The proton conduction behavior of two 1D open-framework metal phosphates with similar crystal structures and different hydrogen bond networks.

Two open-framework zinc phosphates [C3N2H12][Zn(HPO4)2] (1) and [C6N4H22]0.5[Zn(HPO4)2] (2) were synthesized via hydrothermal reaction and characterized by powder X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Both compounds have a similar crystal structure and macroscopic morphology. However, the difference in equilibrium cations, in which the propylene diamine is for 1 and the triethylenetetramine is for 2, results in a significant distinction in the dense hydrogen grid. The diprotonated propylene diamine molecule in 1 is more favorable for forming a hydrogen-bond network in three dimensions than in 2, in which the twisted triethylenetetramine forms a hydrogen bond grid with the inorganic framework only in two dimensions owing to its large steric effect. This distinction further leads to a disparity in the proton conductivity of both compounds. The proton conductivity of 1 can reach 1.00 × 10-3 S cm-1 under ambient conditions (303 K and 75% RH) and then increase to 1.11 × 10-2 S cm-1 at 333 K and 99% RH, which is the highest value among the open-framework metal phosphate proton conductors operated in the same conduction. In contrast, the proton conductivity of 2 is four orders of magnitude smaller than 1 at 303 K and 75% RH and two orders smaller than 1 at 333 K and 99% RH.

Cu-Based Conductive MOF Grown in situ on Cu Foam as a Highly Selective and Stable Non-Enzymatic Glucose Sensor.

A non-enzymatic electrochemical sensor for glucose detection is executed by using a conductive metal-organic framework (MOF) Cu-MOF, which is built from the 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligand and copper acetate by hydrothermal reaction. The Cu-MOF demonstrates superior electrocatalytic activity for glucose oxidation under alkaline pH conditions. As an excellent non-enzymatic sensor, the Cu-MOF grown on Cu foam (Cu-MOF/CF) displays an ultra-low detection limit of 0.076 µM through a wide concentration range (0.001-0.95 mM) and a strong sensitivity of 30,030 mA µM-1 cm-2. Overall, the Cu-MOF/CF exhibits a low detection limit, high selectivity, excellent stability, fast response time, and good practical application feasibility for glucose detection and can promote the development of MOF materials in the field of electrochemical sensors.

Acceleration of the bio-reduction of methyl orange by a magnetic and extracellular polymeric substance nanocomposite.

Extracellular electron transfer (EET) plays an important role in bio-reduction of environmental pollutants. Extracellular polymeric substances (EPS), a kind of biogenic macromolecule, contain functional groups responsible for acceleration of EET. In this study, azo dye-methyl orange (MO) was chosen as a model pollutant, and a Fe3O4 and EPS nanocomposite (Fe3O4@EPS) was prepared to evaluate its promotion on the bio-reduction of MO. The flower-like core-shell configuration of Fe3O4@EPS with a 12 nm of light layer of EPS was confirmed by TEM. The redox ability of EPS was well reserved on Fe3O4@EPS by FTIR and electrochemical test. The application of Fe3O4@EPS on sustained acceleration of MO decolorization were confirmed by batch experiments and anaerobic sequenced batch reactors. Due to biocompatibility of the biogenic shell, the as-prepared Fe3O4@EPS exhibited low toxic to microorganisms by the Live/dead cell test. Moreover, negligible leaching of EPS under high concentration of various anions and less than 10% of EPS was released under extreme acidic and basic pH condition. The results of study provided a new preparation method of biological intimate and environmentally friendly redox mediators and suggested a feasible way for its use on bio-reduction of pollutants.

Energy-saving preparation of a bioflocculant under high-salt condition by using strain Bacillus sp. and the interaction mechanism towards heavy metals.

