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Two metal complexes [Pd(L)Cl] (1) and [Sb(L)Cl2] (2), where HL = 2-benzoylpyridine N4-phenylthiosemicarbazone, have been synthesized. Complex 1 was characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy, and single-crystal X-ray diffraction studies. Complex 1 contains mononuclear neutral molecules composed of one N2S tridentate anionic thiosemicarbazone ligand and one ancillary chloride ion with a four-coordinated palladium ion. Both the two complexes exhibited enhanced cytotoxicity compared to the thiosemicarbazone and complex 2 could distinguish hepatocellular carcinoma HepG2 cells from normal hepatocyte QSG7701 cells.

A diorganotin(IV) complex formulated as [(Me)2Sn(L)] (1) (H2L = 2,6-diacetylpyridine bis(N4-cyclohexylthiosemicarbazone) has been synthesized and structurally characterized by elemental analysis, IR, UV, and NMR spectroscopy, and single-crystal X-ray diffraction. Complex 1 contains mononuclear neutral molecules composed of one N3S2 pentadentate anionic thiosemicarbazone ligand and one (Me)2Sn(IV) group with a seven-coordinated tin ion. In vitro biological studies have indicated that complex 1 exhibited enhanced cytotoxicity compared to the thiosemicarbazone alone against human hepatocellular carcinoma HepG2 cells and could slightly distinguish HepG2 cells from normal hepatocyte QSG7701 cells.

In this article, a new compound H2[{Cu(HL)(H2O)}2(P2Mo5O23)]·5H2O (1) (HL = 2-acetylpyrazine thiosemicarbazone) has been synthesized and structurally characterized by single-crystal X-ray diffraction of and other detection techniques. Interestingly, the structure of 1 is different from many reported copper-based complexes, in which the [P2Mo5O23]6−, two Cu2+ ions and two HL were directly connected by covalent bands. Biological studies demonstrated that 1 indicated moderate antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), and a better cytotoxicity against human hepatic cancer line (SMMC-7721) than Mitoxantrone (Mito), the current clinical anticancer drug. Besides, the antibacterial mechanisms of 1 have been studied by the membrane integrity disruption, the destructive reactive oxygen species generation (ROS), the glutathione (GSH) depletion and the depressed enzymatic activity of respiratory chain dehydrogenases (RCD). These results revealed that the combination of HL, Cu2+, [P2Mo5O23]6− shows a higher antibacterial and cytotoxic activity.

The phenomenon of trapping oil is an inevitable result to ensure oil absorption cavity and oil exhaust cavity are not collude with each other. It directly affects the working performance and service life of the gear pump. This article through analyzing the root cause of it put forward a new way to using an external oil circuit to eliminate it. Adding such an external oil circuit to the gear pump, can make the dead volume linked to oil exhaust cavity when the dead volume is decreasing and make the dead volume linked to oil absorption cavity when the dead volume is increasing. This way eliminates the trapped oil compression and expansion, so as to achieve the purpose of thoroughly eliminate the phenomenon of trapping oil.

Thiophene-2-carbaldehyde N(4)-cyclohexylthiosemicarbazone C12H17N3S2 (HL) and diorganotin(IV) complex [Ph2Sn(L)Cl] (1) have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex 1 contains mononuclear neutral molecule composed of one five-coordinated diorganotin(IV) ion, one NS bidentate anionic thiosemicarbazone ligand, one chloridion, and two phenyl group, respectively. In vitro biological studies have indicated that coupling of HL with Ph2Sn(IV) leads to an enhancement of the cytotoxicity of the free ligand. Importantly, complex 1 could distinguish the human liver hepatocellular carcinoma HepG-2 cells from normal hepatocyte QSG7701 cells.

Cip1-interacting zinc-finger protein1 (Ciz1) is a nuclear matrix protein associated DNA replication factor which has been implicated in breast and lung cancer progression. However, the clinical significance of Ciz1 expression in colon cancer has not been determined. This study aimed to examine Ciz1 expression pattern and its potential as a biomarker of prognosis in colon cancer. Using quantitative PCR, tissue microarray (TMA), and ELISA, we evaluated Ciz1 mRNA and protein levels in tumor tissues from patients with colon cancer and in paired adjacent normal tissues. Ciz1 mRNA expression was significantly upregulated in 22 of 39 paired samples ( P

A new diorganotin(IV) complex formulated as [(Me)2Sn(L) (CH3COO)] (1), where HL = 2-acetylpyridine N(4)-phenylthiose micarbazone, has been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction studies. Schiff base in its deprotonated form coordinates to tin(IV) via pyridine nitrogen atom and the nitrogen atom and sulfur atoms of the thiosemicarbazone moiety. The tin(IV) ion is seven-coordinated and adopts a distorted pentagonal bipyramidal geometry. Biological studies, carried out in vitro against the K562 leukemia cells, have shown that the coupling of HL to Me2Sn(IV) leads to an enhancement of the cytotoxicity of the free ligand.

