Search

Given the safety of synthetic antioxidants, people are increasingly inclined to develop and use natural antioxidants. However, rapid screening and identification of active ingredients from the complex systems of natural products is one of the major challenges for the modernization of traditional Chinese medicine. In this study, online extraction-high performance liquid chromatography-diode array detection-quadrupole time-of-flight mass spectrometry coupled with ABTS antioxidant assay (OLE-HPLC-DAD-QTOF-MS/MS-ABTS), in which sample preparation, separation, detection and antioxidant assay were integrated in a single step, was used to rapidly identify antioxidant components from the different parts of Citrus reticulata, including its peels, leaves, vascular bundies and seeds. After method validation (system adaptability, extraction yield and repeatability), the four samples of different botanical parts were analyzed. As a result, among 49 found chromatographic peaks, 33 peaks displayed varying degrees of antioxidant activity and 39 peaks were tentatively or unambiguously identified based on their retention time, UV spectrum and mass spectrometry information and the comparison with reference substance and data in literature, including 10 phenolic acids, 9 polymethoxy flavonoids, 7 flavonoid-O-glycosides and 13 other ingredients. It is concluded that the established method is simple, fast, and reliable, which not only saves the materials and solvents as well as time, but also reduces the risk of degradation of chemical components during the extraction process, suitable for rapid screening and identification of antioxidant components of complex mixture.

This paper analyses the impact of the poverty alleviation relocation (PAR) program on rural household income and evaluates the heterogeneous income effects of various relocation modes, based on a panel dataset of relocated households from 16 counties in eight Chinese provinces. The results show that participation in the PAR increases the income of both rural and urban resettlers. More specifically, it has a significant positive effect on agricultural and wage income for rural and urban resettlers, respectively. Further analyses show that the income increase for rural resettlers was mainly due to agricultural technology training and that the income increase for town resettlers was attributed to medical security. For the village resettlers, policies should focus on strengthening the development of local industries and training of agricultural technologies. For the urban resettlers, non-agricultural employment and public services in the urban resettlement areas should be promoted.

Targeted poverty alleviation is a unique approach adopted in China to help achieve the vision of a moderately prosperous society in all aspects and the “Chinese Dream”. Industrial development as a means of poverty alleviation is an integral part of the “Five-pronged Poverty Alleviation Measures” Project of targeted poverty alleviation, and a critical foundation for other poverty alleviation measures. In this study, a comprehensive evaluation method was used to measure farmers’ livelihood based on the framework of sustainable livelihood. Specifically, the effects of industrial development on farmers’ livelihood capital were estimated by employing the propensity score matching combined with the difference-in-differences (PSM-DID) approach. Findings suggest that industrial development had a significantly positive effect on the livelihood capital of farmers. Industrial development can significantly enhance farmers’ human, social and financial capital, while it cannot significantly affect the natural and physical capital. Industrial development had heterogeneous effects on farmers’ livelihood capital, more efficiently impacting on the non-poor than the poor. The effects on farmers’ livelihood capital varied across regions, with Guizhou experiencing a larger effect than Sichuan. However, the effect was insignificant for farmers in Gansu. To improve farmers’ livelihood capital, it is necessary to take measures to strengthen their human capital, promote the innovation of financial products, and make good use of their social capital; it is also essential to strengthen the support of industrial development to the poor.

PurposeThis paper aims to examine impacts of the poverty alleviation relocation (PAR) program on diet quality of low-income households in China. We explore the impact mechanism of relocation on diet quality and the heterogeneous effects of different relocation modes.Design/methodology/approachA fixed effects model is constructed using panel data of 1126 low-income households collected over three years in eight provinces of China. The PAR program provides a natural experiment which dramatically changes the living conditions surrounding farmers. We are able to identify the causal effects of relocation on diet quality free from selection bias.FindingsThe empirical results show that the PAR program improves diet quality of low-income households and that better market access and increasing incomes induced by relocation play an important role in this improvement. Improved market access significantly reduces the over-consumption of staple foods, whereas higher income significantly reduces the intake divergences of non-staple foods. The impacts of different relocation modes on diet quality are highly heterogeneous.Practical implicationsOur findings indicate that the PAR program benefits diet quality of low-income households through greater market access and increases in total household income. Market improvements and food subsidies are conducive to improving the diet quality of the low income.Originality/valueDespite widespread evidences of healthy diets being associated with household environments and income, selection bias remains. This paper utilizes an exogenous program to explore the causal impacts of market access and family income on diet quality and to separate their different effects.

