Dual-Valence Characteristics of Be11: Tin/Lead-like Superatom.

To enhance the superatom family, the new superatom analogue Be11 of group IVA elements has been developed. Be11 can exhibit multiple valence states (+2 and +4), similar to carbon-group elements, and is capable of forming stable ionic compounds with other atoms such as carbon, chalcogen, (super)halogen, and hydroxyl. This resembles how tin and lead atoms combine with these elements to form stable molecules. Their special stability can be rationalized from the perspective of a cluster shell model. Sn or Pb could be the nearest atomic analogue to Be11 in group IVA, as the +2 oxidation state is more stable than the +4 oxidation state. This comparative investigation highlights the resemblance between Be11 and carbon-group elements, which encourages additional exploration within the superatom family.

Role of Hydrogen Sulfide and Hypoxia in Hepatic Angiogenesis of Portal Hypertension.

The pathogenesis of portal hypertension remains unclear, and is believed to involve dysfunction of liver sinusoidal endothelial cells (LSEC), activation of hepatic stellate cells (HSC), dysregulation of endogenous hydrogen sulfide (H2S) synthesis, and hypoxia-induced angiogenic responses. H2S, a novel gas transmitter, plays an important role in various pathophysiological processes, especially in hepatic angiogenesis. Inhibition of endogenous H2S synthase by pharmaceutical agents or gene silencing may enhance the angiogenic response of endothelial cells. Hypoxia-inducible factor-1 (HIF-1) is the main transcription factor of hypoxia, which induces hepatic angiogenesis through up-regulation of vascular endothelial growth factor (VEGF) in HSC and LSEC. H2S has also been shown to be involved in the regulation of VEGF-mediated angiogenesis. Therefore, H2S and HIF-1 may be potential therapeutic targets for portal hypertension. The effects of H2S donors or prodrugs on the hemodynamics of portal hypertension and the mechanism of H2S-induced angiogenesis are promising areas for future research.

Highly effective removal of antibiotics from aqueous solution by magnetic ZnFe2O4/activated carbon composite.

Water pollution from antibiotics has attracted a lot of attention for its serious threat to human health. In this study, a magnetic adsorbent (zinc ferrite/activated carbon (ZnFe2O4/AC) was synthesized via microwave method to effectively remove gemifioxacin mesylate (GEM) and moxifloxacin hydrochloride (MOX). Based on the porosity of AC and the magnetism of ZnFe2O4, the resulting ZnFe2O4/AC has high adsorption capacities and can be easily separated from the solid-liquid system via a magnetic field. The largest adsorption capacities for GEM and MOX can reach up to 433.4 mg g-1 and 388.8 mg g-1, respectively, higher than those of reported adsorbents such as MIL-101 and MOF-808. Fastest adsorptions of GEM and MOX were found at 5 min, and solution pH and coexisting salts do not have a significant influence on the adsorption process. The adsorption mechanism analysis indicates that electrostatic interaction and H-bond interaction contribute to the effective adsorption.

The State of the Art on Blood MicroRNAs in Pancreatic Ductal Adenocarcinoma.

Despite enormous advances being made in diagnosis and therapeutic interventions, pancreatic ductal adenocarcinoma (PDAC) is still recognized as one of the most lethal malignancies. Early diagnosis and timely curative surgery can markedly improve the prognosis; hence, there is an unmet necessity to explore efficient biomarkers for patients' benefit. Recently, blood miRNAs (miRNAs) have been reported to be a novel biomarker in human cancers. Part of it is selectively packaged by plasma exosomes released from cells via exocytosis and is highly sensitive to changes in the tumor microenvironment. Furthermore, due to less invasiveness and technical availability, miRNA-based liquid biopsy holds promise for further wide usage. Therefore, this review is aimed at presenting an update on the association between blood miRNAs and the biology of PDAC, then discussing its clinical utilization further.

Efficient separation of vitamins mixture in aqueous solution using a stable zirconium-based metal-organic framework.

