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Gastric cancer is a leading cause of tumor-associated death worldwide. Metastasis and chemoresistance are crucial barriers for gastric cancer treatment. The Forkhead Box M1 (FOXM1) transcription factor has been reported as a promising treatment target for various types of tumors, but its effects on gastric cancer progression are not fully understood. In the present study, we found that FOXM1 expression levels were significantly up-regulated in human gastric cancer cell lines and tissues, and its expression was much higher in patients with metastasis. We then found that suppressing FOXM1 with its inhibitor thiostrepton (THIO) significantly reduced the proliferation of gastric cancer cells, while induced G0/G1 and apoptosis. Moreover, reactive oxygen species (ROS) production, mitochondrial impair and autophagy were remarkably provoked in gastric cancer cells treated with THIO, which were required for the regulation of apoptotic cell death. Furthermore, THIO exposure considerably suppressed the migration, invasion and angiogenesis in gastric cancer cells. The inhibitory effects of THIO on tumor growth and metastasis were confirmed in an established gastric cancer xenograft mouse model without detectable toxicity. Intriguingly, our in vitro studies showed that the anti-cancer effects of THIO on gastric cancer were almost abolished upon FOXM1 over-expression, indicating the necessity of FOXM1 suppression in THIO-inhibited tumor growth. In addition, higher FOXM1 expression was detected in gastric cancer cells with chemoresistance. Both in vitro and in vivo studies illustrated that THIO strongly promoted the drug-resistant gastric cancer cells to chemotherapies, proved by the considerably decreased cell proliferation and epithelial-mesenchymal transition (EMT) process. Together, these findings revealed that FOXM1 was a promising therapeutic target for gastric cancer treatment, and THIO exerted potential as an therapeutic agent for the disease.

The aim of this study is to propose an effective approach to evaluate the stability of a shield tunnel face with tensile strength cutoff by using the upper-bound limit analysis method. Bas...

To analyze the association of stored autologous blood transfusion (SABT) with tumor recurrence in PCa patients after radical prostatectomy and explore the application of SABT in this surgical procedure.Forty-five PCa patients underwent radical prostatectomy in our hospital in recent five years, of whom, 20 received SABT (group A) and the other 25 allogeneic blood transfusion (group B) intraoperatively. After surgery, we followed up the patients regularly for 3－66 months by examination of the levels of total PSA (tPSA) and free PSA (fPSA), digital rectal examination (DRE), and MRI to observe the biochemical recurrence of the tumor. We compared the data obtained between the two groups of patients.In group A, 8 cases were in stages T1a－T1b and 12 in stages T2a－T2c, and in group B, 14 cases were in stages T1a－T1b and 11 in stages T2a－T2c. The volume of transfused blood was 800 ml in group A and 400－1 200 ml in group B. No statistically significant differences were observed between the two groups in the operation time, intraoperative blood loss or postoperative Gleason scores (P0.05), nor in the tPSA level or the results of DRE and MRI at 12, 24, 36, 48 and over 48 months (P0.05).SABT is safe for PCa patients undergoing radical prostatectomy and does not increase the tumor recurrence rate after surgery.

The available theoretical models for evaluating seismic active earth pressures are limited to plane strain analyses and linear failure criterion. To fill this research gap, with a combination of the kinematical approach of limit analysis, the spatial discretization technique as well as the pseudo-static approach, this work develops a discretized three-dimensional failure mechanism of sloping backfills that is composed of an end cap and a central plane-strain insert to estimate the seismic active earth pressure coefficient under nonlinear failure criterion. Compared with the existing three-dimensional kinematically admissible failure mechanisms, the developed one has three significant merits: (1) the normality condition is strictly satisfied in the generation of the end cap; (2) the work rates can be computed by a summation of elementary work rates conveniently instead of tedious integral schemes; (3) the considerations of the nonlinear failure criterion and the sloping backfill. Comparisons with the existing upper bound solutions and experimental results in terms of active earth forces or active earth pressure coefficients are conducted to verify the proposed model. Parametric studies are performed to study the influences of model parameters, including the seismic coefficient, the sloping angle of backfills as well as the nonlinear parameters, on the active earth pressure coefficients.

Pentadentate ligand, N-cyclohexanoylsalicylhydrazide (H3chxshz) (1), and its self-assembled 30-metallacrown-10, [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH (2), have been synthesized. Ten manganese (III) ions and ten deprotonated ligands (chxshz3−) construct a 30-membered ring based on the M-N-N-M linkage in the novel decanuclear manganese(III) metallamacrocycle 2. The chiralities of Mn atoms in the diaza-bridged ring are in alternating Λ and Δ configurations. The magnetic property of the title 30-metallacrown-10 shows a weak antiferromagnetic exchange interaction with an observed μeff of 14.93 μB at 300 K.

A novel high durability epoxy asphalt concrete for bridge deck pavements is introduced in this paper, including the manufacturing process of epoxy asphalt binder and laboratory evaluation for this material. Various laboratory tests were conducted to evaluate the pavement performance of the materials, such as fatigue test, wheel tracking test, moisture susceptibility test and thermal stress restrained specimen test. Test results show that epoxy asphalt concrete has 20137 cycles/mm dynamic stability at 70°C, and-28.4 °C fracture temperature. The fatigue equations of epoxy asphalt concrete at different temperatures were obtained. Findings from the research indicate that the epoxy asphalt concrete is a suitable material for the pavement of long-span steel bridges in China due to its profound performance.