Stem photosynthesis (荒漠植物长期演化过程中保留了枝干光合(

In order to improve the functional properties of walnut protein isolate (WPI), the effect of partial hydrolysis with trypsin, crosslinking with transglutaminase (TGase), and combinations of both treatments on the physicochemical characteristics of WPI was investigated. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) indicated that WPI could be easily digested into smaller peptides by trypsin and could also be crosslinked into aggregates with high molecular weight. Hydrolyzing crosslinked WPI significantly increased its solubility from 9.73% to 54.54%. Scanning electron microscopy indicated that treatment with trypsin or TGase alone had a notable effect whereas the mixture of enzyme and TGase had a relatively lower effect on the microstructure of WPI. Hydrolysis did not affect the sulfhydryl (-SH) content while TGase crosslinking significantly reduced (-SH) content from 92.9 μmoL/g to 47.06 μmoL/g. Hydrolysis markedly increased the surface hydrophobicity (H0), while crosslinking did not significantly change H0. TGase treatment increased the viscosity of hydrolysates, but the viscosity of trypsin hydrolysates was not altered. Treatment of WPI with both TGase and trypsin showed the lowest initial G′ and G″ values due to the highest solubility. Thus, WPI with proteolysis and transglutaminase treatment has great potential for applications in the food industry.

Liposarcoma of the stomach is extremely rare, and only 37 cases have been reported worldwide. We herein report two cases of liposarcoma of the stomach. The first patient was referred to our hospital with upper abdominal discomfort. The endoscopic examination revealed a tumor mass about 3 cm in diameter. The patient underwent a partial gastrectomy and had an uneventful recovery. The histopathological examination revealed a well-differentiated liposarcoma. The second patient had symptoms of upper abdominal discomfort combined with nausea and anorexia. Several palpable masses were found with endoscopy. Endoscopic submucosal dissection was the treatment used, and the postoperative course was uneventful. The histopathological diagnosis was a well-differentiated liposarcoma. The two patients did not undergo any adjuvant therapy. They are both currently in good condition without recurrence. Therefore, we believe that the outcome of liposarcoma of the stomach is positive, and surgical resection may be the first choice for treatment at present.

SUMMARY Protein phosphatase 2A (PP2A) inhibition causes hy-perphosphorylation of tau and APP in Alzheimer’s disease (AD). However, the mechanisms underlying the downregulation of PP2A activity in AD brain remain unclear. We demonstrate that Cancerous Inhibitor of PP2A (CIP2A), an endogenous PP2A inhibitor, is overexpressed in AD brain. CIP2A-mediated PP2A inhibition drives tau/APP hyperphosphorylation and increases APP β-cleavage and Aβ production. Increase in CIP2A expression also leads to tau mislocalization to dendrites and spines and synaptic degeneration. In mice, injection of AAV-CIP2A to hippocampus induced AD-like cognitive deficits and impairments in long-term potentiation (LTP) and exacerbated AD pathologies in neurons. Indicative of disease exacerbating the feedback loop, we found that increased CIP2A expression and PP2A inhibition in AD brains result from increased Aβ production. In summary, we show that CIP2A overexpression causes PP2A inhibition and AD-related cellular pathology and cognitive deficits, pointing to CIP2A as a potential target for AD therapy., In Brief PP2A inactivation plays a key role in AD pathogenesis. Shentu et al. report that endogenous PP2A inhibitor CIP2A is upregulated in AD brains. CIP2A overexpression promotes β-cleavage of APP and tau hyperphosphorylation through PP2A inhibition, leading to impairments in synapse, hippocampal LTP, and memory., Graphical Abstract

In this Letter, we present the Rhodamine B catalyzed direct C–H arylation of indole with aryl diazonium salts. This method only requires green light and room temperature.

Arachin and conarachin-rich fractions of peanut protein were extracted by using cryoprecipitation followed by centrifugation. These two fractions were individually crosslinked using transglutaminase (TG). The physicochemical characteristics including aggregation due to crosslinking, solubility, thermal denaturation temperature (Td) and denaturation enthalpy (△ H), morphology of microstructure and surface hydrophobicity (H0) of TG-treated and untreated arachin and conarachin-rich fractions were determined. The relative contents of arachin and conarachin in arachin and conarachin-rich fractions were 75% and 65%, respectively. Conarachin-rich fractions were found to more conveniently aggregate than arachin-rich from the results of SDS-PAGE. The solubility of treated arachin and conarachin-rich fractions was decreased by 66.13% and 36.91%, respectively. Only marginal increase in Td was observed in the case of crosslinked arachin-rich fraction while significant increase in Td (of the order of 10 °C) was observed in crosslinked conarachin-rich fraction. The H0 values of both crosslinked arachin and conarachin-rich fractions decreased significantly. The treated arachin and conarachin-rich fractions had more compact microstructure compared to their untreated samples. Hence, the comparison of arachin and conarachin-rich in crosslinking and the mechanism of properties enhancement by TG is the aim of the research.

For improving the conditions of single function, low testing precision, complex operation that exists in the tests of leaf spring testing machine, and on the basis of relevant provisions GBT19844-2005 leaf spring, a test bench for leaf spring with multifunction is designed. Through the structure analysis of leaf spring, a structure scheme of test bench named gantry type is put forward, combined with the testing requirements of the national standard and the spring stress characteristics, the hydraulic loading system and PID(Proportion Integration Differentiation) control system is proposed as well. By this test bench, experiments of the leaf spring for "permanent deformation, stiffness, fatigue" and other aspects related can be conducted, with shorter experimental cycle and higher experimental precision.