Two inorganic-organic hybrid materials, [Co(L)2]2Na2[β-Mo8O26]·9H2O (1) and [Fe(L)2]2Na2[β-Mo8O26]·9H2O (2) (HL = 2-acetylpyrazine N4-methyl thiosemicarbazone) have been synthesized and characterized by elemental analyses, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The hybrids 1 and 2 were explored in the oximation of aldehydes and ketones with in situ generated hydroxylamine by a one-pot procedure. In the crystal structures of 1 and 2, N-containing thiosemicarbazide ligands, Lewis acid, and oxidation catalyst octamolybdate coexist within a confined space providing a promising synergistic catalytic way. Hybrids 1 and 2 displayed high catalytic activity and selectivity for the oximation of aldehydes and ketones.

In this work, two magnetic adsorbents Fe3O4@1 and Fe3O4@2 were prepared by combining Fe3O4 nanoparticles and polyoxometalate hybrids [Ni(HL)2]2H2[P2Mo5O23]&middot, 4H2O (1), [H2L]5H[P2Mo5O23]&middot, 12H2O (2) (HL = 2-acetylpyridine-thiosemicarbazone). The temperature-dependent zero-field-cooled (ZFC) and field-cooled (FC) measurements indicated the blocking temperature at 160 K and 180 K, respectively. The Brunauer&ndash, Emmett&ndash, Teller (BET) surface area of Fe3O4@1 and Fe3O4@2 is 8.106 m2/g and 1.787 m2/g, respectively. Cationic dye methylene blue (MB) and anionic dye methyl orange (MO) were investigated for selective dye adsorption on Fe3O4@1 and Fe3O4@2. The two adsorbents were beneficial for selective adsorption of cationic dyes. The adsorption efficiency of MB was 94.8% for Fe3O4@1, 97.67% for Fe3O4@2. Furthermore, the two adsorbents almost maintained the same adsorption efficiency after seven runs. The maximum MB adsorption capacity of Fe3O4@1 and Fe3O4@2 is 72.07 and 73.25 mg/g, respectively. The fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra of the adsorbents collected after adsorption of MB are very similar to the initial as-synthesized Fe3O4@polyoxometalates indicating the high stability of the two adsorbents. The adsorption kinetics indicated that the MB removal followed the pseudo-second-order model. These results showed that the two adsorbents had a potential application in treating wastewater.

Nowadays, the development of anticancer drugs has attracted increasingly attention. Here, a Strandberg-type phosphomolybdate hybrid [Zn(HL)2(H2O)2]2H2[P2Mo5O23] 2H2O (1) (HL = 2-acetylpyrazine-thiosemicarbazone) and its nanocomposite Fe3O4@1 were synthesized and structurally characterized. The synthesized Fe3O4@1 was more cytotoxic with an IC50 value of 18.20 ± 2.80 μg ml−1 against the hepatocellular carcinoma SMMC-7721 cells than that of Fe3O4 (IC50 > 100 μg ml−1) and 1 (IC50 = 28.13 ± 4.76 μg ml−1). A synergistic effect involving Fe3O4 nanoparticles and 1 could probably explain the improved growth-inhibiting properties. Vibrating sample magnetometry (VSM) indicated that the Fe3O4@1 showed magnetic behavior.

An organic-inorganic hybrid based on the α-Keggin anion [BW12O40]5-, [Cu(BIIM)2] {[Cu(BIIM)2(H2O)][Cu(BIIM)2BW12O40]·3H2O}2 (BIIM=2,2´biimidazole) (1) was hydrothermally prepared and characterized by elemental analysis, IR and UV spectra. Compound 1 is composed of [Cu(BIIM)2]2+ and [Cu(BIIM)2(H2O)]2+ cations and a [Cu(BIIM)2BW12O40]3- polyanion, in which the [BW12O40]5- anion is decorated by one [Cu(BIIM)2]2+ cation through one terminal oxygen atom. These components are finally arranged through hydrogen bonds into a twodimensional network. Investigations of the intermolecular interactions by Hirshfeld surface and fingerprint plots indicate that besides the classical N-H···O hydrogen bonds, there are rare W- O(terminal)···π(imidazole ring) interactions stabilizing the structure.

[Zn(L)2] (1) and [(Ph)2Sn(L)(CH3COO)] (2), where HL = 2-benzoylpyridine N(4)-cyclohexylthiosemicarbazone, have been synthesized and characterized. The complexes show different coordination depending on their coordinating preferences. Biological studies carried out in vitro against human leukemia K562 cells show that the diorgantin(IV) complex, 2, has significant cytotoxicity with IC50 = 3.3 ± 0.5 μM.