In order to comparatively study the effect of warm mix modifiers on the road performance of guss asphalt, the guss asphalt mixtures, whose asphalt aggregate ratio were 8.5%,9.0%,9.5% respectively, were mixed with 0%,1%,2%,3% of the RH and Sasobit warm mix modifiers. Then by means of Lueer test, penetration test, wheel track test and low-temperature bending test, the performance of guss asphalt were evaluated. The test results show that: RH and Sasobit can effectively improve the workability of guss asphalt; RH is better than Sasobit in reducing viscosity of guss asphalt; RH reduces the high-temperature properties of guss asphalt; On the contrary, Sasobit can improve the hightemperature performance of guss asphalt; RH and Sasobit have an adverse impact on the crack resistance of guss asphalt in low temperature, so their content should not too high. Guss asphalt has characteristics of high construction temperature and energy consumption. In order to reduce construction temperature, based on energy conservation, low-carbon emission environment, reduce the aging of asphalt principle, warm modifiers could be used to reduce the viscosity of guss asphalt at high temperatures[1-5]. Sasobit modifiers imported from Germany are used much more to improve the workability of guss asphalt. In this paper, 0%, 1%, 2%, 3% RH and Sasobit warm mix modifier were mixed with the aggregate ratio of 8.5%, 9.0%, and 9.5% of the Guss asphalt to compare and analyzed the performance of those two warm modifiers on Guss asphalt.

A cutting slope model can be simplified as plane strain one, the stress field of cutting slope can be analyzed with elastic wedge body theory. By using strength criterion of slope material (Mohr-Coulomb strength criterion with safety reserve and uniaxial tensile strength criterion), the disturbed zone caused by excavation can be calculated in 3D stress state, so all the disturbed zone after each step of excavation from the top down can be searched out. The main analysis steps for judging disturbed zone are described in the paper, including the methods to calculate the stress state of cutting slope, the unloading value and the scope of disturbed zone after last step of excavation. Finally, an example in Suining-Ziyang expressway engineering is chosen to explain detailedly the analytical process with elastic wedge body theory to determine the disturbed zone.

Weathering effects, expansive pressure and pore water pressure are investigated to evaluate their effect on expansive clay slope stability. In particular, the effect of expansive pressure is analyzed to consider its effect on the stability of surface layer of the slope. In this paper, the distribution of expansive pressure in a slope is evaluated and used to analyze the stability of the surface layer of a clay slope. The proposed analysis method is applied in the third ring road project in Chengdu, China, where there are expansive clay slopes. Reasonable results are achieved.

The compatibility of rock asphalt modification agent and matrix asphalt was excellent, while different contents of the rock asphalt had great influence on the mechanics properties of mixture. Based on the aggregate grade of the AC-20 mixture, the mechanical properties of the matrix asphalt mixtures and the rock asphalt mixtures with different quantities of rock asphalt were studied by laboratory tests, including the high-temperature stability, low-temperature anti-cracking performance and water stability. This research is to give reference for the proper rock asphalt quantity of the mixture.

Three palladium (II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd (p-CH3C6H4IBI)2 (1), Pd (C6H5IBI)2 (2) and Pd2Cl2 (C6H5CH2IBI)2 · CHCl3 (3), were prepared and characterized by IR, Raman and X-ray diffraction studies. The geometries around the palladium atoms in the complexes 1 and 2 are distorted trans-PdN4 square planes, and the Schiff base ligands RIBI− are coordinated through their oximo-nitrogen atoms and imino-nitrogen atoms. The week Pd…HC agostic interactions [Pd…H = 0.2764 nm] complete the hexacoordinate environment around palladium in the complex 1. The octahedral deformation of the classical square planar environment of the Pd atom is due to the week Pd…O (1b) interactions [PdO (1b) = 0.3157 (9) nm] in the complex 2. The complex 3 is a first example of binuclear complex with isonitrosoketoimine ligands, in which one of oximo groups is coordinated through oximo-nitrogen and oximo-oxygen atoms.

A lead(II) complex [Pb(Hfysh)2] (1) (H2fysh = furan-2-ylmethylene salicyloyl hydrazone) has been synthesized and characterized. The lead atom is in a holodirected eight-coordinated polyhedron. There are secondary Pb–O interactions that give rise to a novel 3D-diamond-like coordination network. The luminescent property of 1 in the solid state was investigated.

Two vanillin derivatives, 4-hydroxy-3-methoxybenzaldehyde nicotinoylhydrazone (L1) and 4-hydroxy-3-methoxybenzaldehyde salicyloylhydrazone (L2), were synthesized. The two flexible ligands have been employed to assemble with Pb(II), Cu(II), or Co(II) ion, leading to the formation of five coordination polymers varying from zero- to three-dimensional structures. Complex [Pb2(L1)2(NO3)2]·3H2O (1) features a novel 3D diamond-like coordination network based on binuclear units as binodes and hydrazone ligands, L1, as linkers. However, complex Pb2(L1)2(OAc)2(H2O)2 (2) presents a 1D double-strand chain structure. Two factors, the second ligand (acid ligand) and different coordination ability of water molecules, are investigated to further explore its relationship with the resultant crystalline architectures in complexes 1 and 2. The donor atoms in the two lead(II) complexes 1 and 2 can cluster to one side leaving an “open” coordination site to accommodate the stereochemically active 6s2 lone pair. Complex Cu(L2)2 ...

