Two new Co-II-based coordination polymers tuned by the flexible "V"-shaped 3,3'-(1,2-phenylenebis(methyleneoxy)) dibenzoic acid (H2L) and different N-donor spacers, namely, [Co(L)(bib)](n )(1) and [Co-2(L)(2)(phen)(2)(H2O)(2)center dot H2O](n )(2) (bib = 1,4-bis(1-imidazoly)benzene and phen = 1,10-phenanthroline) have been prepared. In 1, the Co-II centers are linked by L to form a Co-L chain, which is further extended into a 2D wave-like layer by bib linkers. In 2, the L linker connected the adjacent Co(II) centers into 1D chain, which is joined into a 3D supramolecular structure through H-bonded and pi-pi stacking interactions. The diverse networks of 1-2 demonstrate that the steric hindrance effect may show significant effect on the final structures. In addition, the title complexes exhibit photocatalytic activity for dye methyl violet (MV) degradation under UV light.

Six new O‐alkyldithiophosphate nickel complexes with dcpf ligand, [(dcpf)Ni(S2P{O}OR)] (dcpf = 1,1′‐bis (dicyclohexylphosphino)ferrocene, R = CH3 (1), CH3CH2 (2), Ph (3), 4‐MeC6H4 (4), PhCH2 (5) and PhCH2CH2 (6)), have been synthesized by the treatment of dcpf with ((RO)2PS2)2Ni in satisfactory yields. These complexes were characterized by elemental analysis, spectroscopy (FTIR, UV–vis, 1H, 13C, and 31P NMR), thermogravimetric analysis and single crystal X‐ray diffraction. The nickel atom in 1, 2·CH2Cl2, 3·CH2Cl2, 4·2CH2Cl2·THF, and 2(5)·hexane adopts a slightly distorted square‐planar coordination environment finished by two phosphorus atoms of dcpf ligand and two sulfur atoms of O‐alkyldithiophosphate ligand. Furthermore, the electrochemical properties for complexes 1–6 were also investigated by cyclic voltammetry. With the addition of 120 mM trifluoroacetic acid (TFA), the turnover frequency (TOF) values for 1–6 are estimated to be 1243.83, 1046.54, 1331.71, 2545.29, 1899.03, and 1191.37 s−1, with the overpotential (η) values of 0.62, 0.58, 0.71, 0.67, 0.60, and 0.56 V, respectively. The result of electrochemical studies indicates that all complexes can be used as efficient molecular eletrocatalysts for the reduction of protons to hydrogen in the presence of TFA in MeCN.

目的 探讨高强度聚焦超声联合单药吉西他滨化疗治疗局部晚期胰腺癌的临床效果及不良反应.方法 将2010年6月至2017年6月六安市人民医院收治的42例局部晚期胰腺癌病人依据治疗措施的不同分为两组,对照组(19例)用单药吉西他滨化疗,吉西他滨1000 mg/m2静脉滴注.观察组(23例)用单药吉西他滨化疗的同时加高能聚焦超声刀治疗.结果(1)对照组治疗前功能状态评分(KPS评分)均值为(74.74±9.05)分,治疗后KPS评分均值为(76.32±8.95)分,组内差异无统计学意义(t=1.000,P=0.331);观察组治疗前KPS评分均值为(72.61±10.10)分,治疗后KPS评分均值为(83.48±7.75)分,组内差异有统计学意义(t=4.800,P=0.000),两组组间比较差异有统计学意义(t=2.896,P=0.006).(2)对照组治疗后的总缓解率为43.75％,观察组为83.33％,组间差异有统计学意义(P=0.030).(3)对照组治疗后的临床受益率为26.32％,观察组为65.22％,差异有统计学意义(χ2=6.313,P=0.012).(4)两组不良反应均为Ⅰ～Ⅱ级骨髓抑制,差异无统计学意义(P>0.05).结论 高能聚焦超声刀联合单药吉西他滨化疗是治疗局部晚期胰腺癌的安全有效方法.

