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Gelatin (GE), a nontoxic and degradable biomass resource, is a multistage hydrolysate of collagen. However, its application in adhesives was always limited by its brittleness and poor water resista...

Two mononuclear copper(II) compounds, [Cu(HL)2](ClO4)2 · (H2L)ClO4 · 3H2O (1) and [CuL2] (2), where L is the monoanionic form of N′-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL), have been ...

Mechanically robust protein-based hydrogels are strongly desired but their construction remains a significant challenge. In this work, gelatin, together with methacrylic acid, is used to construct a novel hydrogen-bonded hydrogel through a facile low-temperature polymerization and a subsequent dry-swell process. The obtained gel is extremely stiff and tough with a high Young's modulus and a fracture energy of 11 MPa and 8.5 kJ m-2, respectively, which are comparable to the performance of tough synthetic hydrogels, rubber, cartilage, and skin. These gels also show recovery and healing properties as well as biocompatibility and stability in physiological saline solutions. The gel is easy to prepare and exhibits a wide range of functional properties, making it a promising load-bearing material for medical applications.

Biopolymer-based functional hydrogels with excellent mechanical properties are desired, but their fabrication remains a challenge. Learning from the tofu-making process, we developed a freely formable hydrogel with high toughness and stiffness from the hydrogen bond-rich coacervation of tannic acid and gelatin through a simple hot-pressing process that transforms the coacervate particles into a bulk hydrogel. The mechanical properties of the obtained gelatin/tannic acid hydrogel (G/T gel) can be controlled by tuning the weight ratio of tannic acid to gelatin in the gel. The G/T gel with optimum mechanical properties possesses high Young's modulus, fracture strain, and fracture energy of ∼60 MPa, ∼10, and ∼24 kJ m-2, respectively. These properties arise from the phase-separated structure and high concentration of dynamic hydrogen bonds with widely distributed bond strengths. These dynamic hydrogen bonds also enable multifunctional properties of the gel, such as self-recovery, self-healing, rebuildability and shape memory. The combination of excellent mechanical properties, good biocompatibility, and useful functionalities into one hydrogel that comes from renewable sources demonstrates the great potential of G/T gels.

Flexible energy storage materials and sensors have become the key equipment of human-machine interface technology. For the preparation of these devices, hydrogel electrodes are relevant because of their unique porous structure, high capacitance, flexibility, small size, and lightweight. In this paper, regular polypyrrole (PPy) is synthesized on a heat-induced phase-separated gel (H-Gel/AS) by the template degradation method, and a gelatin-based PPy hydrogel with high strength, high strain rate, and high conductivity is prepared. Moreover, by adding multiwalled carbon nanotubes (MWCNTs) into a gelatin solution according to the H-Gel/AS method, the electrochemical performance of the resulting H-Gel/AS-MWCNTs-PPy electrode is greatly improved. When the H-Gel/AS-MWCNTs-PPy gel is immersed in an ammonium sulfate solution, wrinkles appear on the surface, resulting in further enhancement of the capacitance. On this basis, a flexible sensor and a solid-state supercapacitor are assembled, and their performance is tested. The sensor can detect tensile, bending, and twisting strains with high sensitivity. Meanwhile, as a flexible solid-state supercapacitor, the specific capacitance is 75 F g-1, and the capacitance retention rate after 5000 cycles is 98.1% under bending conditions. More importantly, the gelatin-based hydrogel shows great potential for application in wearable devices.

High ferrotitanium prepared directly by the thermite method has a disadvantageously high O content (≥ 10 wt%) because of the short slag-metal separation time. In this study, CaO and CaF2 are added to the melt to improve the basicity of the slag and melt separation under heat preservation is performed to strengthen slag-metal separation. The thermodynamics of the step-by-step reduction process of TiO2 in the Ti–Al–Fe–Si–O system whose composition is close to the alloy after melt separation were calculated. Samples of alloys and slags before and after melt separation were systematically analyzed. The result indicates that the reaction that TiO is reduced by Al to Ti is the limited step in the reduction process of TiO2. The O content of the alloys slightly decreases with temperature from 1873 to 2023 K, which agrees with the changes in the law of deoxidation limit. It is mainly attributed to the movement of chemical reactions in the alloy melt at different temperatures and slag-metal interfacial reaction. The addition of Al2O3–CaO–CaF2 slag and high temperature promote the removal of Al2O3 and titanium suboxides. The minimum contents of O and Al in the alloy reach 1.84 wt% and 3.26 wt%, respectively.

Two mononuclear zinc(II) and manganese(II) compounds, [ZnL 2 ] ( 1 ) and [MnL(HL)]ClO 4 ( 2 ), where L is the monoanionic form of N’ -(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL), and HL is the zwitterionic form of HL, have been prepared and characterized by elemental analyses, IR and UV-Vis spectroscopy, and single-crystal X-ray crystallographic determination. Compound 1 contains a neutral [ZnL 2 ] complex molecule. Compound 2 contains a [MnL(HL)] + complex cation and one perchlorate anion. The metal atoms in the complexes are in octahedral coordination. The hydrazone ligands coordinate to the metal atoms through the pyridine N, imine N, and enolate O atoms. The compounds were investigated for their antimicrobial activity against Staphylococcus aureus , Escherichia coli , and Candida albicans .

Ferrotitanium is used as a deoxidizer and alloying agent during steelmaking process, which has a high demand for sulfur control. Sulfur was introduced from raw materials in the process of producing ferrotitanium by thermite method, where CaO was used as fluxing agent. At the same time, CaO has a great desulfurization capability. Effects of CaO addition on the distribution of sulfur in high titanium ferroalloy prepared by thermite method were studied in this work. The equilibrium diagram of Ti–Al–Fe–S system was calculated by FactSage 6.4 software package with FactPS and FTmisc database. The alloy and slag samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma atomic emission spectrometer (ICP-AES), X-ray fluorescence (XRF) and high-frequency infrared ray carbon sulfur analyzer. The result indicates that the sulfur in the alloy firstly exists in the form of liquid FeS, thereafter TiS (s) and eventually Ti2S (s) during cooling. The sulfur is mainly distributed in the alloy, and only a small amount of sulfur remains in the slag. Moreover, it is noted that the sulfur in the alloy does not distribute homogeneously, and it exists in the form of solid solution phase, (Ti, Al, Fe)S. S content in the slag, the sulfur capacity of the slag and the sulfur distribution ratio (LS) all increase with the increment of CaO addition, while S content in alloys decreases.

A new mononuclear dioxomolybdenum(VI) complex, [MoO 2 L 1 ], and a new linear trinuclear nickel(II) complex, [Ni{NiL 2 (μ 1 -η 1 :η 0 -OAc)(μ 2 -η 1 :η 1 -OAc)} 2 ]·H 2 O, where L 1 is the dianionic form of N,N’ -bis(5-fluorosalicylidene)-1,3-propanediamine (H 2 L 1 ), L 2 is the dianionic form of N,N’ -bis(5-fluoro-2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine (H 2 L 2 ), have been synthesized and characterized by elemental analysis, FT-IR spectroscopy, and single-crystal X-ray determination. The Mo atom in the molybdenum complex is coordinated by four donor atoms of the Schiff base ligand, and two oxo groups, forming an octahedral coordination. In the nickel complex, there are three bridges across the Ni-Ni atom pairs, involving two phenolate O atoms of a Schiff base ligand, and an O–C–O moiety of a μ 2 -η 1 :η 1 -OAc group. The central Ni atom is located on an inversion center and has octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and two O atoms from two μ 2 -η 1 :η 1 -OAc ligands in the axial positions. The coordination around the terminal Ni atoms is also octahedral, with two imino N and two phenolate O atoms from a Schiff base ligand defining the equatorial plane, and with two O atoms respectively from a μ 1 -η 1 :η 0 -OAc and a μ 2 -η 1 :η 1 -OAc ligands occupying the axial positions. The molybdenum complex has excellent catalytic property for sulfoxidation reactions.