A highly efficient bioflocculant, i.e., Na-Bsp was successfully prepared by using a tolerant strain-Bacillus sp. under high-salt condition without sterilization. Salt-containing medium was not infected by other strains throughout the whole incubation period in 168 h. The as-prepared Na-Bsp was found to be cation-dependent, exhibiting high flocculant efficiency (FE) i.e., 97.69 ± 0.61%, towards kaolin particles by aid of Fe3+. High FE values were well maintained under a wide pH range and/or boiled water treatment, likely because of the main constituent of polysaccharide. The presence of hydroxyl, carboxyl, and amine groups on the bioflocculant surface were possibly responsible for strong interactions with heavy metals. The adsorption capacities of Pb2+, Cu2+ and Cr6+ were 1000.0, 434.8 and 384.6 mg g-1, respectively. The changing of structure and configuration of bioflocculant during the metal adsorption were explored by the scanning electron microscope with electron energy loss spectroscopy and three-dimensional excitation-emission fluorescence spectrometry. This study provided a novel production method, whereby the conventional sterilization could be avoided, which is of great environmental significance for steam-saving. Furthermore, the as-prepared Na-Bsp exhibited high adsorption capacities toward heavy metals, which sheds lights on its potential usage as an alternative adsorbent.

Expression and Histopathological Significance of Disabled-2 in Aldosterone-Producing Adenoma.

The current pathological diagnosis of aldosterone-producing adenoma (APA) is challenging because no histological markers of aldosterone production are available in routine practice. A previous study demonstrated that Disabled-2 (DAB2) is a specific marker of the zona glomerulosa (ZG) in rodents. The aim of the present study was to investigate the significance of immunohistochemical staining to detect DAB2 in the adrenal tissue of patients with APA. We investigated the expression of DAB2 in 36 adrenal glands with APA, 23 adrenal glands with cortisol-producing adenoma (CPA), and 33 adrenal glands with non-functioning adenoma (NFA). Immunohistochemical staining was performed using anti-DAB2 antibodies on paraffin-embedded sections. We analysed the expression of DAB2 semi-quantitatively by scoring staining intensity, and assessed the correlation of this information with the clinical findings. DAB2 mRNA expression in adenoma tissues was evaluated by RT-PCR. DAB2 was highly expressed in the ZG in normal human adrenal glands. DAB2 expression was heterogeneous in APA, with spotted, strong staining noted in most samples (25 of 36 APA). CPA and NFA also exhibited extensive low or moderate DAB2 expression. DAB2 mRNA was significantly increased and positively correlated with CYP11B2 in APA (p<0.05). In APA, the DAB2 score adjusted for tumour volume was positively correlated with plasma aldosterone (p<0.05). Patients with low or moderate DAB2 staining more frequently exhibited high blood pressure and were diagnosed at a younger age compared with patients with high DAB2 staining. The present study clearly demonstrates that DAB2 is a specific marker of the ZG in normal human adrenal glands but that DAB2 immunostaining is not sufficiently powerful for histopathological diagnosis of APA. DAB2 might be involved in excessive aldosterone biosynthesis and correlate with specific clinical characteristics of APA patients.

[Mid-term follow-up results of laparoscopic radiofrequency ablation for renal cell carcinoma of T1aN0M0 stage].

OBJECTIVE: To determine the effect of laparoscopic radiofrequency ablation of T1aN0M0 renal cell carcinoma (RCC) with regular follow-up. METHODS: All patients underwent surgery from March 2006 to March 2009. Eight cases were solitary kidney. Twenty-two cases of left RCC and 18 cases of right RCC were diagnozed by ultrasonography and CT scanning.All of the cases were T1aN0M0 stage. No metastasis was found by iconography test. By ultrasound positioning, laparoscopic radiofrequency were performed on the renal tumor. All patients were followed up with eGFR and enhanced-CT. RESULTS: All patients underwent laparoscopic radiofrequency ablation surgery successfully. The mean operation time was (101 ± 19) minutes and the mean blood loss was (90 ± 14) ml (no blood transfusion pre- and post-operation). During postoperative follow-up, enhanced CT revealed complete ablation in 39 cases (the success rate was 97.5%), and 1 residue tumor was confirmed by enhanced CT 7 days post operation. This patient was under close surveillance because of solitary kidney. No progression of the residue tumor was found during the follow-up. One case of recurrence was confirmed by enhanced CT in 6 month after operation. The 3-year recurrence rate was 2.5%. No further intervation was performed on this patient and no change was found in the recurrence area during the follow-up. Both 3-year total survival rate and 3-year cancer specific survival rate were 100%. The mean eGFR was (72 ± 9) ml/(min·1.73 m(2)) in 3 years after surgery. There was no significant difference between pre-and post-operation (P > 0.05). CONCLUSION: Mid-term follow-up results show the effectiveness and safety of laparoscopic radiofrequency ablation in the treatment for T1aN0M0 RCC and have no negative influence on the renal function.