High-efficiency separation of niacin (NIA) and nicotinamide (NIC) still faces large challenge up to date. In this work, a stable zirconium-based metal-organic framework (DUT-67) was used to adsorb and separate NIA and NIC in aqueous solutions. The adsorption capacities for NIA and NIC at the concentration ratio of 1:1 were 110.2 mg g-1 and 11.2 mg g-1, respectively. Further study indicates that low ratio of NIA/ NIC is in favor of the separation. High temperature can restrain the adsorptions of NIA and NIC but promote the separation. Besides, DUT-67 can be well regenerated via a simple method. Mechanism analysis indicates that electrostatic interaction plays a critical role in the separation of these vitamins.

A metal-organic framework with large 1-D channels and rich OH sites for high-efficiency chloramphenicol removal from water.

High-efficiency removal of chloramphenicol (CAP) drug from waste water still faces a large challenge up to date. Herein, we report the first metal-organic framework-based adsorbent (PCN-222) for CAP and effective removal was achieved. PCN-222 exhibits a large adsorption capacity of 370 mg g-1, superior to some other MOFs and various reported adsorbents; and more importantly, the adsorption equilibrium can be quickly obtained at only 58 s. Besides, ∼99.0% of CAP can be removed from water in the low concentrations (including the concentrations found in real water). Further investigation indicates that H-bond interaction, electrostatic interaction and the special pore structure of PCN-222 all play important effects on the high-efficiency removal of CAP. Therefore, our work may provide a novel perspective for removing CAP or other antibiotic drugs from contaminated water.

Functionalized metal-organic frameworks for effective removal of rocephin in aqueous solutions.

The porous metal-organic frameworks, MIL-101, MIL-101-SO3H and MIL-101-NH2 were used for the removal of harmful drug (rocephin) from water via adsorption. The kinetics study suggests that the adsorption onto all the MOFs follows the pseudo-second-order model. The adsorption isotherms results suggest that the adsorption onto MIL-101 and MIL-101-NH2 fits well with Langmuir model and the maximum adsorption capacities are calculated to 204.08 mg g-1 and 277.78 mg g-1, respectively; while the adsorption onto MIL-101-SO3H cannot fit well with both Langmuir and Freundlich models and the maximum adsorption capacity in the experiment is 25 mg g-1. Furthermore, the effect of pH as well as the adsorption mechanism was analysed systematically. It was found that electrostatic interaction as well as hydrogen-bond interaction plays dominant roles in adsorption of rocephin, and MIL-101-NH2 with abundant amino groups can exhibit better adsorption capacity and removal percentage towards rocephin than MIL-101, MIL-101-SO3H, and some other common adsorbents. In addition, co-existed Zn(NO3)2 can induce a large improvement of rocephin adsorption performance of MIL-101-NH2. At last, MIL-101-NH2 demonstrates to be a renewable adsorbent. In conclusion, we suggest MIL-101-NH2 is a promising adsorbent for effective removal of rocephin in water.

Embryo and Developmental Toxicity of Cefazolin Sodium Impurities in Zebrafish.

Cefazolin sodium is an essential drug that is widely used in clinical therapy for certain infective diseases caused by bacteria. As drug impurities are considered to be one of the most important causes of drug safety issues, we studied embryotoxicity, cardiotoxicity, and neurotoxicity of nine cefazolin sodium impurities in zebrafish embryo and larvae for the objective control of impurity profiling. LC-MS/MS was employed to analyze the compound absorbance in vivo, and the structure-toxicity relationship was approached. Our results suggested that the structure of MMTD (2-mercapto-5-methyl-1, 3, 4-thiadiazole) is the main toxic functional group for embryo deformities; the 7-ACA (7-aminocephalosporanic acid) structure mainly affects motor nerve function; and both the MMTD and 7-ACA structures are responsible for cardiac effects. Impurity G (7-ACA) presented with the strongest toxicity; impurity A was most extensively absorbed to embryo and larvae; and impurity F (MMTD) exhibited the strongest apparent toxic effect; Therefore, impurities F and G should be monitored from the cefazolin sodium preparations.

Assessment and Implications of Social Withdrawal Subtypes in Young Chinese Children: The Chinese Version of the Child Social Preference Scale.