The Ce(III) ion in the title complex, [Ce(NO(3))(3)(C(13)H(12)N(4)O)(2)], is 12-coordinated by six chelating nitrate O atoms and six donors (2 O and 4 N atoms) of two N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligands, exhibiting a bicapped pentagonal-antiprism-type coordination geometry. The title complex possesses C(2) point symmetry and is located on a twofold crystallographic axis. Each molecule is linked with four surrounding molecules by four N-H...N hydrogen bonds, resulting in an extended two-dimensional layer parallel to the ab plane, while pi-pi interactions between pyridine rings from neighboring complex molecules connect the two-dimensional layers into a three-dimensional cerium-organic supramolecular structure.

Reactions of asymmetric ligand N-phenylacetyl picoloylhydrazide (HL) and copper(II) acetate/chloride give two complexes CuL2 (1) and Cu2Cl2L2 (2). The coordination geometries of Cu(II) in 1 and 2 are a severely distorted octahedron and a distorted square pyramid, respectively. The binuclear copper complex 2 contains a centrosymmetric Cu2(μ-Cl)2 core. Individual molecules of 1 and 2 further self-assemble through non-covalent intermolecular bonds in the solid state to form extended 2-D polymers. The magnetic properties, IR, EA, and solid-state photoluminescence properties of the title complexes are presented.

A lead(II) orotate complex [Pb(HOr)(H2O)]n (1), (H3Or = orotic acid) was synthesized under hydrothermal condition and characterized by X-ray diffraction, IR, solid-state photoluminescence and thermogravimetric analysis. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (48, 66, 8)(413, 62) topology. The complex exhibits photoluminescence at 546 nm (λex = 350 nm).

Six title copper(II)/zinc(II) coordination polymers have been synthesized, using the metal salt with different oxidation states (Cu(NO3)2/CuBr2/CuI/Zn(OAc)2), dicarboxylate ligand (2,3-pyridinedicarboxylic acid (pydc) or 2,3-pyrazinedicarboxylic acid (pzdc)) and the auxiliary ligand (2,2′-bpy, phen or 4,4′-bpy). The dicarboxylate ligand (pydc or pzdc) bridges two neighboring metal atoms to form a 1D chain in complexes 1, 2, 3, 4 and 6 and 2D network in 5, respectively. There are an extended 3D metal-organic framework in 1–5 and an extended 2D network in 6, respectively. The magnetic properties and photoluminescent property of some title complexes were investigated. The factors affecting structural characterizations in the products have been discussed.

In the two title complexes of cinnamaldehyde salicyloylhydrazone [or 2-hydroxy-N'-(3-phenylprop-2-enylidene)benzohydrazide], [Ni(C(16)H(13)N(2)O(2))(2)(CH(4)O)(2)], (I), and [Ni(C(16)H(13)N(2)O(2))(2)(C(5)H(5)N)(2)], (II), the Ni(II) atoms lie on crystallographic inversion centres and have distorted octahedral geometries. The equatorial plane is defined by two carbonyl O atoms and two hydrazine N atoms of two bidentate trans-oriented salicyloylhydrazone ligands. The axial positions are occupied by two O atoms from two coordinated methanol molecules in (I) and by two N atoms from two coordinated pyridine molecules in (II). There is an extended chain structure in (I) resulting from intermolecular O-H...O hydrogen bonds between coordinated methanol molecules and phenol O atoms, while (II) comprises discrete molecules. Complex (I) also exhibits weak pi-pi stacking interactions, and intramolecular O-H...N hydrogen bonds are present in both (I) and (II). The salicyloylhydrazone ligands in (I) and (II) are coordinated to the metal atom through the carbohydrazide O and N(2) atoms, not via the phenol O atom. We have established a link between the reagents used and the nuclearity of the complex formed: the ligand produced by condensation between salicylhydrazide and an aldehyde leads to mononuclear complexes, while replacing the aldehyde in the reaction by a ketone leads to multinuclear complexes.

Five complexes with 3,5-dinitrosalicylate (3,5-(NO 2 ) 2 sal) and N-donor ligand, [Cd{3,5-(NO 2 ) 2 sal}(phen)(H 2 O)] n ( 1 ), Ni{3,5-(NO 2 ) 2 sal}(phen)(H 2 O) 2 ( 2 ), [Co{3,5-(NO 2 ) 2 sal}(4,4′-bipy)(H 2 O)·(H 2 O)] n ( 3 ), [Co{3,5-(NO 2 ) 2 sal}(phen)] n ( 4 ) and [Zn{3,5-(NO 2 ) 2 sal}(phen)] n ( 5 ), have been synthesized by hydrothermal reactions and characterized by single crystal X-ray analysis, where phen = 1,10-phenanthroline and 4,4′-bipy = 4,4′-bipyridine. There are one-dimensional left- and right-handed helical chains in complexes 1 , 4 and 5 , an extended 3D structure in 2 , and a 2D rectangular grid-like network in 3 . The C–H···O hydrogen bonds lead to the formation of 3D supramolecular structures in the five title complexes. The fluorescent spectra study show that compounds 1 and 5 exhibit weak fluorescent emission in the solid state at room temperature.

