2-hydroxyphenyl)-3-methyl-4,5-dihydropyrazol-1-yl) ethanone].

Six solid complexes(TbL3 x 2H2O, TbL2 (phen) x H2O, TbL2 (TPPO), EuL3 x 2H2O, EuL2 (phen) x 2H2O and EuL2 (TPPO) x 2H2O) have been synthesized based on the pyrazole ligand(HL)(phen = 1,10-phenanthroline, TPPO = Tri-phenylphosphine oxide, HL=1-(5-(2-hydroxyphenyl)-3-methyl-4,5-dihydropyrazol-1-yl) ethanone). These complexes were characterized by elemental analysis, IR spectra, and fluorescence spectra. The IR spectra indicated that all complexes exhibited the characteristic peaks of asymmetric stretching vibration v (C=O) and symmetric stretching vibration v (C=N) peaks. The C=O stretching band at 1,644 cm(-1) of HL molecule shifted to lower band in the complexes. The O-H band at 3,072 of the HL ligand is also shifted to lower band. All these shifts indicated that carbonyl group, O-H and C=N take part in coordinating with the rare-earth ion in the form of bridging tridentate. The excitation and emission spectra of the six complexes were determined at room temperature and the results show that EuL2 (Phen) x 2H2O and TbL2 (Phen) X 2H2O display the strongest relative fluorescence intensity with the excited bands at 310 and 320 nm, respectively. Meanwhile, the emission intensities of Eu3+ and Tb3+ complexes were greatly sensitized by phen.

Two novel thioindate-thioantimonate compounds [Ni(dien)2]2In2Sb4S11 and [Ni(dien)2]3(In3Sb2S9)2·2H2O with transition metal complexes.

Two novel thioindate-thioantimonate compounds [Ni(dien)(2)](2)In(2)Sb(4)S(11) (1) and [Ni(dien)(2)](3)(In(3)Sb(2)S(9))(2)·2H(2)O (2) (dien = diethylenetriamine) have been solvothermally synthesized and structurally characterized. 1 contains heterometallic pseudosemicube [In(2)SbS(8)] clusters and bow-like trimeric [Sb(3)S(7)] units, which are linked to form a [In(2)Sb(4)S(11)(4-)](n) chain, whereas 2 consists of chain-like [In(6)S(18)] units and pyramidal SbS(3), which are interconnected to give a [In(3)Sb(2)S(9)(6-)](n) layer with a large rectangle-like 12-ring. The optical properties of 1 and 2 have been investigated by UV-vis spectroscopy.

catena-Poly[[[diaqua-sodium]-di-µ-aqua] 2-(2-pyrid-yl)quinoline-4-carboxyl-ate].

In the title compound, [Na(H(2)O)(4)](C(15)H(9)N(2)O(2)), the Na(+) ion is coordinated by six water mol-ecules in an octa-hedral geometry. The NaO(6) octa-hedra are connected by sharing edges, forming a cationic chain along the b-axis direction. O-H⋯O and O-H⋯N hydrogen bonds link the chains and the 2-(2-pyrid-yl)quinoline-4-carboxyl-ate anions into a two-dimensional network parallel to (100).

Bis[µ-2-(2,4-difluoro-phen-yl)-1,3-bis-(1H-1,2,4-triazol-1-yl)propan-2-olato]dicopper(II) bis-(perchlorate).

The title complex, [Cu(2)(C(13)H(11)F(2)N(6)O)(2)](ClO(4))(2), which was hydro-thermally synthesized, contains a binuclear copper cluster (2 symmetry) with a Cu(2)O(2) rhombus [Cu-O = 1.927 (2) Å] formed by donation of two O atoms from two chelate rings. The tridentate function of each ligand is completed by two N atoms coordinated to the two Cu(II) atoms [Cu-N = 1.933 (2) Å]. The separation distance of two Cu(II) atoms in a cluster is 2.988 (1) Å. The dihedral angle between the six-membered chelate rings is 2.13 (9)°. The perchlorate counter-anion is disordered over two sites in a 0.58 (10):0.42 (10) ratio.

Synthesis, characterization and luminescence properties of Eu(III) and Tb(III) complexes with novel pyrazole derivatives and 1,10-phenanthroline.