catena-Poly[[[bis-(nitrato-κO)copper(II)]-bis-[µ-1,3-bis-(imidazol-1-yl)-5-methyl-benzene-κ(2)N(3):N(3')]] dihydrate].

In the title complex, {[Cu(NO(3))(2)(C(13)H(12)N(4))(2)]·2H(2)O}(n), the Cu(II) atom is located on a crystallographic center of symmetry and adopts an N(4)O(2) octa-hedral coordination geometry with four imidazole N atoms in the equatorial sites and two O atoms in the axial sites. The dihedral angles between the central benzene ring and the imidazole rings are 4.93 (11) and 46.08 (12)°. The 1,3-bis-(imidazol-1-yl)-5-methyl-benzene ligand is bis-monodentate, linking symmetry-related Cu(II) atoms into sheets in the bc plane. These sheets are further bridged into a three-dimensional supra-molecular structure by O-H⋯O and C-H⋯O hydrogen bonds.

N-Benzyl-N,N-dimethyl-octa-decan-1-aminium (2-thioxo-1,3-dithiole-4,5-dithiol-ato-κ(2)S(4),S(5))nickelate(III).

The asymmtric unit of the title compound, (C(27)H(50)N)[Ni(C(3)S(5))(2)], contains two N-benzyl-N,N-dimethyl-octa-decan-1-aminium cations, [BDA](+), and two [Ni(dmit)(2)](-) anions (dmit = 2-thioxo-1,3-dithiole-4,5-dithiol-ate). The C(18) chains in both cations adopt almost ideal extended conformations. The Ni(III) atoms are coordinated by two S,S'-bidentate ligands, generating NiS(4) square planes. Short Ni⋯S [3.734 (2) Å] and S⋯S contacts [3.5438 (15) Å] occur in the crystal structure; if these are considered to be bonding inter-actions, then infinite sheets of anions parallel to (111) arise.

3,5-Dimethyl-1-(4-nitro-benz-yl)pyridinium bis-(benzene-1,2-dithiol-ato-κ(2)S,S')nickelate(III).

The asymmetric unit of the title compound, (C(14)H(15)N(2)O(2))[Ni(C(6)H(4)S(2))(2)], contains one cation and two halves of two centrosymmetric crystallographically independent anions. In the anions, the Ni(III) atoms are coordinated by four S atoms in a distorted square-planar geometry. In the cation, the dihedral angle between the pyridine and benzene rings is 88.66 (17)°. In the crystal, anions and cations inter-act through C-H⋯S and C-H⋯O hydrogen bonds.

1-(2,4-Dichloro-benz-yl)pyridinium bis-(2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ato-κS,S')nickelate(III).

In the title compound, (C(12)H(10)Cl(2)N)[Ni(C(3)S(5))(2)], the Ni(III) atom is chelated by two bidentate 2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ate (dmit) dianions and shows a distorted square-planar geometry. The two dmit ligands are twisted with respect to each other by 3.21 (2)°. In the cation, the two aromatic groups linked by the methyl-ene bridging group form a dihedral angle of 68.09 (2)°. S⋯S [3.6212 (11) and 3.5573 (9) Å] and Ni⋯S [3.566 (2)Å] inter-actions influence the arrangement of the anions in the crystal.

trans-Tetra-aqua-bis-[1,3-bis-(4-pyrid-yl)propane-κN]cobalt(II) biphenyl-4,4'-disulfonate monohydrate.