In this Letter, we present the Rhodamine B catalyzed direct C–H arylation of indole with aryl diazonium salts. This method only requires green light and room temperature.

Intracellular accumulation of the hyperphosphorylated tau is a pathological hallmark in the brain of Alzheimer disease. Activation of extrasynaptic NMDA receptors (E-NMDARs) induces excitatory toxicity that is involved in Alzheimer’s neurodegeneration. However, the intrinsic link between E-NMDARs and the tau-induced neuronal damage remains elusive. In the present study, we showed in cultured primary cortical neurons that activation of E-NMDA receptors but not synaptic NMDA receptors dramatically increased tau mRNA and protein levels, with a simultaneous neuronal degeneration and decreased neuronal survival. Memantine, a selective antagonist of E-NMDARs, reversed E-NMDARs-induced tau overexpression. Activation of E-NMDARs in wild-type mouse brains resulted in neuron loss in hippocampus, whereas tau deletion in neuronal cultures and in the mouse brains rescued the E-NMDARs-induced neuronal death and degeneration. The E-NMDARs-induced tau overexpression was correlated with a reduced ERK phosphorylation, whereas the increased MEK activity, decreased binding and activity of ERK phosphatase to ERK, and increased ERK phosphorylation were observed in tau knockout mice. On the contrary, addition of tau proteins promoted ERK dephosphorylation in vitro. Taking together, these results indicate that tau overexpression mediates the excitatory toxicity induced by E-NMDAR activation through inhibiting ERK phosphorylation.

As conventional technique of cold extruding process face the problems that the equipment must provide large extrusion force during the workpiece extruding process, it has huge flow stress of the material and the frictional force between the mould and blank against the material flow under room temperature. To solve these problems, this article put forward a cold extruding mould with vibration. By simulation analysis of conventional and vibration of cold extrusion of travel load and velocity field, the force of vibration extrusion is reduced by 54% than that of conventional cold extrusion; therefore the forming surface of the parts and the material flow speed of vibration cold extrusion is greatly improved

t is necessary to establish a remote wireless monitoring system for the heading face of coal mine because of the risk of gas outburst and water inrush. This paper introduced a remote wireless monitoring system for heading face of coal mine based on wireless mesh network. The key technology is that the wireless backhaul link of this wireless communication system must remain high bandwidth and low latency after multi-hop in order to support video transmission because the laneway of coal mine is narrow and long. We used the technology of multi-interface multi-channel to design a 2-interface 3-channel backbone network for this wireless communication system. Each node of this backbone network is equipped with two interfaces, and three orthogonal channels of channel 1,6,11 provided by 802.11b/g are used. Compared to single interface single channel chain network, the 2-interface 3-channel wireless mesh backbone network has high throughput and low end to end delay while using appropriate channel allocation algorithm to make the channels of adjacent links non-interfered.

A series of mononuclear gold(I) acetylide complexes with urea moiety, R'(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-R (R' = cyclohexyl, R = NO(2) (2a), CF(3) (2b), Cl (2c), H (2d), CH(3) (2e), (t)Bu (2f), OCH(3) (2g); R' = phenyl, R = NO(2) (3a), OCH(3) (3b); R' = 4-methoxyphenyl, R = H (4a), OCH(3) (4b)), have been synthesized and characterized. The crystal structures of Ph(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-NO(2) (3a) and (4-CH(3)OC(6)H(4))(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(5) (4a) have been determined by X-ray diffraction. Complexes 2a-2g, 3b, and 4a-4b show intense luminescence both in the solid state and in degassed THF solution at 298 K. Anion binding properties of complexes 2a-2g, 3a-3b, and 4a-4b have been studied by UV-vis and (1)H NMR titration experiments. In general, the log K values of 2a-2g with the same anion in THF depend on the substituent R on the acetylide ligand of 2a-2g: R = NO(2) (2a)CF(3) (2b) ≥ Cl (2c)H (2d)CH(3) (2e) ≈ (t)Bu (2f) ≥ OCH(3) (2g). Complex 2a with NO(2) group shows the dramatic color change toward F(-) in DMSO, which provides an access of naked eye detection of F(-).

Mono-, di-, and tri-nuclear gold(I) complexes with dansyl group (dansyl = 5-dimethylamino-naphthalene-1-sulfonyl), 1–3, have been synthesized and their photophysical properties investigated. The crystal structures of complexes 2 and 3 were determined by X-ray diffraction.

Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag3(μ-dppm)3(μn-SR)2](ClO4) [n = 2, R = C6H4Cl-4 (1) and C{O}Ph (2); n = 3, R = tBu (3)], pentanuclear silver(I) thiolate complex [Ag5(μ-dppm)4(μ3-SC6H4NO2-4)4](PF6) (4), and hexanuclear silver(I) thiolate complexes [Ag6(μ-dppm)4(μ3-SR)4]Y2 [Y = ClO4, R =C6H4CH3-4 (5) and C10H7 (2-naphthyl) (7); Y = PF6, R = C6H4OCH3-4(6)], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the 3IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high-energy emission is tentatively attributed to come from the 3IL of thiolate ligands and low-energy emission is tentatively assigned to come from the admixture of metal···metal bond-to-ligand charge-transfer (MMLCT) and metal-centered (MC) excited states.

A series of trinuclear copper(I) acetylide complexes with carbonyl moiety, [Cu 3 (μ-dppm) 3 (μ 3 -η 1 -C CC(O)R) 2 ](ClO 4 ) (R = H ( 1 ), CH 3 ( 2 ), OCH 3 ( 3 ), NH 2 ( 4 ), NEt 2 ( 5 )) (dppm = bis(diphenylphosphino)methane), have been synthesized and characterized. The crystal structures of [Cu 3 (μ-dppm) 3 (μ 3 -η 1 -C CC(O)CH 3 ) 2 ](ClO 4 ) ( 2 ) and [Cu 3 (μ-dppm) 3 (μ 3 -η 1 -C CC(O)NH 2 ) 2 ](ClO 4 ) ( 4 ) were determined by X-ray diffraction. The photophysical properties of complexes 1 − 5 have been studied. Complexes 1 − 5 show luminescence both in the solid state and in acetonitrile solution at 298 K, and their emission energies are in the order: 5 > 4 > 3 > 2 > 1 . Density function theory (DFT) calculations at the hybrid Perdew, Burke, and Ernzerhof functional (PBE1PBE) level were performed on model complex 1 to elucidate the emission origin of complexes 1 − 5 .

The reaction of a racemic four-coordinated nickel(II) complex [Ni(α-rac-L)](ClO4)2 with l-Leu− in acetonitrile/water under basic conditions gave two six-coordinated diastereomers of {[Ni(SS-L)(l-Leu)](ClO4)}n (Δ-1) and {[Ni(RR-L)(l-Leu)](ClO4)}n (a-2). While the reaction of [Ni(α-rac-L)](ClO4)2 with d-Leu− in acetonitrile/water under basic condition generated two six-coordinated diastereomers of {[Ni(RR-L)(d-Leu)](ClO4)}n (Λ-1) and {[Ni(SS-L)(d-Leu)](ClO4)}n (b-2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, Leu− = leucine anion). Δ-1 and Λ-1 belong to supramolecular stereoisomers in which the [Ni(SS-L)(l-Leu)]+ and [Ni(RR-L)(d-Leu)]+ monomers are linked through the intermolecular hydrogen bonding interactions to form 1D homochiral right- and left-handed helical chains, respectively, while the connections of [{Ni(RR-L)}(l-Leu)]+/[{Ni(SS-L)}(d-Leu)]+ in a-2/b-2 through similar intermolecular hydrogen bonding interactions give 1D zigzag chains instead of 1D helical chains. In contrast, ...

Two new complexes: [Cu(dppz)(L-val)(H2O)]ClO4 (1) and [Cu(dppz)(L-tyr)(H2O)]ClO4·1.5H2O (2) (dppz=dipyrido[3,2-a:2′,3′-c]phenazine, L-val=L-valinate, L-tyr=L-tyrosinate) have been synthesized and investigated by elemental analysis, molar conductivity, UV-Vis and IR spectroscopies. Complex 1 has been structurally characterized by the single-crystal X-ray diffraction method, which crystallizes in the triclinic space group P-1 in a unit cell of a=0.9095(2) nm, b=1.3301(3) nm, c=1.3552(3) nm, α =93.518(3) °, β=97.192(3) °, γ=106.361(3) °, V=1.5526(6) nm3, Z=2, Dc=1.598 g·cm−3, µ=0.849 mm−1. The DNA binding and cleavage properties of the complexes have been studied by UV spectroscopy, fluorescence spectroscopy, viscosity measurement and agarose gel electrophoresis. The results show that the complexes can bind DNA by intercalation and cleave pBR322 DNA by free hydroxyl radical induced by the complexes in the presence of ascorbate, giving the order of the binding abilities and cleavage activity of the complexes to DNA: complex 2>1.

The complex [Cu(L-Phe)(TATP)(H2O)]ClO4.0.5H2O has been synthesized and investigated by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where TATP= 1,4,8,9-tetraazatriphenylene and L-phe = L-phenylaninate group. The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a=0.5730(l), b = 1.0190(2), c = 2.1430(4), α= 97.50 (1)°, β = 95.33(3)°, γ= 102.85(1)°, V= 1.1998(4) nm3, R1 = 0.0360, wR2 = 0.0400. The crystal contains two independent [Cu(L-Phe) (TATP)(H2O)]+ complexes Cu1 and Cu2, having essentially the same distorted square-pyramidal structure, where each Cu(II) ion coordinates two nitrogen atoms of TATP and the amino nitrogen and carboxylate oxygen atoms of L-Phe in the equatorial positions and one water oxygen at an axial position.

