Preparation of silver nanoparticles through the reduction of straw-extracted lignin and its antibacterial hydrogel

Silver nanoparticles(Ag NPs)have attracted attention in the field of biomaterials due to their excellent antibacterial property.However,the reducing and stabilizing agents used for the chemical reduction of Ag NPs are usually toxic and may cause water pollution.In this work,Ag NPs(31.2 nm in diameter)were prepared using the extract of straw,an agricultural waste,as the reducing and stabilizing agent.Experimental analysis revealed that the straw extract contained lignin,the structure of which possesses phenolic hydroxyl and methoxy groups that facilitate the reduction of silver salts into Ag NPs.The surfaces of Ag NPs were negatively charged due to the encapsulation of a thin layer of lignin molecules that prevented their aggregation.After the prepared Ag NPs were added to the precursor solution of acrylamide,free radical polymerization was triggered without the need for extra heating or light irradiation,resulting in the rapid formation of an Ag NP-polyacrylamide composite hydrogel.The inhibition zone test proved that the composite hydrogel possessed excellent antibacterial ability due to the presence of Ag NPs.The prepared hydrogel may have potential applications in the fabrication of biomedical materials,such as antibacterial dressings.

Copper complexes of anthrahydrazone bearing pyridyl side chain:Synthesis,crystal structure,anticancer activity,and DNA binding

To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.

Synthesis,structure,and magnetic property of a cobalt(Ⅱ)complex based on pyridyl⁃substituted imino nitroxide radical

A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,elemental analysis,IR,and magnetic properties.X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB-ligands.The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ)and im4-py radical.The magnetic property is explained by the magnetic and structure exchange mechanism.CCDC:976028.

Quantile-based optimization under uncertainties for complex engineering structures using an active learning basis-adaptive PC-Kriging model

The Reliability-Based Design Optimization(RBDO)of complex engineering structures considering uncertainties has problems of being high-dimensional,highly nonlinear,and timeconsuming,which requires a significant amount of sampling simulation computation.In this paper,a basis-adaptive Polynomial Chaos(PC)-Kriging surrogate model is proposed,in order to relieve the computational burden and enhance the predictive accuracy of a metamodel.The active learning basis-adaptive PC-Kriging model is combined with a quantile-based RBDO framework.Finally,five engineering cases have been implemented,including a benchmark RBDO problem,three high-dimensional explicit problems,and a high-dimensional implicit problem.Compared with Support Vector Regression(SVR),Kriging,and polynomial chaos expansion models,results show that the proposed basis-adaptive PC-Kriging model is more accurate and efficient for RBDO problems of complex engineering structures.

Geochemistry and petrogenesis of Mesoproterozoic mafic granulite and amphibolite dykes from Saltora, Bankura district, Chhotanagpur Gneissic Complex, eastern India: Implications for their emplacement in within-plate setting

Distinguishing high-grade mafic-ultramafic rocks originally crystallized from within-plate basaltic magmatism is challenging and crucial because the chemical composition of the igneous rocks has been modified during high-grade metamorphism,causing misidentification of the characters of the parental magma.Proterozoic metamorphosed mafic dykes occur throughout the Chhotanagpur Gneissic Complex(CGC)of eastern Indian shield.The E-W trending mafic dykes from the Saltora area in the southeastern CGC underwent metamorphism in two episodes:M1(650 MPa;770℃)and M2(300 MPa;744℃).The metamafics are enriched in LILE,depleted in HFSE,and display strong fractionation of LREE,nearly flat HREE patterns in a chondrite-normalized REE diagram,and show tholeiitic differentiation trend.Their geochemical affinity is towards rift-related,continental within-plate basalts.About 7%–10%melting of the carbonated spinel-peridotite sub-continental lithospheric mantle(SCLM)produced the parental mafic magma.The pre-existing SCLM was metasomatized by slab-derived fluid during the previous subduction.The upwelling of the asthenosphere in a post-collisional tectonic setting caused E-W trending fractures,lithospheric thinning,and gravitational collapse.These dykes were emplaced during crustal extension around 1070 Ma.The remarkable geochemical similarity between the mafic dykes of Saltora and Dhanbad,the ca.1096 Ma Mahoba(Bundelkhand craton),and the ca.1070 Ma Alcurra mafic dykes in Australia supports a genetic link.

Analysis of electrochemical impedance and XRD spectroscopy for complex self-assembled film on silver

Self-assembled monolayers （SAMs） of （3-mercaptopropy） trimethoxysilane （3-MtrF） chemisorbed on silver surfaces were chemically ＂modified by 1-octadecanethiol to form self-assembled mixed-monolayers （SAMM） and the co-polymer of N-vinylcarbazole and methyl methacrylate ester （to form complex selfassembled film （CSAF））. The oxidation resistance of these barriers on silver surfaces and some influential factors concerned processes were analyzed by electrochemical impedance spectroscopy （EIS） in a 10% NaOH aqueous solution at oxidation potential. X-ray diffraction （XRD） spectroscopy shows that the oxidation occurring on the silver surface may be restrained effectively due to the coating barrier, and CSAF（Ⅱ） is the best one. Studies also reveal that oxide processes of bare silver and a series of modified silver electrodes in a 10% NaOH aqueous solution are of more than two relaxation time constants.