Three trinuclear nickel complexes containing N-salicylyl 4-phenyl-thiosemicarbazide(abbreviated as spt3−) have been synthesized. They are complex [Ni3(spt)2(dpt)2]·2C3H7NO (1) with 2,5-diphenylamiyl 1,3,4 thiodiazone ligand(dpt) and the other two complexes without dpt ligand ([Ni3(spt)2(H2O)4]·2C3H7NO (2) and [Ni3(spt)2(C5H5N)2(H2O)2]·2C3H7NO (3)). Central Ni atom and two terminal Ni atoms in the three complexes are combined by two bridging deprotonated spt3− ligands, forming a strictly linear trinuclear nickel structure unit with a Ni N N Ni N N Ni core. There is an extended 1D structure in 2 and 3 formed by intermolecular hydrogen bonds O H…O. The influence of pH of the reaction medium upon the composition of the final products is discussed.

Reactions among Cu(ClO4)2 · 6H2O, Cu(acac)2/VO(acac)2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu2L(acac)(H2O)2]ClO4 (1), [Cu4L2(acac)2(py)2](ClO4)2 (2) and (VO2)2L2Cu2(acac)2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO4− anion, and an extended 1D structure in complex 2 constructed by weak π⋯π stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1.

Three trinuclear zinc(II)/nickel(II) complexes with two pentadentate ligands, N-p-nitrobenzoylsalicylhydrazidate (H-3-p-nbzshz) and N-o-nitrobenzoylsalicylhydrazidate (H-3-o-nbzshz) have been synthesized and characterized by X-ray crystallography. The complex [Zn-3(p-nbzshz)(2)(C5H5N)(4)](n) (1) molecule exhibits a one-dimensional wave-like chain structure resulting from the linkage of phenolate oxygen donor atoms of the ligands between neighboring motifs. The two nickel(II) complexes, Ni-3(p-nbzshz)(2)(C5H5N)(4) (2) and Ni-3(o-nbzshz)(2)(C3H7NO)(2)(C2H6O)(2) (3) are trinuclear complexes in which three nickel(II) centers exhibit alternating square-planar and octahedral geometries. Complex 2 exhibits a curved Ni-3 metal arrangement with a Ni(1)-Ni(2)-Ni(3) angle of 62.36 degrees, while the three nickel atoms in complex 3 are strictly linear with an angle of 180 degrees. (C) 2007 Elsevier Ltd. All rights reserved.

The reactions between Cd(OAC)(2)/Cu(NO3)(2) and mixed ligands (2,3-pyrazinedicarboxylic acid (pzdc) and N-donor ligands) under different reaction conditions give the three title complexes 1, 2 and 3. There is a (4,8) net 2D network structure and a rectangular grid network structure in the cadmium complexes [Cd(pzdc)(phen)] center dot H2O (1) and Cd-2(pzdC)(2)(4,4'-bpy)(H2O)(2) (2), respectively. The complex [CU4(pzdC)(4)(phen)2(H'0)(4)] - I OH,O (3) has a I D zigzag chain structure. The influences of coordination modes of the pzdc ligand and N-donor ligands on the superstructural diversity have been discussed. Complexes 1 and 2 exhibit strong fluorescent emission bands in the solid state at room temperature. The EPR spectrum of 3 is typical for a square-pyramidal geometry of copper (II) ions. (c) 2007 Elsevier Ltd. All rights reserved.

The hydrothermal reactions of Co(OAc)2 · 4H2O, 3,5-dinitrosalicylate (3,5-(NO2)2sal) and 2,2′-bipyridine (2,2′-bipy) with different reaction periods give metallamacrocycles 1 and 2 with the same chemical formula Co4(2,2′-bipy)4{3,5-(NO2)2sal}4. Replacing Co(OAc)2 · 4H2O with Zn(NO3)2 · 6H2O, using the same synthetic procedures, results in the formation of compound [Zn(2,2′-bipy){3,5-(NO2)2sal}]n (3) with a 1D chain structure and the metallamacrocycle compound Zn4(2,2′-bipy)4{3,5-(NO2)2sal}4 (4). Compounds 1 and 2 crystallize as two different polymorphs of cyclic tetranuclear compounds. Compounds 3 and 4 are polymorphic too. The compounds 1 and 4 are isomorphous. The weak coordination interactions have significant influence on the spacial orientations of the 3,5-(NO2)2sal ligand, and may affect the crystallization processes. There are antiferromagnetic interactions in the cyclic tetranuclear cobalt(II) compounds 1 and 2. Compound 3 exhibits weak fluorescent emission in the solid state at room temperature.