The reactions of 2,2′-bipyridyl-3,3′-dicarboxylic acid (H2bpdc) and 1,10-phenanthroline (phen) with lanthanide (III) salts in different concentrations under hydrothermal conditions formed two series of supramolecular isomers of 1D zigzag chains of [Ln(bpdc)1.5(phen)(H2O)]n·3nH2O (1Ln·3H2O), and 2D frameworks of [Ln(bpdc)1.5(phen)(H2O)]n (2Ln), (Ln = Ho, Er, Tm, and Yb). At lower concentrations, the supramolecular isomers of 1Ln were formed, in which each isomer has a dinuclear centrosymmetric dimeric unit of [Ln2(phen)2(H2O)2(μ2-bpdc)2]2+, and the dimeric units are alternately connected by μ2-bpdc2− to form a 1D zigzag chain of 1Ln. At higher concentrations, the supramolecular isomers of 2Ln were formed. All the compounds of 2Ln are isomorphous, in which two μ3-bpdc2− bridge two [Ln(phen)(H2O)]3+ units to yield a 1D double-chains of [Ln2(phen)2(H2O)2(bpdc)2]n2n+, and [Ln2(phen)2(H2O)2(bpdc)2]n2n+ chains are further connected by μ4-bpdc2− to form a 2D network of [Ln(bpdc)1.5(phen)(H2O)]n. The 2D sheets are combined through the intersheet π–π interactions between the adjacent phen molecules to form a 3D structure of 2Ln. The compounds of Er(III), and Yb(III) exhibit corresponding characteristic photoluminescence in the near-infrared (NIR) region, in which 1Ln and 2Ln show obviously different emission intensity due to their different structures.

Three tetrazole-based coordination polymers, [Zn3(Tz)6(H2O)2]n (1), [Cu2(Tz)3(OH)]n (2), and {[Cu5(Tz)9](NO3)·8H2O}n (3) (Tz = tetrazolate) have been prepared under hydro(solvo)thermal conditions using ethyl tetrazolate-5-carboxylate and corresponding metal salts as building blocks, in which tetrazolate was generated via in situ decarboxylation. The results of X-ray single diffraction analyses indicate that 1 possesses a 2D layer structure with μ2-Tz− bridged six- and four-coordinated Zn(II), forming a rare kagome dual topological layer. Compound 2 is a 3D layer−pillar structure, in which the Cu(II) ions are bridged by μ3-Tz− anions to generate a 2D sheet, and the 2D sheets are further pillared by μ2-Tz− and μ2-OH− to form a 3D framework with a fsc topology net. Compound 3 is a 3D porous framework with an acs topology net. Compound 1 exhibits photoluminescent properties with an emission peak at 467 nm, and compound 3 shows selective H2 and CO2 over N2 adsorption.

A series of cyanido-bridged complexes {[Fe III (phen) (CN) 4 ] 2 -[NiL 1 ]}·4H 2 O (1), {[FeIII(bipy)(CN)4]2[NiLl]}·4H 2 O (2), [Fe III -(bipy)(CN) 4 ] 2 [NiL 2 ] (3), {[Fe III (phen)(CN) 4 ) 2 [CuL 3 ]}·5H 2 O (4), {[Fe II (phen)(CN) 4 ][Ni(ea) 2 ]} 2 ·H 2 O (5), {[Fe II (phen)(CN) 4 ] [NiL 2 ]·2H 2 O} n (6), {[Fe III (bipy)(CN) 4 ] 2 [Ni(H 2 O) 2 ]}·6.5H 2 O} n (7) and {[Fe II (bipy)(CN) 4 ][Ni(ea)2]·H 2 O} n (8) were synthesized using H[Fe(phen)(CN) 4 ]·2H 2 O and H[Fe(bipy)(CN)4].2H20 as precursors [L 1 = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane, L 2 = 3,10-bis(2-phenylethyl)-l,3,5,8, 10,12-hexaazacyclotetradecane, L 3 = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, phen = 1,10-phenanthroline, bipy = 2,2'-bipyridine, ea = ethanolamine). Complexes 1-4 are trinuclear clusters, and 5 is a tetranuclear square. In 6, the [Fe II (phen)(CN) 4 ] 2- anions alternately bridge the [NiL 2 ] 2+ cations to generate a 1D wavy chain. The structure of 7 possesses a 4,2-ribbonlike chain, which contains a Ni II 2 (CN) 4 Fe III 2 square with each Ni II atom shared by two adjacent squares. Each Fell and Ni" atom in 8 acts as a three-connected node through the cyanido-bridges to generate a 2D network with a 4,8 2 topological net. Ferromagnetic couplings are found between the low-spin Fe III ions and the Ni" ions through the cyanido groups in 1-3 and 7, and a meta-magnetic behavior and a frequency dependence of the out-of-phase ac susceptibility are observed in 7.