Developing a paper sizing agent to meet the requirements of low cost, high quality of the paper, and environmental sustainability is significant but remains a challenge. Herein, a novel degradable gelatin-based coating emulsion for paper surface sizing was developed by a simple one-step polymerization and blending process. Poly(methacrylic acid) (PMAA) was first introduced to a gelatin solution to form gelatin-PMAA emulsion (G-PMAA) through the formation of hydrogen bonds between PMAA and gelatin. The addition of PMAA endowed gelatin with the increased hydrophobicity and the decreased upper critical solution temperature. Then, a relatively small amount of the flexible poly(butyl acrylate) (PBA), which imparted the toughness of the formed film, was blended with the G-PMAA emulsion to form G-PMAA/PBA emulsion. The G-PMAA/PBA emulsion with a high gelatin content of 0.2 g/mL was in the sol state at room temperature, which facilitated the application of the G-PMAA/PBA emulsion. The corrugated papers sized by G-PMAA/PBA emulsion exhibited excellent mechanical properties and water resistance.

Hydrogels derived from lignin are typically weak and contain only a small amount of lignin, which limits their broad application prospects. In the present work, a novel lignin/poly(N,N-dimethylacry...

Introduction Dynamin 3 (DNM3) is a large GTPase that possesses mechanochemical properties and has been shown to be involved in malignancies. However, most studies about DNM3 are observational, and knowledge of the precise molecular mechanism of DNM3 remains limited. Materials and methods We constructed a PCDH-CMV-MCS-EF1a-GFP-Puro-DNM3 recombinant eukaryotic expression vector, which was then transfected into SW620 and LoVo cells. One cell line was divided into three groups. DNM3 mRNA and protein expression was analyzed by quantitative real-time PCR and Western blot assay. To investigate DNM3 biological activity in colon cancer SW620 and LoVo cell line, we performed cell proliferation, transwell migration, and invasion assay. Matrix metalloproteinase (MMP)-2 and MMP-9 protein expressions were detected by Western blot. Result We successfully constructed a PCDH-CMV-MCS-EF1a-GFP-Puro-DNM3 recombinant eukaryotic expression vector, and stable DNM3 expression was observed in SW620 and LoVo cell lines. The vector overexpressing DNM3 inhibited the proliferation, weak invasion, and migration ability of colon cancer SW620 and LoVo cells relative to those in the control group (all P

Microplastics from wasted traditional nondegradable plastic mulching films pose a great threat to both the ecological environment as well as human health. Currently, eco-friendly and cost-effective biodegradable films are considered the most promising substitutes for nondegradable plastic mulching films. In this study, we demonstrate a simple and eco-friendly strategy to utilize the gelatin extracted from scrap skin in leather processing and prepare novel biodegradable mulch films. The gelatin chains were covalently cross-linked with tetrakis(hydroxymethyl)phosphonium chloride to reduce the hygroscopicity of gelatin. Then, polyvinyl alcohol (PVOH) was introduced into the gelatin network. The hydrogen bonds between the gelatin and PVOH and several PVOH crystalline domains acted as sacrificial bonds for energy dissipation. Thus, the multi-cross-linked gelatin matrix (GP) films showed high fracture stress (12.03–31.99 MPa) and fracture strain (211.99%–379.73%). Such high mechanical performance is comparable to that of traditional low-density polyethylene mulch films and conforms to the GB/T 35,795 regulatory standards. In addition to their excellent mechanical properties, the mulch films exhibited good water resistance, excellent light transmittance, and good biodegradability in soil. All properties of the GP films are tunable, and their eco-friendliness, low cost, and excellent properties endow them with great application potential as eco-friendly mulch films for agriculture.

We present a novel methodology for preparing as-cast Ti-Al-V alloy directly from titanium-rich material through a thermite reduction. The new method is shown to be feasible through a thermodynamics and dynamics analysis. The as-cast Ti-Al-V alloys synthesized from titanium dioxide, rutile, and high-titanium slag were analyzed by an x-ray diffractometer, a scanning electron microscope, an inductively coupled plasma emission spectrometer, and an oxygen/nitrogen/hydrogen analyzer. The results indicate that the alloy is composed of a Ti-Al-V matrix and Al2O3 inclusions. The Al and V contents in the matrix are close to the mass ratio of Ti-6Al-4V (Al: 5.5–6.8 wt.%, V: 3.5–4.5 wt.%). The Si and Fe in the alloys synthesized from rutile and high-titanium slag can be used as alloying elements in low-cost titanium alloys. The present method is expected to be useful for preparing Ti-Al-V alloys at a low production cost.

A series of Zn(II) complexes with different conjugated systems, [ZnL1Cl2]2 (Zn1), [ZnL2Cl2] (Zn2), [Zn(L3)2]·(ClO4)2 (Zn3), [Zn2L4Cl4] (Zn4), and [ZnL5Cl2] (Zn5), were synthesized and subsequently characterized via single crystal X-ray diffraction, 1H and 13C NMR, FT-IR, elemental analyses, melting point, and PXRD. The X-ray diffraction analyses revealed that the supramolecular frameworks of complexes Zn1–Zn5 are constructed by C–H⋯O/Cl hydrogen bonds and π⋯π interactions. Complexes Zn1–Zn3 feature 3D 6-connected {412·63} topological structures, whereas complex Zn4 exhibits a 3D 7-connected supramolecular framework with a {417·64} topological structure. However, complex Zn5 shows one-dimensional “wave-like” chains. Based on these varied structures, the emission maximum wavelengths of complexes Zn1–Zn5 can be tuned in a wide range of 461–592 nm due to the red shift direction of λem caused by different conjugated systems and their electron donating abilities. Complex Zn3 shows a strong luminescence in the solid state and in the acetonitrile solution. Therefore, a series of Zn3-poly(methylmethacrylate) (Zn3-PMMA) hybrid materials were obtained by controlling the concentration of complex Zn3 in poly(methylmethacrylate) (PMMA). At an optimal concentration of 4%, the doped polymer film of Zn3-PMMA displays strong green luminescence emissions that are 19-fold in the luminescence intensities and 98 °C higher in the thermal stability temperature compared to the Zn3 film.