Two copper(II) complexes, Cu2{3,5-(NO2)2sal}2(2,2′-bipy)2 · 0.5H2O (1) and [Cu2{3,5-(NO2)2sal}2(4,4′-bipy)(H2O)2]n (2) (3,5-(NO2)2sal = 3,5-dinitrosalicylate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), were synthesized by hydrothermal reactions and characterized by single crystal X-ray analysis. There are discrete cyclic binuclear structure in 1 and 2D herringbone-like network structure in 2, although bridging ligand 3,5-(NO2)2sal in 1 and 2 has same coordination model. Variable temperature magnetic measurement reveals small ferromagnetic interactions in complex 1.

To study the expression of the Trp-p8 protein in the prostate tissue of the PSA "grey zone" with different PSA density of the transition zone (PSADTZ) and explore the value of determining Trp-p8 expression and PSADTZ in the early diagnosis of prostate cancer (PCa).This study involved 30 cases of benign prostatic hyperplasia (BPH) and another 30 cases of PCa with different PSADTZ values. Using a data imaging and analysis system, we determined the expression levels of Trp-p8 in BPH and PCa tissues and analyzed their correlation with PSADTZ.The expression of Trp-p8 was weak or negative in the BPH but strong in the PCa tissue and even stronger in the PCa tissue with high PSADTZ (F = 34. 05, P0.05).The Trp-p8 protein is expressed differently in BPH and PCa tissues of the PSA " grey zone" and its expression is positively correlated with PSADTZ. Determination of the Trp-p8 expression and PSADTZ contributes to the early diagnosis of prostate cancer.

One new copper(II) complex with a multidentate Schiff-base ligand salicylaldehyde phenoxyacylhydrazone (H2L), {[Cu4(L)4(DMF)]·DMF}n (1) has been synthesized and structurally characterized. Complex 1 exhibits a coordination polymer with a 1-D infinite chain-like structure, resulting from the Cu(II) centers linked by N–N single bonds. Magnetic behavior of 1 shows that it is antiferromagnetic.

A novel three-dimensional molybdenum(V) phosphate decorated with zinc complex cations, Zn[Mo 6 O 12 (OH) 3 (PO 4 ) 4 ] 2 {Zn 4 (H 2 O) 5 (2,2′-bipy) 2 } 2 ·2H 2 O (2,2′-bipy=2,2′-bipyridine) 1 , has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR, TGA and EPR spectrum. The crystal data are triclinic, space group P 1 ¯ , a =13.0842(7) A, b =14.0065(11) A, c =14.3344(10) A, α =64.445(3)°, β =88.805(3)°, γ =74.099(3)°, V =2264.9(3) A 3 , Z =1, R =0.0283, wR=0.0749. The Zn[Mo 6 P 4 ] 2 units are connected together via additional zinc coordination complex ions to give a novel three-dimensional molybdenum(V) phosphate framework.

A novel 1D molybdenum(V) phosphate with mixed-valence cobalt coordination cation, Co II [Mo 6 O 12 (OH) 3 (PO 4 )(HPO 4 ) 3 ] 2 [Co III (H 2 O)(2,2′-bpy) 2 ] 2 [Co II 3 (OH) 2 (H 2 O) 4 ]·2H 2 O ( 1 ), has been synthesized by hydrothermal and characterized by single crystal X-ray diffraction. The title complex crystallizes in the triclinic system, space group P 1 ¯ , with a =12.8779(6), b =13.6862(10), c =15.1111(8) A, α =97.141(2)°, β =99.1360(10)°, γ =116.719(4)°. The structure of the title polyoxometalate is based on Co II [Mo 6 O 12 (OH) 3 (PO 4 )(HPO 4 ) 3 ] 2 clusters connected together via [Co II 3 (OH) 2 (H 2 O) 4 ] trimers to give a new unusual 1D chain‐like along the c -axis, where the Co[Mo 6 P 4 ] 2 cluster unit is bonded by [Co III (H 2 O)(2,2′-bpy) 2 ] unit.

The title organic–inorganic hybrid cadmium molybdenum(V) phosphate has been hydrothermally synthesized. The sandwich-type units [Cd4(H2O)2(2,2′-bpy)2]Cd[Mo6O12(OH)3(PO4)2(HPO4)2]2 ([Cd4]Cd[Mo6P4]2) are connected by octahedrally coordinated cadmium into a chain {[Cd4]Cd[Mo6P4]2}n. The coordination cations [Mo2O4(2,2′-bpy)2]2+ link to the neighboring chains, forming a 3D open framework structure. The title complex represents the first sandwich-type cadmium hetereopolymolybdate with 3D network.