Two supramolecular complexes, [Ni(rac-L)]3[CrO4]2[ClO4]2·4H2O (1) and [meso-H2L]0.5[VO3]·0.16H2O (2) (L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetra-decane), have been prepared in an aqueous solution, and detected by elemental analysis, IR, TG, and single crystal X-ray diffraction analyses. Compound 1 shows a one-dimensional hexagonal prism formed by the hydrogen bonding interactions between the secondary amines of rac-L and CrO4 2 anion/water molecules. Compound 2 displays a three-dimensional structure constructed by the hydrogen bond linking the helical chains of [VO3] n n− to the secondary amines of meso-L to generate 1D hexagon-shaped channels, and the channels are occupied by guest water molecules.

The reactions of four-coordinated transition metal macrocyclic complexes [ML](ClO(4))(2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, M = Ni, Cu) with NH4VO3 under different conditions gave four coordination polymers of {[(CuL)(0.5)(H2L)(1.5)][H2V10O2)] x 6H(2)O}(n) (1x6H(2)O), {[NiL](3)[V16O38(H2O)] x 6H(2)O}(n) (2 x 6H(2)O), {[NiL][VO(3)](2) x 0.33H2O}(n) (3.0.33H(2)O), and {[CuL][VO(3)](2) x 0.33H(2)O}(n) (4 x 0.33H2O). Single crystal X-ray diffraction analyses reveal that four diverse vanadium polyoxoanions, [H2V1oO28)(4-) cluster, [V16O38(H2O)](6-) cage, [V6O18](6-) ring, and [VO(3)](n)(n-) chain, were obtained from the same reactant NH(4)VO(3) under different conditions. In 1, the cluster anion [H2V10O28](4-) alternately bridges [CuL]2+/[H2L]2+ to form a one-dimensional chain, and the [V16O38(H2O)](6-) cage in 2 links three [NiL]2+ into a two-dimensional sheet. Compounds 3 and 4 show three-dimensional structures, which are constructed by the connections of hexanuclear [V6O18](6-) rings with [NiL]2+ in 3 and [VO3](n)(n-) chains with [CuL]2+ in 4, respectively, generating one-dimensional channels occupied by guest water molecules.

A series of water clusters encapsulated inside a cryptand cavity were obtained in the cryptand-acid supramolecular adducts of [(H2O)2⊂(H6L)][H2PO4]6(H2O)3 (1·3H2O), [(H2O)3⊂(H6L)][H2PO4]6(H2O)11 (2·11H2O), [(H2O)3⊂(H6L)][CH3(C6H4-p)SO3]6(H2O)4 (3·4H2O), and [(H2O)6⊂(H6L)][SO4]3(H2O)13 (4·13H2O) (L = N[(CH2)2NHCH2(C6H4-p)CH2NH(CH2)2]3N). In 1 and 2, H6L6+ is hydrogen bonded to six H2PO4− through its protonated nitrogen atoms to form two (O···H−N−H···)3 rings at two poles of H6L6+. A well encapsulated water dimer, and a circle- and cage-shaped trimer of [H2PO4]3 are formed in 1. A well encapsulated circular water trimer and a bowl-shaped trimer of [H2PO4]3 are formed in 2. In 3, the steric effect of the tolyl group of [CH3(C6H4-p)SO3]− causes a change in the conformation of H6L6+ to generate a favorable environment for a linear water trimer inside the crystand cavity. In 4, H6L6+ bonds three SO42− anions through the protonated nitrogen atoms at the one pole, and a quasi-prismatic hexamer water cluster is fo...

A dinuclear copper(II) complex [Cu 2 (TATP) 2 ( L -Leu) 2 (ClO 4 ) 2 ] 2 ·2H 2 O was synthesized and characterized, where, TATP=1,4,8,9-telraazatriphenylene, and L -Leu= L -leucinate. The complex was crystallized in the triclinic space group p 1, with two independent molecules in a unit cell. Two Cu(II) ions in each complex [Cu 2 (TATP) 2 ( L -Leu) 2 (ClO 4 ) 2 ] molecule were found to be in different coordination geometries, i.e. , Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of. TATP, the amino nitrogen and one carboxylate oxygen of L -Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L -Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalativc mode and cleave pBR322 DNA in the presence of ascorbatc.

Three new complexes, [Cu(phen)(L-argH+)Cl]Cl · 2.5H2O (1), [Cu(phen)(L-leu)(H2O)]Cl ·2.5H2O (2) and [Cu(phen)(L-met)(H2O)]Cl · 2H2O (3), where phen = 1,10-phenanthroline, L-arg = L-argininate, L-leu = L-leucinate, and L-met = L-methioninate, were synthesized and characterized by elemental analysis, molar conductivity, IR and UV-Vis spectroscopies. Complex 1 was structurally characterized by single-crystal X-ray diffraction. The superoxide dismutase (SOD)-like activities of the three complexes were determined by the improved NBT method. The results show that the complexes have high superoxide dismutase-like activities and may act as good mimics for superoxide dismutases.