A series of lanthanide coordination polymers(LnCPs) containing both light and heavy rare-earth elements, namely {[Eu2(pydc)3(H2O)]·2H2O}n (1-Eu, H2pydc = pyridine-2,3-dicarboxylic acid), [Ln(pyc)2(Hpyc)(NO3)]n (Ln = Nd (2-Nd), Sm (3-Sm), Eu (4-Eu), Gd (5-Gd), Tb (6-Tb), Ho (7-Ho), and Er (8-Er), Hpyc = pyridine-3-carboxylic acid), has been synthesized under hydro(solvo)thermal conditions and fully characterized. The crystal structure analysis indicates that in situ decarboxylation of H2pydc occurred in the synthesis process of 2-Nd–8-Er. Coordination polymer 1-Eu displays a 3-D pcu network with central-symmetric quad-core structural units [Eu4(COO)6] linked by 1-D chains. 2-Nd–8-Er are of triple helical chain enantiomeric pair 61/65 axis, and can be further linked through two separate kinds of H⋯bonding interaction to form a mirror symmetrical 3-D framework; the final topological symbol of the jointly connected network is rare {47·68}. Solid-state luminescence studies show that the emission spectra of these LnCPs cover both the visible and near-infrared luminescence region. 2-Nd exhibits characteristic 4F3/2 → 4IJ/2 (J = 9, 11, 13) transition NIR emission. 1-Eu and 4-Eu provide characteristic 5D0 → 7FJ intense and bright red luminescence, while 4-Eu exhibits better luminescence performance because of the presence of the O–H oscillators within 1-Eu. 6-Tb exhibits characteristic 5D4 → 7FJ intense and bright green luminescence. Furthermore, through doping with PMMA polymer, the luminescence properties of 4-Eu and 6-Tb are all improved. The results show the best doping concentration is 4%. The thermal stabilities of 4-Eu-PMMA and 6-Tb-PMMA increased from 270 to 315 °C when compared with single coordination polymers 4-Eu and 6-Tb. The co-doping of 4-Eu, 5-Gd, and 6-Tb (0.92/0.04/0.04) with PMMA at a total concentration of 4% resulted in a tunable luminescence material W(4-Eu,5-Gd,6-Tb)-PMMA film. When excited at 285 nm, W(4-Eu,5-Gd,6-Tb)-PMMA shows white-light emission with the CIE chromaticity coordinates of (0.33, 0.35). The lifetime of Eu3+ ions in W(4-Eu,5-Gd,6-Tb)-PMMA increased from 1032.24 μs to 1272.26 μs when compared with 4-Eu-PMMA, and the efficiency of energy transfer (ηET) from Tb3+ to Eu3+ within the co-doping PMMA film could be estimated to be 29.9%.

Sensory neuron membrane proteins (SNMPs) play a critical role in the insect olfactory system but there is a deficit of functional studies beyond Drosophila. Here, we use a combination of available genome sequences, manual curation, genome and transcriptome data, phylogenetics, expression profiling and gene knockdown to investigate SNMP superfamily in various insect species with a focus on Lepidoptera. We curated 81 genes from 36 insect species and identified a novel lepidopteran SNMP gene family, SNMP3. Phylogenetic analysis shows that lepidopteran SNMP3, but not the previously annotated lepidopteran SNMP2, is the true homologue of the dipteran SNMP2. Digital expression, microarray and qPCR analyses show that the lepidopteran SNMP1 is specifically expressed in adult antennae. SNMP2 is widely expressed in multiple tissues while SNMP3 is specifically expressed in the larval midgut. Microarray analysis suggest SNMP3 may be involved in the silkworm immunity response to virus and bacterial infections. We functionally characterized SNMP1 in the silkworm using RNA interference (RNAi) and behavioral assays. Our results suggested that Bombyx mori SNMP1 is a functional orthologue of the Drosophila melanogaster SNMP1 and plays a critical role in pheromone detection. Split-ubiquitin yeast hybridization study shows that BmorSNMP1 has a protein-protein interaction with the pheromone receptor (BmorOR1), and the co-receptor (BmorOrco). Concluding, we propose a novel molecular model in which BmorOrco, BmorSNMP1 and BmorOR1 form a heteromer in the detection of the silkworm sex pheromone bombykol.

Five novel three-dimensional lanthanide metal–organic frameworks (Ln–MOFs) constructed by 4-(3′,5′-dicarboxylphenoxy) phthalic acid (H4dcppa), namely, {[Eu(Hdcppa)(H2O)2]·H2O}n (Eu-1), [Eu1.5(dcppa) (HCOO)0.5(H2O)2]n (Eu-2), {[Ln2K2(dcppa)2(H2O)6]·mH2O}n (Ln = Eu-3, Tb-4, Gd-5, m = 5 for Eu-3 and Tb-4; m = 4 for Gd-5) (HCOOH = formic acid) have been prepared by hydro(solvo)thermal method and fully characterized. Structural analyses indicated that H4dcppa ligand took four different coordination fashions in 1–5 and, thus, resulted in diversity of the targeted Ln–MOFs: Eu-1 displays the rare 3D (5,5)-connected vbk net, containing one-dimensional left- and right-handed helical chains; Eu-2 possesses a 3D (3,8)-connected tfz-d topology constructed by trinuclear paddlewheel [Eu3(CO2)6] SBUs; 3–5 are isostructural and show 3D (Ln-dcppa4–) + 2D (K-dcppa4–) → 3D (LnK-dcppa4–) structure. Eu-3, with regular 1D channels and open Lewis basic oxygen atoms on the pore surface was utilized for specific sensing and bindin...

Using five Schiff base ligands (E)-N-(pyridine-2-yl) (CH═NPhR) (where R = 4–CH3, L1; 2,6-(CH3)2, L2; 2,4,6-(CH3)3, L3; 2,6-(C2H5)2, L4; 2,6-(i-C3H7)2, L5), nine Zn(II)/Cd(II) complexes, namely, Zn1–Zn3, Cd1, Cd2, Cd3a, Cd3b, Cd4, and Cd5, have been successfully synthesized. The structures of the Zn(II)/Cd(II) complexes have been established by single crystal X-ray diffraction and further physically characterized by 1H NMR, FT–IR, and elemental analysis. The crystal structures of these complexes indicate that the structures of ligand and anions can directly influence the formation of 1D → 3D supramolecular metal–organic frameworks (SMOFs) via C–H···O/C–H···Cl hydrogen bonds and π···π interactions. Upon irradiation with UV light, the nine Zn(II)/Cd(II) complexes display deep blue emissions of 401–436 nm in acetonitrile solution and light blue or bluish green emissions of 485–575 nm in the solid state, respectively. The photoluminescence properties of nine Zn(II)/Cd(II) complexes can be finely and predictabl...

Two novel transition metal complexes formulated as [Cu(4,5–Himdc)(phen)]n (1) and [Mn(5,6–Hbidc)(H2O)]n (2) (4,5–H3imdc = imidazole–4,5–dicarboxylic acid, 5,6–H3bidc = 1H–benzimidazole–5,6–dicarboxylic acid, phen = 1,10–phenanthroline,) have been synthesized under hydro(solvo)thermal method at a relatively low temperature and characterized by elemental analysis, IR spectroscopy, and X–ray single–crystal diffraction. 1 based on 4,5–H3imdc displays one–dimensional zigzag chain structure. 2 based on 5,6–H3bidc features a two–dimensional framework with 4–connected topology. Thermal stabilities and luminescence properties of the two complexes were investigated.