The first tetranuclear nickel complex with the oxamato ligand, {[Ni(en)2]4[H4L]}(ClO4)4·7H2O (1) (L = N, N′, N″, N‴-methanetetrayltetrakismethylenetetrakis (oxamato)), has been prepared and determined by single-crystal X-ray analysis. 1 crystallizes in the tetragonal space group I41/a, with a = 15.2744(9), c = 31.3748(2) A and Z = 4. Each nickel (II) ion is in a distorted octahedral donor atom environment, which comprises four nitrogen atoms of two en molecules and two oxygen atoms of oxamato bridge. The shape of the entity looks like a propeller. The temperature-dependent magnetic susceptibilities were analyzed by the Curie-Weiss law; the following values were found C = 4.36 cm3 K mol-1, θ = -24.7 K, respectively. Der erste sechsfach koordinierte, vierkernige Nickel-Komplex, {[Ni(en)2]4[H4L]}(ClO4)4·7H2O, mit Tetrakis-bidentater Oxamato-Brucke Der erste vierkernige Nickel-Komplex, {[Ni(en)2]4[H4L]}(ClO4)4·7H2O (1) mit dem Oxamato-Liganden L(L = N, N′, N″, N‴-methantetrayltetrakismethylentetrakis (oxamato)) wurde prapariert und durch Einkristall-Rontgenstrukturanalyse charakterisiert. 1 kristallisiert in der tetragonalen Raumgruppe I41/a, mit a = 15.2744(9), c = 31.3748(2) A und Z = 4. Jedes Nickel(II)-Ion ist in verzerrt oktaedrischer Koordination von vier Stickstoffatomen der zwei en-Molekule und zwei Sauerstoffatomen der Oxamato-Brucke umgeben. Die Molekulform ahnelt einem Propeller. Die temperaturabhangigen magnetischen Suzeptibilitaten wurden mittels dem Curie-Weiss-Gesetz analysiert - es wurden die Werte C = 4.36 cm3 K mol-1, θ = -24.7 K bestimmt.

The hydrothermal reactions of H3TMA (or Na3TMA) with metal acetate yield three novel coordination polymers [Cd3(TMA)2(H-PRZ)(H2O)3(OH)] · H2O (1), Cd2Na2(TMA)2(H2O)4 (2) and [Cd2Co(TMA)2(H2O)4] · 2H2O (3) (TMA=trimesic acid, PRZ=piperazine). The three Cd(II) centers in 1 are bridged by TMA ligands and a μ3-O atom of coordinated hydroxide to generate a sandwich-liked tri-layer motif. These motifs with a Cd3O core are further interlinked by hydrogen bond interactions to stack in a 3D coordination framework with a porous dimension of ca. 7.5 × 5.5 A. Complex 2 is a three-dimensional polymer based on tetranuclear heterometallic clusters. The centrosymmetric tetranuclear heterometallic cluster contains a Cd2Na2 parallelogram cluster core. These clusters are connected through the coordination of carboxylate oxygen atoms of TMA ligands to form a 3D coordination framework. Complex 3 represents the first structural characterization of a trimesate complex containing two different transitional metals. Each TMA3− ligand in the Cd2Co(C9H3O6)2(H2O)4 structure unit of 3 binds to other three structure units, resulting in a 3D coordination polymer. The three complexes exhibit strong fluorescent emission bands at 420 nm (λex=314 nm) for complex 1, 424 nm (λex=314 nm) for complex 2, and 419 nm (λex=308 nm) for complex 3 in the solid state at room temperature. The preliminary magnetic property of complex 3 has been investigated.

An unexpected dimerization of a cryptand L with N 5 O 3 donors, C 3 3 H 4 5 N 5 O 3 , was observed in aqueous solution when L was treated by hydrochloric acid in MeOH and washed with EtOH. The crystal dimerization product is acomplex (H 2 L 2 ) 2 + .2Cl - .5HCl.18H 2 O (1) (where the neutral dimeric cryptand L 2 is C 6 6 H 9 0 N 1 0 O 6 ). The crystal complex L 2 .2HCl .3H 2 O (2) was obtained when complex 1 was neutralized with aqueous solution of NaOH. The two complexes have been characterized by X-ray diffraction, NMR and MS. The conformation of L 2 in 1 is endo-endo-endo-endo, and the two nitrogen atoms of four bridgehead tertiary nitrogen atoms of L 2 are protonated. However, conformation of L 2 in 2 is endo-exo-endo-exo, and the L 2 is neutral.

[NH4]2[MoS4] reacts with CuBr and [Bu4N]Br in the solid state to afford an intermediate product with proposed constitution [Bu4N]4[MoS4Cu6Br8] (1). Treatment of cluster (1) with an equal equivalent of dppf in CH3CN–DMF solution resulted in the formation of a pentanuclear cluster [MoS4(Cudppf)2]·2DMF·CH3CN (2). Cluster (2) crystallizes in the monoclinic space group P21/n with four formula units in a cell of dimensions a = 13.1267(8), b = 38.040(2), c = 15.2661(9) A, and β = 97.6030(10)°. Refinement by full-matrix least-squares techniques gave final residuals R = 0.0567 and wR = 0.1679. The structure of (2) can be described as two (Cudppf)+ units linked through MoS42− to form a pentanuclear folding-ruler array. Reaction of (1) with excess Ph2PPy in CH3CN solution resulted in the formation of a trinuclear cluster [MoS4Cu2(Ph2PPy)4] (3). Cluster (3) crystallizes in the tetragonal space group I41/a with cell constants a = 17.427(6), b = 17.427(6), c = 21.344(5) A, and Z = 4. Final residuals R = 0.0337 and wR = 0.0616. The structure of (3) is built up from two Cu(Ph2PPy)2+ units bridged by a MoS42− ligand to form a trinuclear symmetrical linear molecule. Clusters (2) and (3) exhibit strong optical absorption (effective α2 = 1.6 × 10−9 m W−1 (2) and 1.2 × 10−9 m W−1 (3)) and optical self-defocusing effects (n2 = −1.35 × 10−17 m2 W−1 (2) and −6.84 × 10−17 m2 W−1 (3)), their limiting thresholds were determined to be 0.35 J cm−2 (2) and 0.65 J cm−2 (3), which are about four and two times, respectively, better than that of C60.