In the title compound, [Co(C(13)H(14)N(2))(2)(H(2)O)(4)](C(12)H(8)O(6)S(2))·H(2)O, the cation, anion and uncoordinated water mol-ecule have crystallographically imposed twofold symmetry. The cobalt(II) atom exhibits a slightly distorted octa-hedral coordination geometry provided by two N atoms from two 1,3-bis-(4-pyrid-yl)propane ligands and the O atoms from four water mol-ecules. The dihedral angle between the pyridine rings in the ligand is 86.14 (11)°, whereas the dihedral angle formed by the symmetry-related benzene rings in the anion is 35.81 (12)°. In the crystal, cations, anions and water mol-ecules are linked into layers parallel to the ac plane by O-H⋯O and O-H⋯N hydrogen-bond inter-actions. The layers are further connected into a three-dimensional network by C-H⋯O hydrogen bonds.

1-(3,4-Dichloro-benz-yl)pyridinium bis-(2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ato-κS,S')nickelate(III).

The title compound, (C(12)H(10)Cl(2)N)[Ni(C(3)S(5))(2)], is an ion-pair complex consisting of 1-(3,4-dichloro-benz-yl)pyridinium cations and [Ni(dmit)(2)] anions (dmit = 2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ate). In the anion, the Ni(III) ion exhibits a square-planar coordination involving four S atoms from two dmit ligands. In the crystal, weak S⋯S [3.368 (2) and 3.482 (3) Å], Ni⋯S [3.680 (2) Å] and Cl⋯S [3.491 (2) Å] inter-actions and C-H⋯S hydrogen bonds lead to a three-dimensional supra-molecular network.

1-(4-Iodo-benz-yl)-3-methyl-pyridinium bis-(benzene-1,2-dithiol-ato)nickelate(III).

The asymmetric unit of the title compound, (C(13)H(13)IN)[Ni(C(6)H(4)S(2))(2)], contains half each of two centrosymmetric anions and a single cation in a general position. In the anions, the Ni(III) ions are surrounded by four S atoms in a distorted square-planar geometry. In the crystal, the anions exhibit two different packing modes by stacking along the a axis in face-to-face and side-by-side fashions. Inter-ionic C-H⋯S hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.6947 (5) Å] are observed.

[Inhibitory effect of TRPV6 silencing on prostate cancer cell line LNCaP in vitro].

OBJECTIVE: To explore the effects of the TRPV6 gene silencing by small interfering RNA (siRNA) on the proliferation, cell cycle and apoptosis of human prostate cancer LNCaP cells. METHODS: We constructed two siRNA sequences (siTRPV6-1 and siTRPV6-2) targeting the TRPV6 gene and then transfected them into LNCaP cells mediated by liposome. The transcription of TRPV6 mRNA was detected by RT-PCR, and the effects of siRNA on the proliferation, cell cycle and apoptosis of the LNCaP cells were determined by MITT and flow cytometry. RESULTS: Both siTRPV6-1 and siTRPV6-2 significantly suppressed the expression of TRPV6 mRNA in the LNCaP cells, and the expression was decreased with the extension of time, by 73 and 77% respectively at 72 h after transcription with siTRPV6-1 and siTRPV6-2 as compared with the blank control group (P < 0.01). The proliferation inhibition rates were the highest (34.53 and 29.32%) at 48 h in comparison with 24 and 72 h (P < 0.05). The number of cells was significantly increased in the GO and G1 phases and decreased in the S phase after siTRPV transfection (P < 0.01). The apoptosis rates of LNCaP cells were 14.45 and 12.73% respectively at 48 h after transfected with siTRPV6-1 and siTRPV6-2, significant higher than in the blank control and negative control groups (P < 0.05). CONCLUSION: TRPV6-targeted siRNA can effectively inhibit the transcription of TRPV6 mRNA, inhibit the proliferation of LNCaP cells, arrest their cycles in the G0 and G1 phases, and induce their apoptosis.

Bis{1,2-bis-[2-(1H-imidazol-1-yl)eth-oxy]ethane-κN,N}dichloridocadmium(II) monohydrate.