1D chain macrocyclic Ni(II) complex of {[Ni(L)(CrO4)] · 5H2O} n (1) (L=3,10‐bis(2‐hydroxyethyl)‐1,3,5,8,10,12‐hexaazacyclotetradecane) was prepared and characterized by single crystal X‐ray analysis. The coordination geometry of Ni atom is slightly distorted octahedral, with four nitrogen atoms of the macrocyclic ligand L occupying the equatorial plane and two oxygen atoms of two different chromate anions situated at the axial sites. Each Cr(VI) atom is four‐coordinated with four oxygen atoms, forming a slightly distorted tetrahedral geometry. The [CrO4]2− anions alternately bridge the Ni(II) cations to form a 1D infinite zigzag chain of [Ni(L)(CrO4)]n. The chains are further linked by interchain hydrogen bonds to generate a 3D coordination framework, in which novel 2D water sheets consisting of dodecameric water rings are formed between the chains.

The reactions of a racemic four-coordinated nickel(II) complex [Ni(alpha-rac-L)](ClO4)2 (containing equal amount of SS and RR enantiomers) with l- and d-phenylalanine in acetonitrile/water gave two less-soluble six-coordinated enantiomers of {[Ni( f-SS-L)(l-Phe)](ClO4)}n (Delta-1) and {[Ni(f- RR-L)(d-Phe)](ClO4)}n (Lambda-1), respectively. Evaporation the remaining solutions gave two six-coordinated diastereomers of {[Ni 3(f- RR-L)3(l-Phe)2(H 2O)](ClO4)4}n (a-2) and {[Ni3(f- SS-L)3(d-Phe)2(H2O)](ClO4)4}n (b-2), respectively (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, Phe(-) = phenylalanine anion). The reaction of [Ni(alpha-rac-L)](ClO4)2 with dl-Phe(-) gave a conglomerate of c-1; in which, the SS and RR enantiomers preferentially coordinate to l- and d-Phe(-) respectively to give a racemic mixture of Delta-1 and Lambda-1, and the spontaneous resolution occurs during the reaction, in which each crystal crystallizes to become enantiopure. Removing Phe(-) from Delta-1 and Lambda-1 using perchloric acid gave two enantiomers of [Ni(alpha-SS-L)](ClO4)2 (S-3) and [Ni(alpha-RR-L)](ClO4)2 (R-3). Dissolving S-3 and R-3 in acetonitrile gave two six-coordinated enantiomers of [Ni( f-SS-L)(CH3CN)2](ClO4)2 (S-4) and [Ni( f- RR-L)(CH3CN)2](ClO4)2 (R-4), while dissolving [Ni(alpha-rac-L)](ClO4)2 in acetonitrile gave a racemic twining complex [Ni(f-rac-L)(CH3CN)2](ClO4)2 (rac-4). Delta-1 and Lambda-1 belong to supramolecular stereoisomers, which are constructed via hydrogen bond linking of [Ni( f-SS-L)(l-Phe)](+) and [Ni(f-RR-L)(d-Phe)](+) monomers to form 1D homochiral right-handed and left-handed helical chains, respectively. The reaction of S-3 with d-Phe(-) gave {[Ni(f-SS-L)(d-Phe)](ClO4)}n (5), which shows a motif of a 1D hydrogen bonded zigzag chain instead of a 1D helical chain. Compound a-2/ b-2 contains dimers of [{Ni(f-RR-L)}2(l-Phe)(H2O)](3+)/[{Ni( f- SS-L)}2(d-Phe)(H2O)](3+) and 1D zigzag chains of {[Ni(f-RR-L)(l-Phe)](+)}n /{[Ni(f-SS-L)(d-Phe)](+) n . The homochiral nature of Delta-1/Lambda-1, a-2/b-2, S-3/R-3, and S-4/R-4 are confirmed by the results of circular dichroism (CD) spectra measurements.

Hydrothermal reactions of imidazole-4,5-dicarboxylic acid (H3IDC), 4,4′-bipyridine (bpy), and Cd(NO3)2·4H2O under different conditions yielded four novel three-dimensional (3D) porous metal−organic frameworks (MOFs) of {[Cd5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O}n (1), [Cd5(HIDC)2(IDC)2(py)2]n (2), {[Cd5(IDC)3(bpy)2(H2O)2]·NO3·3.5H2O}n (3), and {[KCd4(IDC)2.5(bpy)2(H2O)2]·1.5NO3·3H2O}n (4). X-ray single-crystal structural analyses revealed that IDC3− and HIDC2− in 1–4 exhibit six different types of coordination modes, among them two modes are first reported in this presentation. In 1 and 4, the cadmium ions are interconnected by μ5-IDC3− in two different asymmetrical coordination modes to produce two different infinite two-dimensional (2D) layers, which are further pillared by μ2-bpy (in 1) or μ5-IDC3− and μ2-bpy alternately (in 4) to form 3D porous MOFs of 1 and 4, in which the two asymmetrical coordination modes of μ5-IDC3− have not been reported. In 2 and 3, the cadmium ions are interconnected by μ5-...