The hydrothermal reaction of V2O5, Ni(NO3)2·6H2O, ethylenediamine and H2O in the molar ratio of 1∶1∶3.5∶519 at 180 °C yields black plates of [Ni(en)2][V6O14]. This compound has been characterized structurally, magnetically, electrically, and spectroscopically. The crystal structure consists of novel mixed-valence vanadium oxide layers and interlayer metal coordination complexes. Each of the three VO5 square pyramids share two edges to form a V3O11 group. The V3O11 groups are connected through sharing edges to produce a linear ribbon. Adjacent strips share corners to form a layer structure. The two oxygen atoms from the neighbouring vanadium oxide layers are coordinated to each nickel atom in a trans-fashion, and form a three-dimensional framework structure. An EHT (Extended Huckel Theory) calculation was performed to analyze the electronic structure, and the electrical resistivity measurements confirmed the expected semiconducting behavior of [Ni(en)2][V6O14].

K3[Cr(CN)6] reacts with the mononuclear MnIII complex Mn(salen)ClO4 · 2H2O [salen: N,N′-ethylenebis(salicylideneiminato)dianion] to give a bimetallic heptanuclear complex cation salt [Cr{(CN)Mn(salen · H2O)}6][Cr(CN)6]6H2O. In the complex anion, [Cr{(CN)Mn(salen · H2O)}6]3+, six MnIII ions coordinate to a CrIII center via cyano bridges, forming a spherical species with 3 symmetry. A study of magnetic properties shows the presence of antiferromagnetic interaction through the cyanide bridge between CrIII (S = 3/2) and MnIII (S = 4/2) and results in a ground state S = 21/2.

A new mercury iodide complex of dppf, [HgI2(dppf)] (adduct 1, dppf = 1,1-bis(diphenylphosphino)ferrocene) was prepared and characterized. Single crystal X-ray diffraction analysis established that the compound crystallizes in the monoclinic system, space group C2c, with a = 34.992(3), b = 10.236(5), c = 18.765(4) A, β = 99.410(2)°, Z = 8, V = 6631.2(9) A3. The coordination about the mercury atom is tetrahedral with two equivalent Hg–I and Hg–P bonds. Dppf functions as a chelating ligand. The nonlinear optical (NLO) properties were studied with an 8 ns-pulsed laser at 532 nm. Its optical responses to the incident light exhibit weak optical absorptive and strong refractive effects, with n2 = 6.86 × 10–18 m2 · W–1 in a 2.48 × 10–4 mol · dm–3 DMF solution. Ein neues Quecksilberiodid-Addukt mit 1,1-Bis(diphenylphosphino)ferrocen: Synthese, Kristallstruktur und nichtlineare Brechungseigenschaften Ein neuer Quecksilberiodid-Komplex von dppf, [HgI2(dppf)] (Addukt 1, dppf = 1,1-Bis(diphenylphosphino)ferrocen) wurde hergestellt und charakterisiert. Nach der Einkristall-Rontgenstruktur-Analyse kristallisiert 1 monoklin in der Raumgruppe C2c mit a = 34,992(3), b = 10,236(5), c = 18,765(4) A, β = 99,410(2)°, Z = 8, V = 6631,2(9) A3. Die Koordination am Quecksilber-Atom ist tetraedrisch mit zwei aquivalenten Hg–I- und Hg–P-Bindungen. Dppf fungiert als Chelat-Ligand. Die nichtlinearen optischen Eigenschaften (NLO) wurden mit Hilfe eines 8 ns-Puls-Lasers bei 532 nm ermittelt. Gegenuber dem einfallenden Licht werden in 2,48 × 10–4 mol · dm–3 DMF-Losung schwache optische Absorption und ein starker Brechungseffekt mit n2 = 6,86 × 10–18 m2 · W–1 beobachtet.

A novel macrocyclic hexanuclear iron(III) 18-azametallacrown-6 compound, [Fe6(C9H7N2O3)6(CH3OH)6]·8CH3OH·2H2O, has been prepared using a trianionic pentadentate ligand N-acetylsalicylhydrazide (ashz3−) and characterized by X-ray diffraction. Due to the meridional coordination of the ligand to the Fe3+ ion, the ligand enforces the stereochemistry of the Fe3+ ions as a propeller configuration with alternating Λ/Δ forms. The disc-shaped hexanuclear ring shows about 6.20 A in diameter at entrance, about 9.31 A at its largest diameter at the center of the cavity, respectively. There are many kinds of intramolecular and intermolecular hydrogen bonds in the title compound. The OH⋯O hydrogen bond distances range from 2.609(5)–2.901(5) A. The magnetic susceptibility (4–275K) study indicates antiferromagnetic exchange interactions between the adjacent Fe3+ ions around the ring.