Nickel (II) complexes of 5, 7, 7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca4, 11-diene ([Ni(us-htde)](ClO4)(2)) and 5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetrazacyclotetradecane ([Ni(s-htde)](ClO4)(2)) are synthesized and confirmed by elemental analysis. Here, the thermal stability of the two nickel (II) complexes are investigated by TG/DSC technology. Moreover, the corrosion inhibition of [Ni(s-htde)](ClO4)(2) in 1.0 M HCl is evaluated by weight loss method and potentiodynamic polarization measurement. The study results show that the thermal decomposition process of the [Ni(us-htde)] (ClO4)(2) and [Ni(s-htde)](ClO4)(2) heated in N-2 and air atmospheres all proceeded in three steps, which is not affected by N-2 and air atmospheres. The thermal stability of the [Ni(s-htde)](ClO4)(2) is better than [Ni(us-htde)](ClO4)(2), which can be stable at the temperature below 283 degrees C and 270 degrees C in N-2 and air atmospheres. Meanwhile, the study results show that [Ni(s-htde)](ClO4)(2) can act as an effective mixed-type corrosion inhibitor, and it adsorption on Q235 steel surface can be described by Langmuir isotherm, which belongs to physic- and chemisorption.

In this study, the nickel (II) complex of 5, 7, 7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetrad-eca4, 11-diene ([Ni(htde)](ClO 4 ) 2 ) is synthesized and the thermal stability of [Ni(htde)](ClO 4 ) 2 also studied by TG/DSC technology, while its corrosion inhibition for mild steel (MS) in 1.0 M HCl and H 2 SO 4 solutions is studied by potentiodynamic polarization and weight loss measurements. Results findings that the thermal decomposition process of [Ni(htde)](ClO 4 ) 2 in N 2 and air atmospheres all proceeded in three steps, and the thermal decomposition is not affected by N 2 and air atmospheres, which can be stable at the temperature below 270 °C under these two atmospheres. [Ni(htde)](ClO 4 ) 2 is a mixed-type inhibitor, the inhibition efficiency increases with the increase of [Ni(htde)](ClO 4 ) 2 concentration. And the adsorption of [Ni(htde)](ClO 4 ) 2 on MS surface can be described by Langmuir isotherm, which belongs to physic- and chemisorption.

The new corrosion inhibitor of S-benzyl-O,O'-bis( p -tert-butyl phenyl)dithiophosphate (SOBP) was synthesized and characterized by elemental analysis, FT-IR, 1 H NMR, 13 C NMR, 31 P NMR and single crystal X-ray diffraction. Meanwhile, the corrosion inhibition and mechanism of SOBP for Q235 steel in 1.0 M HCl were studied by weight loss and potentiodynamic polarization measurement, also the crystal structure of corrosion inhibitor was presented. The potentiodynamic polarization measurement result indicates that SOBP is a mixed-type inhibitor. The two methods all reveal that the inhibition efficiency increases with the concentration of SOBP, which is an effective corrosion inhibitor. The adsorption of SOBP on Q235 steel surface in 1.0 M HCl belongs both physisorption and chemisorption.

In present work, the target compounds of S-benzyl-O,O'-dialkyldithiophosphates including S-benzyl-O,O'-diphenyldithiophosphate (Inhi-1), S-benzyl-O,O'-dibenzyldithiophosphate (Inhi-2), S-benzyl-O,O'-di(2-phenylethyl)dithiophosphate(Inhi-3) and S-benzyl-O,O'-di(4-methylphenyl)dithiophosphate (Inhi-4) were prepared, which acting as corrosion inhibitor for mild steel (MS) in HCl solution were investigated by weight loss measurement, potentiodynamic polarization measurement and electrochemical impedance spectroscopy. The potentiodynamic polarization measurement indicates that the four synthesized compounds are all the mixed-type inhibitor for MS corrosion in HCl solution. Furthermore, all measurements in this study show that the inhibition efficiency increases with inhibitor concentration increasing. Weight loss measurement reveals that inhibition efficiency decreases with HCl concentration and temperature increasing. In addition, the adsorption of Inhi-1, Inhi-2, Inhi-3 and Inhi-4 on MS surface obeys Langmuir isotherm, which are mixed adsorption involving both physisorption and chemisorption.