The authors' goals were to evaluate the psychometric properties of the Chinese version of the Child Social Preference Scale (CSPS; R. J. Coplan, K. Prakash, K. O'Neil, & M. Armer, 2004) and examine the links between both shyness and unsociability and indices of socioemotional functioning in young Chinese children. Participants included of two samples recruited from kindergarten classes in two public schools in Shanghai, China. Both samples included children 3-5 years old (Sample 1: n = 350, Mage = 4.72 years, SD = 0.58 years; Sample 2: n = 129, Mage = 4.40 years, SD = 0.58 years). In both samples, mothers rated children's social withdrawal using the newly created Chinese version of the CSPS, and in Sample 2, teachers also provided ratings of socioemotional functioning. Consistent with previous findings from other cultures, results from factor analyses suggested a 2-factor model for the CSPS (shyness and unsociability) among young children in China. In contrast to findings from North America, child shyness and unsociability were associated with socioemotional difficulties in kindergarten. Some gender differences were also noted. Results are discussed in terms of the assessment and implications of social withdrawal in early childhood in China.

Poly[diaqua-bis-(nitrato-κ²O,O')bis-(1,10-phenanthroline-κ²N,N')-µ3-succinato-dicadmium].

In the title coordination polymer, [Cd2(C4H4O4)(NO3)2(C12H8N2)2(H2O)2](n), the Cd(II) ion is seven-coordinated within a distorted penta-gonal-bipyramidal O5N2 environment. The succinate anions, located on an inversion centre, adopt a bis-monodentate bridging mode, leading to the formation of rods along [100]. The rods are connected by O-H⋯O hydrogen bonds between the coordinating water mol-ecules and nitrate O atoms of adjacent rods; the same type of hydrogen bonds are also observed between water and carboxyl-ate O atoms within the rods. π-π stacking inter-actions with a minimum plane-to-plane separation of 3.462 (2) Šoccur between phenanthroline ligands.

Di-µ-benzoato-κO,O':O';κO:O,O'-bis-[(benzoato-κO,O')(1,10-phenanthroline-κN,N')cadmium].

The dinuclear title compound, [Cd(2)(C(7)H(5)O(2))(4)(C(12)H(8)N(2))(2)], lies on a crystallographic twofold axis. The Cd(II) ions are connected by two bridging benzoate anions and each ion is seven-coordinated by five O atoms from three benzoate ligands and by two N atoms from 1,10-phenanthroline. The benzoate ligands adopt two different coordination modes, acting as bidentate and bridging tridentate ligands. The discrete neutral mol-ecules further extend their structure into a three-dimensional supra-molecular framework by inter-molecular π-π [inter-planar distances of 3.392 (4) Å] and C-H⋯π stacking inter-actions [H-mean plane = 2.567 (4) and 2.781 (4) Å].

Poly[[triaqua-(µ(3)-4-oxidopyridine-2,6-dicarboxyl-ato)thulium(III)] monohydrate].

In the title coordination polymer, {[Tm(C(7)H(2)NO(5))(H(2)O)(3)]·H(2)O}(n), the Tm(III) atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxyl-ate trianion, two monodentate anions and three water mol-ecules, forming a distorted bicapped trigonal-prismatic TmNO(7) coordination geometry. The anions bridge adjacent Tm(III) ions into double chains. Adjacent chains are further connected into sheets. O-H⋯O hydrogen bonds involving both coordinated and uncoordinated water mol-ecules generate a three-dimensional supra-molecular framework.

Poly[[triaqua-(µ(3)-4-oxidopyridine-2,6-dicarboxyl-ato)holmium(III)] mono-hydrate].

In the title coordination polymer, {[Ho(C(7)H(2)NO(5))(H(2)O)(3)]·H(2)O}(n), the Ho(III) atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxyl-ate trianion, two monodentate anions and three water mol-ecules, forming a distorted bicapped trigonal-prismatic HoNO(7) coordination geometry. The anions bridge adjacent Ho(III) ions into double chains. Adjacent chains are further connected into sheets. O-H⋯O hydrogen bonds involving both coordinated and uncoordinated water mol-ecules generate a three-dimensional supra-molecular framework.

Di-µ-benzoato-κO,O':O;κO:O,O'-bis-[(benzoato-κO,O')(1,10-phenanthroline-κN,N')lead(II)].