The asymmetric unit of the title compound, [CdCl(2)(C(12)H(18)N(4)O(2))(2)]·H(2)O, contains one water mol-ecule and two halves of a [CdCl(2)(BIEE)(2)] complex mol-ecule {BIEE is 1,2-bis-[2-(1H-imidazol-1-yl)eth-oxy]ethane}, with the Cd(II) atoms lying on inversion centres. Each metal atom displays an elongated octa-hedral coordination geometry provided by two trans-arranged chloride anions and four N atoms from two BIEE ligands. Weak O-H⋯Cl hydrogen-bond inter-actions contribute to the stability of the crystal packing.

4,4'-Dimethyl-1,1'-(p-phenyl-enedimethyl-ene)dipyridinium bis-[7,7,8,8-tetra-cyano-quinodimethanide(1-)].

In the title salt, C(20)H(22)N(2) (2+)·2C(12)H(4)N(4) (-), the cations and anions stack along the b axis into segregated columns. In the cation, which has a crystallographically imposed centre of symmetry, the dihedral angle between the benzene and pyridine rings is 89.14 (4)°. Centrosymmetrically related anions form dimers by π-π stacking inter-actions, with centroid-centroid separations of 3.874 (4) Å. The crystal packing is stabilized by inter-columnar C-H⋯N hydrogen bonds.

1-(3,4-Dichloro-benz-yl)-3-methyl-quinolin-1-ium 7,7,8,8-tetra-cyano-quinodimethanide.

In the title salt, C(17)H(14)Cl(2)N(+)·C(12)H(4)N(4) (-), cations and anions stack along the a axis into segregated columns by π-π stacking inter-actions, with alternating centroid-centroid separations of 3.5957 (7) and 3.7525 (7) Šfor the cation column and 3.4252 (6) and 4.1578 (7) Šfor the anion column. In the cation, the dihedral angle between the benzene ring and the quinoline ring system is 76.35 (4)°. The crystal packing is stabilized by inter-columnar C-H⋯N hydrogen bonds.

Dichloridobis(phenyl 2-pyridyl ketone oxime)nickel(II) acetone solvate.

The Ni atom in the title compound, [NiCl(2)(C(12)H(10)N(2)O)(2)]·C(3)H(6)O, adopts a distorted octa-hedral geometry, being ligated by four N atoms from two different phenyl 2-pyridyl ketone oxime ligands and two Cl atoms. In the crystal structure, inter-molecular O-H⋯Cl hydrogen bonds link the mol-ecules into a chain structure along [010]. There is a π-π contact between the pyridine rings [centroid-centroid distance = 3.824 (5) Å].

1-(4-Cyano-benz-yl)-4-methyl-pyridinium bromide.

In the title compound, C(14)H(13)N(2) (+)·Br(-), the 1-(4-cyano-benz-yl)-4-methyl-pyridinium cation has a Λ-shaped conformation, and the dihedral angle between the benzene and pyridinium rings is 75.8 (2)°. In the crystal, two cations form a dimer through π-π inter-actions between pyridine rings [the centroid-centroid distance is 3.685 (1) Å].

Poly[aqua[µ(2)-1,2-bis-(imidazol-1-yl-methyl)benzene-κN:N](µ(2)-5-bromo-benzene-1,3-dicarboxyl-ato-κO,O:O)nickel(II)].

In the two-dimensional title coordination polymer, [Ni(C(8)H(3)BrO(4))(C(14)H(14)N(4))(H(2)O)](n), the Ni(II) atom adopts a distorted octa-hedral geometry, being ligated by three O atoms from two different 5-bromo-benzene-1,3-dicarboxyl-ate ligands, two N atoms from two 1,2-bis-(imidazol-1-ylmeth-yl)benzene ligands and one coordinated water mol-ecule. The Ni atoms are bridged by the 5-bromo-benzene-1,3-dicarboxyl-ate ligands, forming chains, which are further linked by 1,2-bis-(imidazol-1-ylmeth-yl)benzene, generating a layer structure parallel to (001).