A new 2D Co(II) based coordination polymer (CP), {[Co-2(tib)(2)(NO3)(3)(H2O)(2)center dot NO3](n) (1), has been synthesized using 1,3,5-tris(1-imidazolyl)benzene (tib) ligand. The single crystal X-ray diffraction study indicates that 1 possesses an infinite 2D layer, which is further extended into a 3D supramolecular network via O-H center dot center dot center dot O hydrogen bonding interactions. Additionally, the thermogravimetric analysis (TGA) of CP indicates its decomposition temperature was about 268 degrees C. The UV/Vis diffuse-reflection spectrum of 1 indicates its semiconducting nature on the basis of which the photocatalytic properties of 1 against photodecomposition of organic dyes have been studied. The possible mechanism associated with the photocatalytic activity of 1 against organic dyes is addressed using density of states (DOS) calculations. [GRAPHICS]

Here, S-allyl-O,O′-diphenyldithiophosphate(SOD1), S-allyl-O,O′-dibenzyldithiophosphate (SOD2) and S-allyl-O,O′-di(2-phenylethyl)dithiophosphate(SOD3) were successful synthesized and characterized, which acting as the novel corrosion inhibitors for mild steel in hydrochloric acid (HCl) solution were evaluated by electrochemical measurements, weight loss measurement and scanning electron microscopy. Potentiodynamic polarization measurement indicates that the synthesized inhibitors are effective mixed-type inhibitors. The inhibition efficiency increases with inhibitor concentration increasing, decreases with HCl concentration and temperature increasing. The adsorption of SOD1, SOD2 and SOD3 on mild steel surface obeys Langmuir isotherm. The adsorption of SOD1 and SOD3 on mild steel surface is a mixed adsorption involving both physisorption and chemisorption, and that the adsorption of SOD2 on mild steel surface belongs to chemical adsorption.

A new tripodal carboxylic ligand, 2-(4-carboxylphenoxy) terephthalic acid, readily (H3L) reacts with Cd(II) salts in the presence of N-donor ligands to afford three different metal-organic frameworks of {Cd3(L)2(H2O)4·2CH3CN}n (1), {Cd3(L)2(2,2′-bipy)4·2H2O}n (2), and {Cd3(L)2(phen)2·2CH3CN}n (3). The structure of 1 consists of a 1D metal chain extending to three-dimensional network. The structures of 2 and 3 can be described as a repetition of a trinuclear core with subtle differences. 1–3 exhibit impressive chemical stability, pH stability and strong luminescence, making them excellent candidates as multifunctional fluorescent sensors for selective and sensitive detection of Hg2+, nitroaromatics as well as Cr2O72-. 1–3 are all extremely responsive to Hg2+ ion at a parts per million level, the limits of detection towards Hg2+ ion are 2.55 × 10−6M, 2.72 × 10−6M, and 9.79 × 10−7M for 1–3, respectively. The KSV value for 3 (5.155 × 104M−1) is the highest among most MOFs reported to date. 1–3 represent the first case on the recyclable luminescent probe for Hg2+ ion. Furthermore, the photocatalysis properties of 1–3 for degradation of the Rhodamine B (RhB) have also been examined.

A new 2D Zn(II) metal-organic framework of {[Zn(L)(4,4′-bipy)·CH3CN]n (1) has been developed using 5-aminoisophthalic acid (H2L) and 4,4′-bipyridine ligands. The single crystal X-ray diffraction study indicates that 1 is composed of infinite 2D layer. The chemically stable 1 behaves as a highly selective and sensitive fluorescence chemosensor for detection of Hg2+ and 4-nitrotoluene (4-NT) analyte. Furthermore, the photocatalytic properties of 1 for degradation of the methyl violet (MV) and Rhodamine B (RhB) have been explored.

A novel diiron S-(−)-1-phenylethylazadithiolate complex, Fe2[(μ-SCH2)2NCH(CH3)Ph](CO)6 (1), has been prepared by the condensation of Fe2(μ-SH)2(CO)6, CH2O and S-(−)-1-phenylethylamine. Furthermore, the reaction of complex 1 and phosphine ligands (PPh3, P(C6H4-4-F)3, dppe) in the presence of the decarbonylation agent Me3NO·2H2O resulted in the formation of the phosphine-substituted diiron S-(−)-1-phenylethylazadithiolate complexes Fe2[(μ-SCH2)2NCH(CH3)Ph](CO)5(PPh3) (2), Fe2[(μ-SCH2)2NCH(CH3)Ph](CO)5[P(C6H4-4-F)3] (3) and {Fe2[(μ-SCH2)2NCH(CH3)Ph](CO)5}2(Ph2PCH2CH2PPh2) (4). Complexes 1–4 have been fully characterized by elemental analysis, FTIR and NMR (1H, 13C, 31P) spectroscopies, and for 1, 2 and 4 by X-ray crystallography. Moreover, complexes 1 and 2 were found to be catalysts for hydrogen production in the presence of acid under electrochemical conditions. According to the electrochemical observations, a possible catalytic mechanism for complexes 1 and 2 was proposed.