Based on azabicyclo ligands, four 3D supramolecular lanthanide complexes have been synthesized through hydro(solvo)thermal reactions, generally formulated as [Dy(bipy) (NO3)3]2 (1·Dy), [Dy(bipy)2(NO3)3] (2·Dy), [Dy2(bpdc)3(DMF)(H2O)]2·(DMF)10(H2O) (3·Dy) and [Eu4(bpdc)6(CH3NH2)3(DMSO)(H2O)] (4·Eu) (Bipy = 2,2′-bipyridine; H2bpdc = 2,2′-bipyridine-5,5′-dicarboxylic acid, DMF = N,N-dimethylformamide), and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and powder X-ray diffraction (PXRD). There are three kinds of hydrogen bonding, C2–H2A⋯O6, C4–H4A⋯O4 and C8–H8A⋯O8 along the a/c, b, c axis, respectively in complex 1·Dy. They connect the 1·Dy complex into a 3D 6-connected pcu supramolecular network. 2·Dy is connected into a 3D network with 8–connected bcu architecture by two kinds of hydrogen bonding: C2–H2A⋯O1 and C9–H9A⋯O3. In order to connect the polymer to form a 3D complex, H2bpdc has been chosen in the synthesis and design of the crystal. In the network of 3·Dy, two kinds of Dy(III) cations in different coordination models construct the different binuclear [Dy2O14(DMF)2] and [Dy2O12(H2O)2], and further form the (4,4,6)-connected 3D architecture. The isostructural complex 4·Eu has been synthesised simultaneously. The property of luminescence in solid state or different solvents of the four complexes has been studied in detail. The four complexes show the unique emission peaks of lanthanide cations. Futhermore, in 3·Dy and 4·Eu, the ligand shows a rare bimodal emission, which can sensitize the emission of europium cations as an “antenna effect”, and the shorter one keeps its blue emission though coordinated with Dy(III) cations. Based on the synthesis of green or red color materials, multicolored photoluminescence tuning has been studied in detail through growth of a series of bimetallic complexes, the crystal formula as [Dy2nEu′2−2n(bpdc)3(DMF)(H2O)] (M-1–M-9; 0 < n < 1). We achieved dichromatic fine-tuning among the triangle region of red, green and white. The linear dependence of the emissions has been analyzed, and the mathematical matrix model is useful to calculate the ratio and excitation wavelength for a given color in need.

A series of different alkyl substituted of Zn(II) complexes, [ZnL1Cl2] (Zn1), [ZnL2Cl2] (Zn2), [ZnL3Cl2] (Zn3), [ZnL4Cl2] (Zn4), [ZnL5Cl2] (Zn5) ((E)-N-(pyridine-2-yl)(CMeNPhR), where R = H, L1; 2-CH3, L2; 2,6-(CH3)2, L3; 2,4,6-(CH3)3, L4; 2-OCH3, L5) have been synthesized and characterized by single crystal X-ray diffraction, 1H NMR, FT-IR, and EA. The X-ray diffraction analyses revealed that although are all constructed by C–H⋯Cl/π hydrogen bonds and π⋯π interactions, the dimensions of these supramolecular frameworks complexes Zn1–Zn5 are quite different. Complexes Zn1 and Zn5 feature 3D 5-connected {46·64} and {44·66} topology structures, respectively, while complexes Zn2 and Zn3 feature 2D supramolecular layer with {63} topology structures. Complex Zn4 exhibits two different one-dimensional helix-shaped chains. Obviously, these results show that steric hindrance has a great impact on the final structures of the supramolecular architectures. Based on these varied structures caused by different alkyl substitutions, the emission maximum wavelengths of complexes Zn1–Zn5 can be tuned in a large range of 400–514 nm. The λem shift in the red direction after the substitution of alkyl is attributed to the HOMO–LUMO energy gap of complexes being effectively decreased due to the electron-donating ability of alkyl. These results are confirmed by the density functional theory calculations.

By reacting an asymmetric semi-rigid V-shaped linker H3dpob (H3dpob = 3-(2′3′-dicarboxylphenoxy)benzoic acid) and Ln(NO3)3·6H2O, nine novel Ln-based luminescent materials, from 1D to 3D, namely {[Eu(dpob)(phen)]·H2O}n (1), {[Ln(Hdpob)(ox)0.5(H2O)2]}n (Ln = Eu(2), Sm(3), Gd(4), Tb(5)), {[Eu(dpob)(H2O)2]·0.5H2O}n (6), and {[Ln(dpob)(H2O)2]·mH2O}n (Ln = Eu(7), Gd(8), Tb(9), m = 0.5 for 7 and 9; m = 1 for 8) (phen = 1,10-phenanthroline; H2ox = oxalic acid) have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, infrared (IR) spectroscopy, elemental analysis, and PXRD. The crystal structures of 1–9 indicate that the coordination modes and coordination configuration of the H3dpob ligand play critical roles in the formation of the lanthanide architectures. Complexes 1–5 display multiple structures from double-stranded 1D chains to 4-connected 2D layers, through [Eu2(CO2)4] or [Eu2(CO2)2] dinuclear units with different auxiliary ligands. Complexes 6 and 7 are genuine supramolecular isomers which are induced by the concentration effect. 6 possesses a 2D kgd network with a Schlafli symbol of (43)2(46·66·83) built from 6-connected [Eu2(CO2)2] units and 3-connected H3dpob, which further connects to a (3,8)-connected tfz-d topology through O–H⋯O hydrogen bonds. 7 displays a 3D (3,6)-connected rtl network with the Schlafli symbol (4·62)2(42·610·83). Eu complexes 1, 2, 6, and 7 as well as Tb complexes 5 and 9 could provide intense and bright characteristic 5D0 → 7FJ/5D4 → 7FJ red/green luminescence under UV excitation in the solid state at 298 K and 77 K. The calculated singlet and triplet energies of H3dpob as well as phen and H2ox ligands indicate that these ligands act as antenna chromophores that are able to efficiently absorb and transfer energy to Ln(III) ions. In complexes 1, 2 and 5, ligand-to-metal energy transfer processes could occur in mixed ligands. However, these processes occurred in a single H3dpob ligand in complexes 6 and 7. With careful adjustment of the relative concentration of the lanthanide ions and by varying the excitation wavelengths of {[Gd0.92Eu0.04Tb0.04(dpob)(H2O)2]·0.5H2O}n (10), tunable yellow (CIE coordinate: 0.51, 0.40) to white-light (CIE coordinate: 0.33, 0.34) emission has been obtained.

Carbamazepine (CBZ) is a typical pharmaceutical residue commonly found in aqueous environments, but its removal through activated carbon or advanced oxidation processes is often disrupted by co-existing organic matter. An imprinting system which consisted of the target pollutant CBZ (template molecule) and 10 different kinds of functional monomers was constructed via molecular simulation to screen for appropriate monomers, thereby addressing CBZ removal disruptions. An annealing method simulation was used to search for stable, low-energy conformations of the template-monomer interaction system to calculate the binding energy of these different monomers with CBZ. The order of binding affinity calculated was: 4-vinylbenzoic acid > itaconic acid > methacrylic acid, which was consistent with the experimental observations. The adsorption capacity of the molecular imprinted polymer (MIP) prepared using 4-vinylbenzoic acid reached 28.40 mg/g, and the imprinting factor reached 2.72. The simulation and measurement of the ultraviolet spectrum of the imprinting system showed that a new interaction system was formed between the template and monomers, and that multiple binding conformations between them took place when specific recognition occurred. Energy calculation and hydrogen bond analysis revealed that the van der Waals force, including the π-π conjugate and electrostatic forces including hydrogen bonding, played an important role during selective adsorption, which was confirmed by infrared spectroscopy analysis.

Platelets (PLTs) are classically used in the clinical setting to maintain hemostasis. Recent evidence supports important roles for PLTs in host inflammatory and immune responses, and PLT-rich plasma has been demonstrated to inhibit the growth of bacteria in vitro and in vivo; however, few studies have examined whether PLTs can inhibit bacterial growth directly, and related mechanisms have not been elucidated further. Accordingly, in this study, we evaluated the effects of PLTs on bacterial growth. We washed and purified PLTs from peripheral blood, then confirmed that PLTs significantly inhibited the growth of Staphylococcus aureus when cocultured in vitro. Moreover, PLTs damaged DNA and blocked cell division in S. aureus. During coculture, PLT-derived TGF-β1 was dramatically down-regulated compared with that in PLT culture alone, and the addition of TGF-β1 to the coculture system promoted the inhibition of PLTs on S. aureus. Analysis of a murine S. aureus infection model demonstrated that the depletion of PLTs exacerbated the severity of infection, whereas the transfusion of PLTs alleviated this infection. Our observations demonstrate that PLTs could directly inhibit the growth of S. aureus by damaging DNA and blockage cell division, and that PLT-derived TGF-β1 may play an important role in this machinery.-Xu, J., Yi, J., Zhang, H., Feng, F., Gu, S., Weng, L., Zhang, J., Chen, Y., An, N., Liu, Z., An, Q., Yin, W., Hu, X. Platelets directly regulate DNA damage and division of Staphylococcus aureus.