Synthesis and Structural Study of a N-Heterocyclic Carbene Trinuclear Silver(Ⅰ)Complex

The bis-benzimidazolium salt bis[2-（N-ethylbenzimidazoliumyl）ethyl]amine hexafluorophosphate（LH2·（PF6）2） and its N-heterocyclic carbene silver（Ⅰ） complex[L2Ag3]（PF6）3（1）have been prepared and characterized.In complex 1,a trinuclear silver（Ⅰ） architecture is formed by two tridentate ligands and three silver（I） atoms,in which one 12- and two 7-membered rings are contained.In the crystal packing of 1,1D chain and 2D supramolecular layer are formed via intermolecular weak interactions,including π…π interactions and C-H…π contacts.Additionally,the fluorescence emission spectra of LH2-（PF6）2 and 1 are described.

Luminescence intensification of lanthanide complexes by silver nanoparticles incorporated in sol-gel matrix

We present how the luminescence of europium RR-2-P-oxides complexes can be increased by interaction of electronic levels of the complex with the radiation field of silver nanoparticles （NPs）. The procedure by which silver NPs are formed in a sol-gel polyurethane matrix precursor was elaborated. The formed Ag NPs were combined with Eu complex incorporated in ormocer matrix. The emission spectra of the complexes without silver NPs were compared with spectra of the same complexes with addition of silver NPs. As the result of the interaction of the electronic levels of lanthaaide ligands with silver plasmons, dramatic increase of luminescence was observed.

Syntheses and Crystal Structures of Silver(I) Complexes by Depolymerizing [Ag(C≡CPh)]_n with a NP_3 Ligand

Two silver(I) complexes were prepared by the reaction of [Ag(C≡CPh)]n with NP3 [NP3 = N(CH2CH2PPh2)3] or with NP3 and [Cu(CH3CN)4]ClO4. Complex 1 [(Ag2Cl(NP3)2)(Ag5- (C≡CPh)6)] contains both NP3 and PhC≡C- ligands. The complex cation is (Ag2Cl(NP3)2)+, in which two Ag(NP3)+ cations were bridged by a Cl- donor. The anion is (Ag5(C≡CPh)6)-, where five Ag+ ions are linked by six C≡CPh- to form a pentanuclear cluster. Complex 2 only contains NP3 ligand, where the silver center adopts a trigonal-bipyramidal geometry. Crystal data for 1: C133H116Ag7Cl3- N2P6, Mr = 2789.54, triclinic, space group P1, a = 13.0780(2), b = 15.3678(2), c = 31.2041(3) ?, α = 91.3928(7), β = 90.9328(8), γ = 96.0244(4)o, V = 6233.8(1) ?3, T = 293(2) K, Z = 2, Dc = 1.486 g/cm3, F(000) = 2796, μ = 1.266 mm-1, the final R = 0.0746 and wR = 0.1953 for 16475 observed reflections with I > 2σ(I). Crystal data for 2: C42H42AgClNO4P3, Mr = 861.00, trigonal, space group R3, a = 17.451(1), b = 17.451(1), c = 11.3985(7) ?, V = 3006.0(3) ?3, T = 293(2) K, Z = 3, Dc = 1.427 g/cm3, F(000) = 1326, μ = 0.731 mm-1, the final R = 0.0251 and wR = 0.0663 for 1499 observed reflections with I > 2σ(I).

Dinuclear Silver(Ⅰ) Complex Based on 1-Picolyl-3-propylbenzimidazolium Salt: Crystal Structure and Weak Interactions

1-Picolyl-3-propylbenzimidazolium bromide （LBr） was prepared from benzimida- zole by alkylation with 2-chloromethyl-pyridine in the presence of NaH, followed by quaternization with 1-bromopropane. Ligand LBr was treated with AgBr in CH2Cl2 to afford a dinuclear silver（I） complex L2Ag2Br4 （1）. In complex 1, a 2-D supramolecular layer is formed through two types of π-π stacking interactions. Fluorescent emission spectra of ligand LBr and complex 1 are described.