N,N-Diethylammonium O,O′-di(p-methoxyphenyl)dithiophosphate (EAPP) as a new corrosion inhibitor was synthesized in the present work. The corrosion inhibition of EAPP in hydrochloric acid for carbon steel was evaluated by potentiodynamic polarization measurements, electrochemical impedance spectroscopy, weight loss measurements, and scanning electron microscopy. The results indicate that the EAPP is mixed type inhibitor, and the adsorption of EAPP on carbon steel surface obeys Langmuir isotherm. In addition, the inhibition efficiency increases with increasing the concentration of inhibitor and decreases with increasing the hydrochloric acid concentration, temperature, and storage time.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Here, the macroporous silicon (macro-pSi) was successfully prepared by electrochemical anodization silicon wafers in the etching solution of 1:1 HF(40%)/EtOH(99.5%)(v/v). Results show that macro-pSi with different thickness and porosity exhibit the different photocatalytic activity for methyl orange degradation, and the maximum value of decolorization efficiency is 66.62%. Especially, the influence factors including photocatalysts dosage, current density, thermal treatment temperature, pH and recyclability for photocatalytic activity of macro-pSi as photocatalysts slice were systematically investigated. Furthermore, the decolorization kinetic equation is also presented in this work.

Three diiron and tetrairon azadithiolate complexes as models for the active site of [FeFe] hydrogenase were prepared. Reaction of complex Fe-2(SCH2OH)(2)(CO)(6) and NH2CH2CH2CH2OCH3 resulted in the diiron azadithiolate hexcarbonyl complex Fe-2[(SCH2)(2)NCH2CH2CH2OCH3](CO)(6) (1) in moderate yield. Furthermore, treatment of complex 1 with mono phosphine ligand PPh3 and diphosphine ligand Ph2PCH2CH2PPh2 in the presence of decarbonylation reagent Me(3)NO2H(2)O yielded the phosphine-substituted azadithiolate complexes Fe-2[(SCH2)(2)NCH2CH2CH2OCH3]CO)(5)(PPh3) (2) and {Fe-2[(SCH2)(2)NCH2CH2CH2OCH3](CO)(5)}(2)(Ph2PCH2CH2PPh2) (3) respectively. The new complexes 1-3 were fully characterized by elemental analysis, IR, H-1, C-13, P-31 NMR spectroscopy and X-ray crystallography. It is worthy to note that the crystallographic studies show the unusual difference of the methoxypropanyl substituent on the N atom of complexes 1 and 2, largely because of the affection of phosphine ligand PPh3. In addition, complex 1 was found to be a catalyst for H-2 production under electrochemical condition.

Three novel diiron azadithiolate complexes Fe2[(μ-SCH2)2NCH2CH2CH(CH3)2](CO)6 (1), Fe2[(μ-SCH2)2NCH(CH2CH3)2](CO)6 (2) and Fe2[(μ-SCH2)2NCH2CH2CH2SCH3](CO)6 (3) have been synthesized by treatment of Fe2(μ-SCH2OH)2(CO)6 with primary amines RNH2 (R=CH2CH2CH(CH3)2, CH(CH2CH3)2, CH2CH2CH2SCH3). Meanwhile, reaction of Fe2(μ-SCH2OH)2(CO)6 and diphosphine ligand Ph2PCH2PPh2 (dppm), followed by the addition of amines NH2CH2CH2CH(CH3)2 and NH2CH(CH2CH3)2 resulted in the formation of the target phosphine-substituted diiron azadithiolate complexes Fe2[(μ-SCH2)2NCH2CH2CH(CH3)2](CO)5(dppm) (4) and Fe2[(μ-SCH2)2NCH(CH2CH3)2](CO)5(dppm) (5). Complexes 1–5 have been fully characterized by elemental analysis, FTIR, and NMR (1H, 13C, 31P) spectroscopies, and particularly for 1–3 by X-ray crystallography. In addition, complexes 1–5 were found to be catalysts for hydrogen production under electrochemical conditions.

Three new d10 based MOFs using 5-[bis(3-carboxybenzyl)-amino]isophthalic acid were synthesized and their sensing behavior towards nitroaromatics was evaluated.