The pathogenesis of atherosclerosis is multifactorial. The proliferation and migration of vascular smooth muscle cells (VSMCs) are significant in the genesis and development of atherosclerosis plaques, and the degradation of VSMCs plays a crucial role in the process. Mimecan is a member of the Keratan sulfate family of proteoglycans, which are leucine-rich proteoglycans. It has been demonstrated that mimecan is associated with arteriogenesis and atherosclerosis. In the present study, the effect of mimecan on the characteristics of cultured human aortic smooth muscle cells (HASMCs) was investigated. In vitro, human mimecan was stably overexpressed in HASMCs using a lentiviral system. It was observed that the proliferation rate of HASMCs transduced with mimecan was lower compared with that of control cells; overexpression of mimecan induced HASMC apoptosis. To determine the effect of mimecan on HASMC migration, a Transwell cell culture chamber and sterile cloning cylinder assays were used, and it was noted that mimecan enhanced the migration of HASMCs horizontally and vertically. These data indicated that mimecan may be involved in the pathogenesis of atherosclerosis by regulating the proliferation, apoptosis and migration of VSMCs.

Six novel luminescent materials In(III)-2,3-H2qldc/phen metal–organic assemblies (MOAs), namely, [In2(phen)3Cl6]·CH3CN (In1), [In2(phen)3Cl6]·CH3CN·2H2O (In2), [In2(phen)2Cl6] (In3), [In(3-qlc)2(phen)Cl] (In4), [In(3-qlc)2(2,2′-bipy)Cl]·2H2O (In5) and [In(3-qlc)3(phen)]·H2O (In6) (2,3-H2qldc = quinoline-2,3-dicarboxylic acid; 3-Hqlc = quinoline-3-carboxylic acid, which is formed from the decarboxylation reaction of 2,3-H2qldc; phen = 1,10-phenanthrolin; 2,2′-bipy = 2,2′-bipyridine) have been hydro(solvo)thermally synthesized and characterized by single-crystal X-ray diffraction, infrared (IR), elemental analysis, 1H NMR spectra, and thermogravimetric analysis (TGA). The crystal structures of In1–In6 indicate that the hydrogen bonding and π···π stacking interactions play critical roles in the formation of the extended supramolecular array. In1 displays the rare hexatomic ring 3D (4,5)-connected supramolecular architecture through twofold interpenetrating of 2D cell membrane-like structures. In2 exhibits a ...

A series of lanthanide complexes with formulae {[KEu(Hqlc)(qlc)(H2O)6(OH)]2+·2Cl−}n (1·Eu), {[Eu(qlc)2(phen)(H2O)2]+·Cl−}·CH3CN (2·Eu), [Eu(qlc)2(phen)(NO3)]·H2O (3·Eu), [Ln(qlc)2(H2O)4]·(qlc)·(H2O) (Ln = Eu(4·Eu), Sm(5·Sm), Gd(6·Gd), Tb(7·Tb), Dy(8·Dy), Ho(9·Ho)) (Hqlc = quinoline-3-carboxylic acid, phen = 1,10-phenanthrolin) are synthesized under solvo(hydro)thermal conditions and characterized by single-crystal X-ray diffraction, infrared spectra, elemental analysis, and powder X-ray diffraction. Complex 1 exhibits two-dimensional (6,3)-connected hcb networks and possesses a stable structure through typical O/C–H⋯Cl intermolecular hydrogen bonds. Complexes 2–4 display three diverse dimer structures, due to the synergistic effect from coordination modes of Hqlc ligand and anion effect. Complexes 5–9 are isostructural with complex 4. Eu-complexes 1–4 could provide intense and bright characteristic 5D0 → 7FJ red luminescence under UV excitation in the solid state at 298 K and 77 K. In complexes 2 and 3, the coordinate phen ligand could play the antenna role in the energy transfer process. Therefore, the luminescence lifetimes of complexes 2 (779.62 and 792.65 μs) and 3 (947.21 and 1095.59 μs) are longer than those of complexes 1 (456.93 and 499.33 μs) and 4 (283.70 and 46 469 μs) in the solid state at 298 K and 77 K. Complexes 5, 7 and 8 exhibit characteristic Sm3+, Tb3+ and Dy3+ ion luminescence. Furthermore, through controlling the concentration of complexes 3 and 4 in poly(methyl methacrylate) (PMMA), a series of 3–PMMA and 4–PMMA hybrid materials are obtained, respectively. They all display strong and characteristic red luminescence emissions at a concentration of 8%. Compared with 3 and 4, the luminescence intensities and luminescence lifetimes of 3–PMMA and 4–PMMA are increased, due to the replacement of water molecules by PMMA.

Three one-dimensional (1D) Ag(I)/Cu(I) coordination polymers, formulated as [Ag(2,3-Hqldc)]n (Ag1), [Ag(3-qlc)]2n (Ag2) and [CuI(3-Hqlc)]n (Cu1) based on the ligand quinoline-2,3-dicarboxylic acid (H2qldc), were synthesized through hydrothermal (solvothermal) method and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Molecular structural analysis reveals that Ag1 was a 1D + 1D → 1D infinite chain synthesized at a relatively low temperature 80 °C, which further forms a three-dimensional (3D) structure by π–π stacking interactions. Ag2 forms a 1D dimer chain structure and via π⋯π packing interactions shows a two-dimensional (2D) supramolecular network. Both Ag1 and Ag2 display stable blue luminescent in the solid state and in organic solvents (DMSO, CH3CN and CH3OH) at 298 K and 77 K. However, Cu1 possess a 1D ladder chain structure, which further forms a 2D structure by hydrogen bonding interactions. Cu1 shows tunable luminescence at 298 K and 77 K in the solid state with a large red-shift of 70 nm and the CIE color shifts from bright yellow (0.51, 0.48) to red (0.67, 0.30), indicating thermochromic luminescence for Cu1. After doping with poly(methylmethacrylate) (PMMA), not only are the luminescence intensity and lifetimes enhanced, but the thermal stability is also increased in comparison with Cu1. After Cu1 was doped with PMMA (Cu1@PMMA), the lifetime of the polymer film material Cu1@PMMA increases and reaches a maximum at 1.0% (τ = 95.57 μs), which is more than eight times longer than that of Cu1 (τ = 13.78 μs). Cu1@PMMA is confirmed as a bright yellow luminescent polymer film material.