Hydrothermal Synthesis and X-ray Characterization of Silver(I) Complex:Diacetylthiocarbamide Silver(I) Nitrate, [Ag(CH_3CONHC(S)NH_2)_2](NO_3)

The title compound [Ag(CH3CONHC(S)NH2)2](NO3) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. It crystallizes in mo-noclinic, space group P21/c with Mr = 406.20 (C6H12Ag N5O5S2), a = 12.0680(6), b = 6.8056(5), c = 18.0173(1) ? b = 111.383(4), V = 1377.9(2) 3, Z = 4, Dc = 1.958 g/cm3 , F(000) = 808, = 1.789 mm-1, R = 0.0361 and wR = 0.1015. Of 4185 reflections ((2)max = 55.00?, 3147 were unique (Rint = 0.0174) and 2820 with I > 2(I) were used to solve the structure. The silver(I) atom adopts V-shape geometry with the AgS bond distance of 2.4271(7) and 2.7229(9) , respectively. Seven atoms of one acetylthiocarbamide ligand are coplanar, while only four atoms of another acetylthio-carbamide ligand are fairly planar. The [Ag(CH3CONHC(S)NH2)2]+ cation and nitrate anion NO3- are connected by hydrogen bonds to form a three dimensional hydrogen bonding network..

Syntheses and Crystal Structures of Two Silver(Ⅰ) Complexes with Organic Carboxylic Acid and Bidentate N-donor Ligands

The title complexes（NH4）[Ag（dpe）（H2bptc）]（1） and Ag2（bpy）（ox）·7H2O（2） were synthesized via slow evaporation at room temperature,and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in triclinic,space group P1 with a = 8.3959（7）,b = 11.8088（12）,c = 12.8175（13） ,α = 85.507（2）,β = 79.245（1）,γ = 84.174（2）o,V = 1239.7（2） 3,Z = 2,C28H22AgN3O8,Mr = 636.36,Dc = 1.705 g/cm3,F（000） = 644 and μ（MoKα） = 0.874 mm-1.The final R = 0.0479 and wR = 0.1426 for 3632 observed reflections with I 〉2σ（I） and R = 0.0559 and wR = 0.1503 for all data.The crystal of 2 crystallizes in orthorhombic,space group Pnna with a = 17.2291（17）,b = 7.5289（6）,c = 21.369（2）,V = 2771.9（4） 3,Z = 4,C22H30Ag2N4O11,Mr = 742.24,Dc = 1.779 g/cm3,F（000） = 1488 and μ（MoKα） = 1.476 mm-1.The final R = 0.0648 and wR = 0.2058 for 1996 observed reflections with I 〉2σ（I） and R = 0.0769 and wR = 0.2192 for all data.X-ray diffraction reveals that in complexes 1 and 2,both 1,2-di（4-pyridyl）ethylene and 4,4＇-bipyridine act as typical bidentate N-donor ligands to link two Ag centers.3,3＇4,4＇-Biphenyltetracarboxylate and oxalate anions play the role of organic linkers and counter-ions to balance the cationic charge of AgI.The rich hydrogen-bonding interactions and ligand-unsupported Ag…Ag interactions as well as π-π stacking interactions contribute to the construction of three-dimensional sandwich-like frameworks.

A Silver Complex of 6,7-Dicyanodipyridoquinoxaline:π-Stacking Interactions and Luminescence

The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.

Synthesis, DNA-binding, and Photocleavage of 2,3-Di-2-pyridylquinoxaline-silver(Ⅰ) Complex

A new dinuclear complex, [Ag（L）（CH3CN）]2（ClO4）2·2H2O（L=2,3-di-2-pyridylquinoxaline）, was prepared and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. The interaction of the complex with calf thymus DNA（CT-DNA） was investigated by absorption, fluorescence spectroscopies, and viscosity measurement. The results suggested that the complex was bound to DNA via an intercalative mode. The intrinsic binding constant value Kb was found to be approximately 1.48×10^3 L·mol^-1. Moreover, the Ag（I） complex could cleave the plasmid pUC19 DNA from the supercoiled Form Ⅰto the nicked FormⅡ under irradiation at 365 nm.

NON-POLLUTION PROCESS FOR COMPLEX REFRACTORY SILVER-GOLD ORES

ＮＯＮ－ＰＯＬＬＵＴＩＯＮＰＲＯＣＥＳＳＦＯＲＣＯＭＰＬＥＸＲＥＦＲＡＣＴＯＲＹＳＩＬＶＥＲ－ＧＯＬＤＯＲＥＳＸｕＳｈｅｎｇｍｉｎｇ；ＺｈａｎｇＣｈｕａｎｆｕ；ＬｉＺｕｏｇａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＮｏｎｆｅｒｒｏｕｓＭｅｔａｌｌｕｒｇｙ，Ｃｅ...