To search for a simple and effective surgical approach to the management of moderate to severe pediatric concealed penis in children.We used Devine's technique via incision between the penis and scrotum in the treatment of 68 cases of moderate to severe pediatric concealed penis. The patients were aged 3 -13 (mean 6.5) years, 30 with moderate and 38 with severe pediatric concealed penis.This strategy achieved good near- and long-term effects and satisfactory appearance of the penis, which was similar to that of circumcision. At 3 months after surgery, the penile length was 3 - 5.2 cm, averaging (2.35 +/- 0.35) cm.Devine's technique via incision between the penis and scrotum is a simple and effective surgical option for moderate to severe pediatric concealed penis in children.

[Ni(L−1)(HL)(H2O)2].ClO4 with a Schiff base ligand L (HL = 3-p-tolylimino-2-butanone oxime) was prepared and structurally characterized by IR, cyclic voltammetry and X-ray diffraction methods. The nickel atom has distorted octahedral coordination consisting of four nitrogen atoms and two oxygen atoms. The equatorial plane is formed by two oxime nitrogen atoms and two imine nitrogen atoms of two Schiff base ligand (L−1 and HL) with Ni‐ N bond distances between 2.01(1) and 2.11(1)A. Water oxygen atoms occupy axial positions with Ni‐ O bond distances of 2.06(1) and 2.15(1) A. The oxime groups in the Schiff base ligands are coordinated to Ni atom through their nitrogen atoms. One asymmetric intramolecular hydrogen bridge between the two oxime groups is found in the title complex.

Two new metavanadates, Cu(tn)2(VO3)2 (tn=1,3-diaminopropane) and Ni(NH3)2(VO3)2, have been prepared under hydrothermal conditions and their single-crystal structures determined by X-ray diffraction. Both structures consist of corner-sharing VO4 tetrahedral chains with complex cations occupying the interchain positions. While there dominantly exist electrostatic interactions between the Cu(tn)2 2+ fragments and the vanadium oxide chains in Cu(tn)2(VO3)2, the Ni(NH3)2 2+ moieties in the Ni(NH3)2(VO3)2 bridge the vanadium oxide chains into a three-dimensional framework structure by Ni–O covalent interactions. The magnetic properties were measured in the temperature ranging from 4 to 275 K. It is shown that Cu(tn)2(VO3)2 possesses well-separated Cu2+ centers and that the magnetic behavior of Ni(NH3)2(VO3)2 can be explained based on a one-dimensional Ising model.

The hydrothermal reaction of V 2 O 5 , NiCl 2 ·6H 2 O, ethylenediamine and H 2 O in the mole ratio 1:1:4.9:120 at 150°C for 55 h produced violet prismatic crystals of Ni(en) 3 (VO 3 ) 2 . The crystal of the title compound is hexagonal P 6 1 , a =8.986(1), c =34.031(2) A, V =2379.8(5) A 3 , Z =6, D calc =1.829 g cm −3 and R =0.0609 for 1406 observed reflections. The structure of Ni(en) 3 (VO 3 ) 2 consists of spiral anion (VO 3 ) ∞ chains formed by corner-sharing VO 4 tetrahedra with Ni(en) 3 2+ complex cations occupying the interchain positions, where there are electrostatic interactions and hydrogen bonds between the anion chain and the complex cation. The title compound is the first example of a vanadium compound, in which the repeat unit of the chain is 12-nuclear corner-sharing tetrahedra, V 12 O 36 . The magnetic susceptibility of the title compound has been studied.

Three mononuclear copper complexes of 9-hydroxy-9H-fluorene-9-carboxylic acid, [Cu(C14H9O3)2(C5H5N)2]·2CH3OH (I), [Cu(C14H9O3)2(C2H5OH)(H2O)]·C2H5OH·CH3OH (II) and [Cu(C14H9O3)2(C6H16N2)]·C2H5OH (III), were synthesized and characterized by IR and Raman spectra. Complex I was also characterized by X-ray diffraction. The main vibration frequencies in the free 9-hydroxy-9H-fluorene-9-carboxylic acid and the three title complexes have been assigned. The COO antisymmetric and symmetric frequencies of the α-hydroxylated acid complexes were identified in the regions 1630–1605 and 1365–1340 cm−1, respectively. The frequency shift of hydrogen bonds in the title complexes is discussed. The copper atom in title complex I is octahedrally coordinated by four oxygen atoms and two nitrogen atoms. The molecules of title complex I are connected through hydrogen bonds, resulting in an infinite chain. The coincidence between spectra and structural characters has been discussed.

The Cd(II) centre in the title complex, [Cd(C(14)H(13)N(3)O(2))(2)(H(2)O)(4)](NO(3))(2), occupies a crystallographic inversion centre and is coordinated by two donor N atoms from two 2-methoxybenzldehyde isonicotinoylhydrazone ligands and by four O atoms from four coordinated water molecules, giving a slightly distorted octahedral geometry. There is an extended three-dimensional network structure resulting from O-H...O hydrogen bonds between coordinated water and nitrate anions, and between coordinated water and carbonyl O atoms, and from N-H...O hydrogen bonds between NH groups and nitrate O atoms.