A ternary Cu(II) complex with dipyrido[3,2-a : 2′3′-c]phenazine(dppz) and L-tryptophanate (L-trp) has been synthesized and investigated by elemental analysis, molar conductivity, IR and X-ray diffraction. The complex crystallizes in the monoclimic space group P21 with two molecules in a unit cell of dimensions, a = 7.949(2) A, b = 10.724(3) A, c = 18.580(5) A, β = 93.697(5)°, V = 1580.7(8) A3, R 1 = 0.0310, and wR 2 = 0.0382. The central copper(II) ion has a distorted square-pyramidal geometry, in which the N,O-donor tryptophanate and N,N-donor heterocyclic base dppz are in the basal plane and a water molecule is coordinated at the axial site. DNA binding properties of the complex were studied by electronic absorption spectroscopy, fluorescence spectroscopy, and viscosity measurement. The DNA cleavage of the complex was investigated by agarose gel electrophoresis. The results show that the complex can bind DNA by intercalation and cleave pBR322 DNA in the presence of ascorbate.

Four new ternary complexes: [Cu(IP)(L-Val)(H2O)]ClO4·1.5H2O (1), [Cu(IP)(L-Leu)(H2O)]ClO4 (2), [Cu(IP)(L-Tyr)(H2O)]ClO4·H2O (3) and [Cu(IP)(L-Trp)(H2O)]ClO4·1.5H2O (4) have been synthesized and characterized by elemental analysis, molar conductivity, infrared absorption spectroscopy, electronic absorption spectroscopy and cyclic voltammetry, where IP=imidazo[4,5-f][1,10] phenanthroline, L-Val=L-valinate, L-Leu=L-leucinate, L-Tyr=L-tyrosinate and L-Trp=L-tryptophanate. Complex 3 was structurally characterized by X-ray diffraction method, which crystallizes in orthorhombic space group P21212 in a unit cell of dimensions a=3.0567(4) nm, b=0.74079(9) nm, c=1.06198(13) nm, V=2.4047(5) nm3, Z=4, μ=0.1084 cm−1. The SOD-like activities of catalytic dismutation of superoxide anions (O−2) by the complexes were determined by means of modified nitroblue tetrazolium (NBT) photoreduction. The IC50 values of complexes 1, 2, 3 and 4 are 0.072, 0.147, 0.429 and 0.264 µmol·L−1, respectively.

The asymmetric unit of the title compound, C18H15N63+·3Cl−·2.5H2O, contains two independent (1,3,5-triazine-2,4,6-triyl)tripyridinium cations. Both cations are approximately planar, the r.m.s. deviations of fitted non-H atoms being 0.045 and 0.051 Å. In the crystal, extensive O—H...Cl, O—H...O, N—H...Cl and N—H...O hydrogen bonds and weak C—H...Cl and C—H...O interactions link the organic cations, Cl−anions and water molecules into a three-dimensional supramolecular architecture. π–π stacking between the pyridine rings of adjacent cations is also observed, the centroid-to-centroid distance being 3.7578 (8) Å.

The preparation and crystal structures of five cyano-bridged Fe-Mn complexes, [(bipy)2Fe(II)(CN)2Mn(II)(bipy)2]2(ClO4)4 (1), [(bipy)2Fe(II)(CN)2Mn(II)(DMF)3(H2O)]2(ClO4)4 (2), {[(Tp)Fe(III)(CN)3]2Mn(II)(DMF)2(H2O)}2 (3), {[(Tp)Fe(III)(CN)3]2Mn(II)(DMF)2}n (4), and Na2[Mn(II)Fe(II)(CN)6] (5) (bipy = 2,2'-bipyridine, Tp = tris(pyrazolyl)hydroborate), are reported here. Compounds 1-4 contain the basic Fe2(CN)4Mn2 square building units, of which 1-3 show the motif of discrete molecular squares of Fe2(CN)4Mn2 and 4 possesses a 1D double-zigzag chain-like structure, while compound 5 is a 3D cubic framework analogous to that of Prussian blue. Compounds 1 and 2 show weak ferromagnetic interactions between two Mn(II) ions through the bent -NC-Fe(II)-CN- bridges. Compound 3 shows weak antiferromagnetic coupling between the Fe(III) and Mn(II) ions, while compound 4 displays a metamagnetic-like behavior with TN = 5.2 K and Hc = 10.5 kOe. Compound 5 exhibits a ferromagnetic ordering with Tc= 3.5 K, coercive field, Hc, = 330 G, and a remnant magnetization of 503 cm3 Oe mol(-1).