Nine IIB group complexes, [ZnL1Cl2] (Zn1), [CdL1Cl2]2 (Cd1), [HgL1Cl2] (Hg1), [ZnL2Cl2] (Zn2), [CdL2Cl2] (Cd2), [HgL2Cl2] (Hg2), [ZnL3Cl2] (Zn3), [CdL3Cl2] (Cd3) and [HgL3Cl2] (Hg3), have been synthesized from the corresponding ortho-(6-methoxy-pyridyl)(CH[double bond, length as m-dash]NAr) (where Ar = 2,6-iPr2C6H3, L1; 4-MeC6H4, L2; 2-OMeC6H4, L3) Schiff base and structurally characterized by elemental analysis, FT-IR, (1)H NMR and X-ray single-crystal analysis. Crystallographic studies reveal that the center metal of the complexes adopts a distorted tetrahedron geometry (except for Cd1 and Cd3, which display square pyramidal geometry) and C-HCl hydrogen bonds and ππ stacking interactions contribute to three-dimensional supramolecular structures. The series of complexes exhibit tunable luminescence from blue, through green, to light yellow by varying the temperature (298 K and 77 K), both in solution and in the solid state. Moreover, the quantum yields range from 0.027 to 0.422, and decrease according to the order of the periodic table (ZnCdHg). These results indicate that the center atom of the complexes leads to the geometry differences and hence to the tunable luminescence properties. Because Zn1-Zn3 exhibited higher molar extinction coefficients and a distinct absorption region, they were employed as co-sensitizers in ruthenium dye N719-sensitized photoanodes to deliver light-electricity efficiency enhancement, being assembled with counter-electrodes and electrolyte to prepare ZnX/N719 (where ZnX = Zn1, Zn2, and Zn3) co-sensitized dye sensitized solar cell (DSSC) devices. The prepared co-absorbent could overcome the deficiency of N719 absorption in the low-wavelength region of the visible spectrum, and offset competitive visible-light absorption of I3(-). Application of these prepared complexes in N719-sensitized solar cells enhanced their performance by 10-36%, which indicated a potential application of these types of complexes in DSSCs.

Based on a new design of 4-cyanobenzyl-based 1,2,4-triazole ligand 4-(1,2,4-triazolylmethyl) cyanobenzene (TMCB), a series of cadmium complexes 1–5′ from a mononuclear to three-dimensional (3D) structure have been synthesized through hydro(solvo)thermal reactions; they were generally formulated as [Cd(TMCBA)2]n (1), [Cd(TMCB)(1,4-bda)(H2O)]n (2), {[Cd2(TMCB)4(1,4-bda)2(H2O)2]n·3H2O}n (3), {[Cd(TMCB)4(H2O)2]·(NO3)2·(H2O)2}n (4), [Cd1.5(1,4-bda)1.5(DMF)2]2n (5) and [Cd1.5(1,4-bda)1.5(DMF)2]2n (5′) (TMCBA = 4-(1,2,4-triazolylmethyl) benzoic acid, which is formed from the hydrolysis of TMCB; 1,4-H2bda = 1,4-benzenedicarboxylic acid; the difference between two genuine supramolecular isomers of 5 and 5′ is the use of TMCB as the additive agent for the reaction). Complexes 1–5′ exhibit tunable luminescence with emission maxima containing deep blue, blue, light blue, green and deep green region at 298 K or 77 K in both different solvents (polarity: DMSO > CH3OH > CHCl3) and solid state. Interestingly, the good thermal stability accompanied by their compensated adsorption to ruthenium complex N719 in the region of low wavelength, enabled 1 and 4 to serve as co-sensitizers in combination with N719 in dye sensitized solar cells (DSSCs). After co-sensitization with N719, the overall conversion efficiency of 1 and 4 were found to be 7.68% and 6.85%, which are 40.40% and 25.23% higher than that for DSSCs only sensitized by N719 (5.47%) under the same conditions, respectively. The improvement in efficiency is attributed to the fact that complexes 1 and 4 overcome the deficiency of N719 absorption in the low wavelength region of ultraviolet and blue-violet, offset competitive visible light absorption of I3− and reduce charge recombination due to the formation of an effective cover layer of the dye molecules on the TiO2 surface. As a result, the synthesized complexes are promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.

In the present study, exopolysaccharides (EPS) production and pellet morphology of Pycnoporus sanguineus was investigated in a 5-L stirred-tank (STR) and a 5-L airlift reactors (AR). Maximum EPS production (2.92 g/L) was obtained after 4 days of cultivation in STR, whereas, EPS concentration was maximal (2.14 g/L) after 2 days in AR. The morphological form of the fungal pellets in AR was more hairy than those in the STR. Furthermore, monosaccharide composition analysis indicated that purified EPS from STR was mainly composed of mannose and glucose, while purified EPS from AR mainly composed of glucose. Then, FT-IR spectral analysis of the purified EPS revealed prominent characteristic groups. Dye-inclusion studies with Congo red indicated that each EPS existed in a random coil conformational state. Furthermore, thermo gravimetric analysis (TGA) indicated the degradation temperature (Td) of the EPS from STR (152 °C) was higher than that of EPS from AR (116 °C). In addition, the antioxidant activities of the polysaccharides from different bioreactors were investigated. EPS from STR exhibited the higher antioxidant ability than EPS from AR, which might be attributed to the molecular weight, monosaccharide composition and the configuration of glycosidic bond in the EPS groups.

Ubiquitin-fold modifier 1 (Ufm1) is a new member of the ubiquitin-like protein family, and its biological function remains largely unknown, particularly in macrophages. In this study, we demonstrate that Ufm1 expression is increased in diabetic mouse resident peritoneal macrophages (RPMs) and in the mouse macrophage cell line, Raw264.7, subjected to endoplasmic reticulum (ER) stress. Following treatment of the cells with the ER stress inducers, thapsigargin (TG) or tunicamycin (TM), the lentiviral short hairpin RNA (shRNA)-mediated knockdown of Ufm1 increased the apoptosis of Raw264.7 cells. Furthermore, these cells had higher expression levels of immunoglobulin heavy chain-binding protein (BiP) and C/EBP homologous protein (CHOP), which are markers of the ER stress response. The overexpression of Ufm1 induced by lentiviral infection in the Raw264.7 cells treated with the ER stress inducers, TG or TM, resulted in the opposite effect. Taken together, our results suggest that Ufm1 is upregulated in diabetic mouse RPMs and in Raw264.7 cells in response to ER stress and that Ufm1 protects macrophages against apoptosis. Thus, Ufm1 may be a novel gene that protects against ER stress-induced apoptosis in macrophages.

Two new lanthanide coordination polymers formulated as [Ln(BDC)1.5(DMF)(H2O)]n [Ln = Tb (1), Gd (2)] [H2BDC = 1,4-benzenedicarboxylic acid, DMF = N,N′-dimethylformamide] were synthesized under solvothermal conditions. The coordination polymers were characterized by IR spectroscopy, elemental analysis and X-ray single-crystal diffraction. The two coordination polymers are isostructural and exhibit twofold interpenetrating pcu three-dimensional open frameworks constructed by tetradentate ligand of H2BDC. The fluorescence properties of 1 and 2 were investigated at 298 or 77 K both in solid state and in CH2Cl2 solvent dispersed as suspensions. Coordination polymer 1 exhibits characteristic Tb3+ ions emission transitions of 5D4 → 7FJ (J = 6–2) at 77 or 298 K both in the solid-state and in CH2Cl2 solvent. Moreover, the vibrational structure of 1 is more defined at 77 K, which exhibits another two 5D4 → 7F1 and 5D4 → 7F2 transitions more than that at 298 K. The lifetimes of 1 are longer at 77 K (915.2 μs in the solid state and 874.11 μs in the CH2Cl2 solvent) than that at 298 K (866.31 μs in the solid state and 801.04 μs in the CH2Cl2 solvent), which may be caused by the increase of radiative rate and decrease of non-radiative rate at low temperature. The singlet excited state (28,653 cm−1) and the lowest triplet energy level (23,641 cm−1) of H2BDC ligand were calculated based on the UV–Vis absorbance edges of ligand and the phosphorescence spectrum of Gd3+ coordination polymer (2) at 77 K, showing that the effective extent of energy transfer from H2BDC ligand to Tb3+ ion. Finally, thermal behaviors of the two coordination polymers were studied by thermogravimetric analysis, which exhibit thermal stability to 250 °C.