Two novel pyrazole-derived ligands, 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid (CDPA) and 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-phenylpicolinamide (CDPP) were prepared by 3,6-dichloropicolinic acid (DCPA). Their complexes with terbium(III) and europium(III) were synthesized. The complexes were characterized by elemental analysis, infrared spectra, (1)H NMR and TG-DTG. Furthermore, the above complexes using 1,10-phenanthroline as a secondary ligand were also synthesized and characterized. The luminescence properties of these complexes in solid state were investigated. The results suggested that Tb(III) complexes exhibit more efficient luminescence than Eu(III) complexes and the fluorescence of the complexes with 1,10-phenanthroline as a secondary ligand was prominently stronger than that of complexes without this ligand., and the three ligand (DCPA), (CDPP) and (CDPA) are excellent sensitizers to Eu(III) and Tb(III) ion.

Diaqua-(5-methyl-1H-pyrazole-3-carboxyl-ato)(4-nitro-benzoato)copper(II).

In the title complex, [Cu(C(7)H(4)NO(4))(C(5)H(5)N(2)O(2))(H(2)O)(2)], the Cu(II) ion is coordinated in a slightly distorted square-pyramidal enviroment. The basal plane is formed by an N atom and an O atom from a 5-methyl-1H-pyrazole-3-carboxyl-ate ligand and by two O atoms from two water ligands. The apical position is occupied by a carboxylate O atom from a 4-nitro-benzoate ligand. In the crystal structure, inter-molecular O-H⋯O and N-H⋯O hydrogen bonds link complex moleclues, forming extended chains parallel to the a axis.

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κO,N,N']copper(II) tetra-hydrate.

In the title complex, [Cu(C(11)H(9)ClN(3)O(2))(2)]·4H(2)O, the Cu(II) atom is in a distorted octa-hedral coordination environment, coordinated by four N atoms and two O atoms from two tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The mol-ecules are linked via inter-molecular O-H⋯O hydrogen bonds involving water mol-ecules to form extended chains along [010], and there are short Cl⋯Cl contacts [3.153 (4) Å].

Nitrato(1,10-phenanthroline)(1H-1,2,4-triazole-3-carboxyl-ato)copper(II).

In the title complex, [Cu(C(3)H(2)N(3)O(2))(NO(3))(C(12)H(8)N(2))], the Cu(II) ion is coordinated by an N and an O atom from a bidentate 1H-1,2,4-triazole-3-carboxyl-ate (TRIA) ligand, two N atoms from a 1,10-phenanthroline (phen) ligand, and an O atom from a nitrate ligand in a slightly distorted square-pyramidal environment. In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link mol-ecules into one-dimensional chains propagating along the b axis direction.

Tris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]gadolinium(III) methanol hemisolvate 2.5-hydrate.

In the title complex, [Gd(C(11)H(10)N(3)O(2))(3)]·0.5CH(4)O·2.5H(2)O, the Gd atom is coordinated by six N atoms and three O atoms derived from three tridentate monoanionic 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The mol-ecules are linked together via hydrogen bonds involving the solvent water and methanol mol-ecules.

Diaqua-bis[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κN,N',O](nitrato-κO,O')lanthanum(III) monohydrate.

In the title complex, [La(C(11)H(10)N(3)O(2))(2)(NO(3))(H(2)O)(2)]·H(2)O, the La atom is coordinated by four N atoms and six O atoms derived from two 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands, one nitrate anion and two water mol-ecules. The mol-ecules are linked together via hydrogen bonds involving the water mol-ecules, forming a three-dimensional network.

Aqua-tris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]-κN,N',O;κO-dysprosium(III) trihydrate.

In the title complex, [Dy(C(11)H(10)N(3)O(2))(3)(H(2)O)]·3H(2)O, the Dy(III) atom is coordinated by four N atoms and four O atoms derived from three tridentate deprotonated 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands and one water mol-ecule. The complex and solvent water mol-ecules are linked together via O-H⋯O, O-H⋯N, C-H⋯O and C-H⋯π hydrogen-bonding inter-actions, forming a three-dimensional network structure.

Bis[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κN,O]cadmium(II) 1.75-hydrate.

In the title complex, [Cd(C(11)H(10)N(3)O(2))(2)]·1.75H(2)O, the Cd atom is coordinated by four N atoms and two O atoms from two tridentate 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands in a distorted cis-N(4)O(2) octa-hedral geometry. Three water mol-ecules, with occupancies of 1.0, 0.5 and 0.25, complete the asymmetric unit. The components of the crystal structure are linked via hydrogen bonds, forming a three-dimensional network.