Structure and Luminescent Property of a Tetrahedral Silver(Ⅰ) Cluster Complex Based on Phosphor and Sulphur Mixed-ligand System

A tetrahedral silver(I) cluster complex {Ag4[HC(PPh2)3](S2PPh2)3}ClO4(1,HC(PPh2)3 = 1,1,1-tris(triphenylphosphino)methane, S2PPh2 = diphenyldithiophosphinate) was synthesized by assembling silver ion with phosphor and sulphur mixed-ligand system. The complex was characterized by single-crystal X-ray crystallography, high-resolution mass spectroscopy and thermal analysis. In the crystal structure, an inverted tetrahedron was constructed from Ag4 metal skeleton. The Ag4 cage was stabilized by three diphenyldithiophosphinate ligands and one 1,1,1-tris(triphenylphosphino)methane ligand. 1 exhibits luminescent properties in solid state. A bright yellow-green emission centered at 533 nm has been observed in solid state. Large Stokes' shifts with long range of emissive lifetime indicate that the emission likely originates from a triplet state parentage.

DNA-binding Studies of Two Silver(I)-sulfonate Complexes Constructed by In Situ Reaction

Two silver（I）-sulfonate complexes,[Ag（NO3）（4,4＇-bipy）][Ag（HL）（4,4＇-bipy）]·2H2O（1） and[Ag（H2O）（4,4＇-bipy）][AgL（4,4＇-bipy）]·2H2O（2）,have been synthesized by in situ reaction（H2L = 2-formylbenzenesulfonic acid,4,4-bipy = 4,4-bipyridine）.1 displays two parallel 1D chains expending to a 3D supramolecule by n—n interactions and O-H…O hydrogen bonds,in which the[Ag（NO3）]or[Ag（HL）]units are joined by bridging 4,4＇-bipy molecules,respectively.The interactions between the complexes and DNA were studied by means of fluorescence spectra and surface-enhanced Raman scattering（SERS） spectra.The special configuration and intercalation effects between 1 and DNA are stronger than that between 2 and DNA.

Synthesis,Crystal Structure and Luminescence of a Novel One-dimensional Silver(Ⅰ)Sulfonate Complex with Pyrazine Ligand

The title complex,[Ag 2 （L1） 2 （Pyr）·2.5H 2 O] 1 （L1=6-amino-1-naphthalenesulfonate anion,Pyr=pyrazine）,has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in triclinic,space group P1,with a=7.339（5）,b=13.105（5）,c=14.097（5）,α=84.377（5）,β=76.921（5）,γ=79.628（5）°,V=1296.7（11） 3,C 48 H 50 Ag 4 N 8 O 17 S 4,M r=1570.68,Z=1,D c=2.011 g/cm 3,μ=1.732 mm-1,F（000）=782,S=1.148,the final R=0.0436 and wR=0.1181 for 4130 observer reflections （I 2σ（Ⅰ））.Compound 1 shows a rare one-dimensional （1D） double chain,and the chains are further connected through secondary bonding,hydrogen bonds,and π-π interactions to generate a three-dimensional （3D） supramolecular structure.The luminescent property of 1 was also studied in the solid state at room temperture.

Synthesis, Structural Characterization and DFT Studies of Silver(I) Complex Salt of Bis(4,5-dihydro-1<i>H</i>-benzo[g]indazole)

A new silver complex salt [Ag(N2C11H10)2]NO3 (where N2C11H10 = 4,5-dihydro-1H-benzo[g]indazole), has been synthesized and characterized by elemental and thermal analyses, IR and 1HNMR spectroscopies, single crystal X-ray structure determination and DFT studies. Its molecular structure comprises of a silver center coordinated to two nitrogen atoms from two 4,5-dihydro-1H-benzo[g]indazole molecule giving rise to a cationic complex entity, [Ag(N2C11H10)2]+ with as counter ion. The bulk structure is consolidated by N–H…O, C–H…π, Ag…π and Ag…O intermolecular interactions, thus generating a pseudo-helical network. The optimized structure, frontier molecular orbitals (HOMO and LUMO) and global reactivity descriptors were investigated by performing DFT calculations.

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Disilver Complex with Pyrazinyl Oxime Ligand

A novel binuclear Ag（I） complex [Ag2（C6H6NaO）2（C6H7N3O）2]·2CH3CN （1） was synthesized by the evaporation reaction of silver nitrate and （E）-1-（pyrazin-2-yl）ethanone oxime （HL）. The complex was characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction analysis. It crystallizes in the monoclinic space group C2/c with a = 22.7089（3）, b = 11.5443（7）, c = 16.1468（4）/A, β = 127.7150（10）°, V= 3348.6（2） A^3, Dc = 1.675 g/cm^3, Mr = 844.42, Z = 4, F（000） = 1696.0,μ = 1.226 mm^-1, the final R =0.0250 and wR = 0.070. The coordination around the silver（I） atom is a distorted trigonal-bipyramidal geometry involving one protonated pyrazinyl oxime ligand （HL）, one deprotonated oxime ligand （L^-） and one CH3CN solvate molecule in the asymmetric unit of complex 1.