In the centrosymmetric dinuclear title compound, [Pb(2)(C(7)H(5)O(2))(4)(C(12)H(8)N(2))(2)], two Pb(2+) ions are connected by two tridentate bridging benzoate anions. The Pb(2+) ion is seven-coordinated by five O atoms from three benzoate anions and two N atoms from the 1,10-phenanthroline ligands. The benzoate anions adopt two different coordination modes, one bidentate-chelating and one tridentate bridging-chelating. The three-dimensional supra-molecular framework is achieved by inter-molecular π-π stacking inter-actions, with a shortest centroid-centroid distance of 3.617 (4) Å.

Poly[diaqua-tris-(µ(4)-1,3-phenyl-ene-diacetato)-dicerium(III)].

In the title coordination polymer, [Ce(2)(C(10)H(8)O(4))(3)(H(2)O)(2)](n), each Ce(III) atom is nine-coordinated by eight O atoms from six different 1,3-phenyl-enediacetate (pda) bivalent anions and one O atom from a coordinated water mol-ecule, forming a distorted tricapped trigonal-prismatic coordination geometry. Eight Ce(III) ions and twelve pda ligands form a large [Ce(8)(pda)(12)] ring, and four Ce(III) ions and six pda ligands form a small [Ce(4)(pda)(6)] ring. The rings are further connected by the coordination inter-actions of pda ligands and Ce(III), generating a three-dimensional supra-molecular framework.

Poly[[triaqua-(µ(3)-4-oxidopyridine-2,6-dicarboxyl-ato)terbium(III)] monohydrate].

In the title coordination polymer, {[Tb(C(7)H(2)NO(5))(H(2)O)(3)]·H(2)O}(n), the Tb(III) atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxyl-ate trianion, two adjacent monodentate anions and three water mol-ecules, forming a distorted bicapped trigonal-prismatic TbNO(7) coordination environment. The anions bridge adjacent Tb(III) ions into double chains. Adjacent chains are further connected into sheets parallel to (10). O-H⋯O hydrogen bonds involving both coordinated and uncoordinated water mol-ecules generate a three-dimensional network.

Poly[diaqua-tris-(µ(4)-1,3-phenyl-enediacetato)-dineodymium(III)].

In the title coordination polymer, [Nd(2)(C(10)H(8)O(4))(3)(H(2)O)(2)](n), each of the two Nd(III) ions is nine-coordinated by eight O atoms from six different 2,2'-(m-phenyl-ene)diacetate (pda) bivalent anions and by one O atom from a water mol-ecule, forming a distorted tricapped trigonal-prismatic coordination geometry. Eight Nd(III) ions and 12 pda ligands form a large [Nd(8)(pda)(12)] ring, and four Nd(III) ions and six pda ligands form a small [Nd(4)(pda)(6)] ring. These rings are further connected by the coordination inter-actions of pda ligands and Nd(III), generating a three-dimensional supra-molecular framework.

Triaqua-(1,10-phenanthroline-2,9-dicarboxyl-ato)cobalt(II) dihydrate.

The title compound, [Co(C(14)H(6)N(2)O(4))(H(2)O)(3)]·2H(2)O, has two-fold crystallographic symmetry. The Co(II) atom is in a distorted penta-gonal-bipyramidal coordination environment with two N atoms and two O atoms from a tetradentate 1,10-phenanthroline-2,9-dicarboxyl-ate ligand and one O atom from a water mol-ecule forming the penta-gonal plane, and two O atoms from two water mol-ecules occupying axial positions. In the crystal, adjacent mol-ecules are linked by O-H⋯O hydrogen bonds, forming a three-dimensional network.

Piperazine-1,4-diium bis-(hydrogen 2-propyl-1H-imidazole-4,5-dicarbox-ylate) monohydrate.

The title compound, C(4)H(12)N(2) (2+)·2C(8)H(9)N(2)O(4) (-)·H(2)O, is a hydrated proton-transfer compound obtained from 2-propyl-1H-imidazole-4,5-dicarb-oxy-lic acid and piperazine. The asymmetric unit contains one half-cation, one anion and half a water mol-ecule. There is a centre of inversion at the centre of the cation ring and the water molecule O atom lies on a twofold rotation axis. In the crystal, inter-molecular N-H⋯O and N-H⋯N hydrogen bonds help to construct a three-dimensional framework. Almost symmetrical, intramolecular O-H⋯O inter-actions are also observed.