Ethnopharmacological relevance Osteoking is a Traditional Chinese Medicine consisting of seven types of medicinal herbs originated from Yi nationality and has been used in clinic to treat bone diseases for thousands of years in China. Osteoking shows excellent clinical therapeutic effects on osteoporosis, but it is not clear whether Osteoking could exhibit beneficial effects against osteoporosis via reducing reactive oxygen species (ROS). Aim of the study: To explore whether the protective effects of Osteoking on osteoporosis related to ROS, we investigated the effects of Osteoking on osteogenesis differentiation under oxidative stress. Materials and methods The ovariectomized (OVX) osteoporosis model was established by ovarian surgery, and Osteoking was orally administrated for 84 days. Then the pathogenesis changes of femur were analyzed by Hematoxylin and eosin (H&E) and Masson's trichrome staining. The levels of ROS, malondialdehyde (MDA) and superoxide dismutase (SOD ) from rats' serum were further measured. In vitro, mouse pre-osteoblastic MC3T3-E1 cells pre-treated with or without 0.25 mM tert-butyl hydroperoxide (t-BHP) for 2 h were cultured and treated with different dilutions of Osteoking or 20 μM N-Acetyl-L-cysteine for another 24 h, respectively. The intracellular ROS production and markers of oxidative damage of the MC3T3-E1 cells were determined using corresponding kits, respectively. The expressions of alkaline phosphatase (ALP), collagen type I, osteoprotegerin (OPG), TGF-β1, β-catenin, receptor activator of nuclear factor-κB ligand (RANKL) and interleukin-6 (IL-6) were further analyzed by qRT-PCR and western blotting upon treatment. Results Our results showed that Osteoking significantly improving trabecular microstructure by promoting collagen fiber repair and new bone or cartilage regeneration was demonstrated in OVX osteoporosis rat models by micro-CT analysis and histological staining results. Osteoking supplementation reduced the levels of ROS and MDA in OVX rat serum and increased SOD activities. In addition, Osteoking could also up-regulate the proteins expression levels of Runx2, osteocalcin (BGP) and osteoprotegerin (OPG) but reducing the expression of tartrate-resistant acid phosphatase (TRAP). In vitro, Osteoking could effectively inhibit the t-BHP-induced intracellular excessive ROS production and protect cells from oxidative stress in mouse pre-osteoblastic MC3T3-E1 cells. Meanwhile, the mRNA expressions of ALP, collagen type I, OPG, TGF-β1 and β-catenin were also up-regulated whereas the RANKL and IL-6 were down-regulated in Osteoking-treated MC3T3-E1 cells. Conclusions A novel therapeutic mechanism of Osteoking on osteoporosis reveals by present investigation. Clinic effects of Osteoking to treat osteoporosis are closely related to its ability to reduce oxidative stress.

Two new two–dimensional (2D) dysprosium coordination polymers [Dy(2,4′-bpdc)(DMF)2(NO3)]n (1) and {[Dy(2,4′–bpdc)(1,4-BDC)0.5(DMF)(H2O)] 1.5H2O}n (2) (2,4′-H2bpdc=2,4′–biphenyldicarboxylic acid, 1,4-H2BDC=1,4–benzenedicarboxylic acid, DMF=N,N′-dimethylformamide) were synthesized under solvothermal condition and stucturally characterized by means of single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. Single-crystal X-ray analysis revealed that the two coordination polymers possess two types of 2D layered structures. From the viewpoint of network topology, the structures of 1 and 2 can be simplified as (4,4) network. We discuss the effect of solvents and temperature on luminescence properties. The fluorescence spectra of 1 at room temperature and 77 K in the solid-state are almost the same, except the stronger emission intensities derived from ligand–centered at 77 K. It is because the quenching by O3H oscillators was protected at low temperature. Coordination polymer 2 displays characteristic Dy3+ ion yellow–green luminescence under 290 nm excitation in DMSO (dimethyl sulfoxide), CH3CN, and CH3OH solvents. The fluorescence intensities of 2 increased in the order of DMSO>CH3CN>CH3OH. We also studied the fluorescence lifetimes of 1 and 2, and the results revealed that the lifetime in DMSO solvent at room temperature reached to 9.53 μs. Compared with the dysprosium coordination polymers, coordination polymer 2 presents a longer lifetime. Additionally, we calculate the triplet state T1 datum from the emission spectrum of the Gd3+ coordination polymer and discuss the energy transfer mechanisms. The energy transfer process from the lowest triplet state energy level of 2,4′-H2bpdc ligand to the 4F9/2 state energy level of Dy3+ ion is inefficient for both 1 and 2. The energy transfer process is effective after we introducing the chelating ligand 1,4-H2BDC to the construct of coordination polymer 2, which is ascribe to 1,4-H2BDC may participate in the process of energy transfer.

Jin-Hua Zhang,1,2,* Zhao-Shui Shangguan,3,* Chao Chen,4 Hui-Jie Zhang,4 Yi Lin1 1College of Chemical Engineering, Huaqiao University, 2Department of Pharmacy, Xiamen Medical College, 3Central Laboratory, The First Affiliated Hospital of Xiamen University, 4Xiamen Diabetes Institute, The First Affiliated Hospital of Xiamen University, Xiamen, People’s Republic of China *These authors contributed equally tothis work Abstract: The present study was aimed to investigate the effects of guggulsterone (GS) on proinflammatory responses as well as the underlying molecular mechanisms in macrophage upon lipopolysaccharide (LPS) stimulation. Effects of GS on viability of Raw264.7 cells were examined using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. Real-time polymerase chain reaction (PCR) was employed to examine the mRNA expression of cytokines, including interleukin 1β (IL-1β), tumor necrosis factor-alpha (TNF-α), and inducible nitric oxide synthase (iNOS). Phosphorylations of extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK), p38 mitogen-activated protein kinases (p38), and inhibitor of nuclear factor kappaB (IκB) were determined using immunoblotting. The results revealed that GS was not toxic to Raw264.7 cells at designated concentrations. We demonstrated that GS significantly suppressed the elevated mRNA expression of proinflammatory cytokines, including IL-1β, TNF-α, and iNOS in a dose-dependent manner. GS treatment reduced the level of IκB phosphorylation in LPS-stimulated macrophages in a dose-dependent manner. Use of BAY 11-7082, an inhibitor of nuclear factor-kappaB (NF-κB), led to significantly suppressing effects on IL-1β and TNF-α expression similar as that of GS-treated cells. Our findings suggest that GS possesses anti-inflammatory activity, which may be attributed to downregulation of iNOS and inhibition of NF-κB activity in LPS-stimulated Raw264.7 cells. Keywords: Anti-inflammatory effects, guggulsterone, lipopolysaccharides, NF-κB, IL-1β, TNF-&alpha

From 1-D to 3-D zinc coordination polymers based on multifunctional flexible 4-(1,2,4-triazole-methylene)-benzonitrile (tzbt), {[Zn(tzbt)2(bdc)]·2H2O}n (1), [Zn(tzbc)2]n (2), and [Zn(bpdc)(H2O)]n (3) (bdc = 1,4-benzenedicarboxylic acid, tzbc = 4-(1,2,4-triazole-methylene)-benzoic acid, bpdc = 4,4′-biphenyldicarboxylic acid), were synthesized under hydrothermal conditions. The tzbt was synthesized by N-alkylation and hydrolyzed in situ to produce tzbc (in 2). Single-crystal X-ray diffraction analysis reveals that 1 displays 1-D wave-like chains based on [Zn(bdc)]n. 2 is a chiral twofold interpenetrating 2-D architecture constructed with “V”-shaped tzbc. 3 is a 3-D chiral compound constructed from achiral H2bpdc with right-handed helical chains. 1–3 display stable blue-emitting luminescence with emission maxima ranging from 383 to 410 nm, depending on ligand-centered π*→π transitions. The effects of different polarity solvents and temperature on luminescence are discussed. TGA and VT-XPRD reveal that 2 has thermal stability to 360 °C.

Three novel two–dimensional (2–D) coordination polymers {[Ln (bpdc) (BDC)0.5 (DMF) (H2O)]·1.5H2O}n [Ln = Tb (1), Sm (2), Gd (3); H2bpdc = 2,4′–biphenyldicarboxylic acid; H2BDC = 1,4–benzenedicarboxylic acid, and DMF = N,N′–dimethylformamide] have been successfully synthesized by the reactions of metal source Ln(NO3)2·5H2O with mixed aromatic carboxylate ligands named, H2bpdc and H2BDC in the mixed solution of DMF and H2O. Complexes 1–3 were characterized by element analyses, IR spectroscopy and single–crystal X–ray diffraction. The results reveal that three complexes are isostructural. In the molecular structure of 1, the neighboring Tb3+ cations are connected by the edge sharing fashion from two three-bridging μ3–oxygen atoms to construct a dinuclear polyhedron. The adjacent dinuclear units are linked by two bpdc2– ligands to form an infinite double zigzag chain containing quadrangular grids. These chains are linked by BDC2–, which acted as pillar to form a 2-D layered structure containing (4, 4) networks. The solid–state luminescent properties of complexes 1 and 2 were investigated at room temperature. Complexes 1 and 2 have displayed their characteristic emissions and decay lifetimes.

Using Schiff-base ligands (E)-N-(6-methoxypyridin-2-yl)(CH═NAr) (where Ar = C6H5, L1; 2-MeC6H4, L2; 2,4,6-Me3C6H2, L3), six Zn(II)/Hg(II) complexes, namely, [ZnL1Cl2] (Zn1), [HgL1Cl2] (Hg1), [ZnL2Cl2] (Zn2), [HgL2Cl2] (Hg2), [ZnL3Cl2] (Zn3), and [HgL3Cl2] (Hg3) have been synthesized under solvothermal conditions. The structures of six complexes have been established by X-ray single-crystal analysis and further physically characterized by EA, FT-IR, (1)H NMR, and ESI-MS. The crystal structures of these complexes indicate that noncovalent interactions, such as hydrogen bonds, C-H···Cl, and π···π stacking, play essential roles in constructing the resulting supramolecular structures (1D for Hg3; 2D for Zn2, Hg2; 3D for Zn1, Hg1, and Zn3). Upon irradiation with UV light, the emission of complexes Zn1-Zn3 and Hg1-Hg3 could be finely tuned from green (480-540 nm) in the solid state to blue (402-425 nm) in acetonitrile solution. It showed that the ligand and metal cation can influence the structures and luminescence properties of complexes such as emission intensities and maximum wavelengths. Since these ligands and complexes could compensate for the absorption of N719 in the low-wavelength region of the visible spectrum and reduce charge recombination of the injected electron, the ligands L1-L3 and complexes Zn3/Hg3 were employed to prepare cosensitized dye-sensitized solar cells devices for investigating the influences of the electron-donating group and coordination on the DSSCs performance. Compared to DSSCs only being sensitized by N719, these prepared ligands and complexes chosen to cosensitize N719 in solar cell do enhanced its performance by 11-41%. In particular, a DSSC using L3 as cosensitizer displays better photovoltaic performance with a short circuit current density of 18.18 mA cm(-2), corresponding to a conversion efficiency of 7.25%. It is much higher than that for DSSCs only sensitized by N719 (5.14%).

Poly(methylmethacrylate) (PMMA) doped with Tb-based imidazole derivative coordination polymer {[Tb(3)(L)(μ(3)-OH)(7)]·H(2)O}(n) (1) (L = N,N'-bis(acetoxy)biimidazole) was synthesized and its photophysical properties were studied. The L'(L' = N,N'-bis(ethylacetate)biimidazole) ligand was synthesized by an N-alkylation reaction process followed by ester hydrolysis to produce ligand L. Polymer 1 and ligand L' have been characterized by (1)H NMR and IR spectroscopy, elemental analysis, PXRD and X-ray single-crystal diffraction. Coordination polymer 1 is the first observation of a CdCl(2) structure constructed with hydroxy groups and decorated by ligand L in lanthanide N-heterocyclic coordination polymers. In the 2D layered structure of 1, each Tb3 metal center is connected with three Tb1 and three Tb2 metal centers by seven hydroxyl groups in different directions, resulting in a six-membered ring. After doping, not only the luminescence intensity and lifetime enhanced, but also their thermal stability was increased in comparison with 1. When 1 was doped into poly(methylmethacrylate) (1@PMMA), polymer film materials were formed with the PMMA polymer matrix (w/w = 2.5%-12.5%) acting as a co-sensitizer for Tb(3+) ions. The luminescence intensity of the Tb(3+) emission at 544 nm increases when the content of Tb(3+) was 10%. The lifetime of 1@PMMA (914.88 μs) is more than four times longer than that of 1 (196.24 μs). All τ values for the doped polymer systems are higher than coordination polymer 1, indicating that radiative processes are operative in all the doped polymer films. This is because PMMA coupling with the O-H oscillators from {[Tb(3)(L)(μ(3)-OH)(7)]·H(2)O}(n) can suppress multiphonon relaxation. According to the variable-temperature luminescence (VT-luminescence) investigation, 1@PMMA was confirmed to be a stable green luminescent polymer film material.

Two rare 2D Ga/In-based coordination polymers in which one metal center coexists with three distinct aromatic ligands were synthesized. Helical channels along the 21 screw axis are exhibited to form a hcb net. The compounds exhibit tunable fluorescence from blue, green, white to yellow light by varying the temperature and solvents.

We compared food choice and the initial response to deterrent treated diet between fifth instars of Helicoverpa armigera, a polyphagous generalist pest, and Bombyx mori, an oligophagous specialist beneficial. Bombyx mori was more behaviorally sensitive to salicin than to caffeine. The relative sensitivities were reversed for H. armigera, which was tolerant to the highest levels of salicin found in natural sources but sensitive to caffeine. A single gustatory receptor neuron (GRN) in the medial styloconic sensillum of B. mori was highly sensitive to salicin and caffeine. The styloconic sensilla of H. armigera did not respond consistently to either of the bitter compounds. Phagostimulants also were tested. Myo-inositol and sucrose were detected specifically by two GRNs located in B. mori lateral styloconic sensillum, whereas, in H. armigera, sucrose was sensed by a GRN in the lateral sensillum, and myo-inositol by a GRN in the medial sensillum. Myo-inositol responsiveness in both species occurred at or below 10−3 mM, which is far below the naturally occurring concentration of 1 mM in plants. Larval responses to specific plant secondary compounds appear to have complex determinants that may include host range, metabolic capacity, and gustatory repertoire. Electronic supplementary material The online version of this article (doi:10.1007/s10886-013-0303-2) contains supplementary material, which is available to authorized users.