2-Benzoylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its binuclear copper(II) complex [Cu2(L)2(CH3COO)](ClO4) (1) have been synthesized and structurally characterized. Biological studies, carried out in vitro against human leukemia K562 cells have indicated that 1 indicates significant cytotoxicity with IC50 = 0.37 ± 0.028 μM comparable to cisplatin. Complex 1 promotes a dose-dependent apoptosis in HepG2 cells and the apoptosis is associated with an increase in intracellular reactive oxygen species (ROS) production and reduction of mitochondrial membrane potential (MMP).

This paper proposed a location algorithm based on nodes distance difference, it gets the distance difference from the blind node to every beacon node by wireless communication module Rf grouping, then, makes use of the improved Trilateral positioning method to work out Node coordinates, so as to realize the node localization of long-distance range, precision controlled, low-cost, and to analyze the positioning performance. The simulation experiments shows this algorithm has high feasibility and positioning performance, and it is also a complement of WSN Positioning technology.

We investigate the molecular structure, vibrational and electronic absorption spectra, and electronic hyperpolarizabilities of trans and cis isomers of 4-hydroxyazobenzene (HOAB) via density functional theory. Results show that the azo dye exhibits a high third-order nonlinear optical response and good optical transparency. Both the basis set and the functional are important influences on the results obtained when calculating the absorption spectrum and NLO response. We also study the effect of the solvent on the electronic absorption spectrum to assess the ability of the functional to reproduce the experimental spectrum in combination with a suitable solvent model. Our calculations show that the SMD model of Truhlar et al. handles the electrostatic and the non-electrostatic effects of hydrogen-bonding solvents on the absorption spectrum better than the traditional polarizable continuum model does. In addition, our results indicate that the dye trans-HOAB exhibits a high second hyperpolarizability and excellent optical transparency. Also, although the second hyperpolarizability of cis-HOAB is much lower than that of trans-HOAB, it is non-negligible when calculating the optical nonlinearity of HOAB under an optical pump. We also examine the effect of frequency dispersion on second harmonic generation. This study provides the basis for further research on the spectroscopic and nonlinear optical properties of novel azo dyes and other π-conjugated compounds.

This study reviews some published literatures to seek the relationship between the parameters of indoor environments and the energy consumption. The indoor thermal environments are categorized and defined as different indices and variables. The building energy can be determined by indoor air temperature, occupant-area ratio and working days. Several parameters of indoor thermal environments such as air velocity, neutral temperature, predicted mean vote, indoor air quality, and set point temperature, are summarized for their influence on the energy consumption. It can be concluded that the increased local air velocity, enhanced neutral temperature, and enlarged set point temperature may be beneficial to reduce the energy consumption.

Transition metal complexes formulated as [Co(L)2]ClO4 (I) and [Ni(L)2] · H2O (II), where HL = pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone, have been synthesized. Complex I was characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. In complex I, the ligand is N2S tridentate, coordinating to the metal center through pyridine nitrogen, imine nitrogen and sulfur atoms. Hydrogen bonds link the different components to stabilize the crystal structure. Preliminary in vitro screening indicated that the free ligand was active against various bacteria and fungi and all the tested compounds showed significant antitumor activity against K562 leukaemia cell line, and can therefore be candidates for further stages of screening in vitro and/or in vivo.

Main group metal complex [Bi(HL)(NO3)3] (1), where HL = 2-acetylpyrazine N(4)-pyridylthiosemicarbazone, has been synthesized and characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. The interesting monomeric 8-coordinate bismuth(III) complex 1 is depicted with one electron pair (6 s2) of the bismuth(III) atom, one N2S tridentate neutral thiosemicarbazone, two monodentate and one bidentate nitrate ions, respectively. In vitro biological studies have indicated that the bismuth complex 1 has shown effective antibacterial and anticancer activities especially with MIC = 15.6 μg/mL against Gram positive bacteria Bacillus cereus and IC50 = 1.6 μM against K562 leukemia cell lines, respectively, comparable to positive control.

The diorganotin(IV) complex [Ph2Sn(L)(CH3COO)] (1), where HL = 2-acetylpyrazine N4-methyl thiosemicarbazone, has been synthesized and characterized by elemental analysis, IR, UV/Vis and NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Complex 1 contains mononuclear neutral molecules composed of one N2S tridentate anionic thiosemicarbazone ligand, one acetato group, and one Ph2Sn(IV) group with a seven-coordinated tin atom. In vitro biological studies have indicated that complex 1 shows effective cytotoxicity with IC50 = 5.4 μM against the K562 leukaemia cell line.

A novel two-dimensional complex based on the mono-vacant Keggin anion [PW11O39]7−, [Ni(BIIM)3]3[{Ni(BIIM)2}2(PNiW11O39)2(BIIM)]・H2O (BIIM = 2,2ʹ-biimidazole), was hydrothermally synthesized and characterized by elemental and thermo-gravimetric analysis, IR and UV spectroscopy. Each [PW11O39]7− anion captures an Ni2+ ion forming a [PNiW11O39]5− polyanion, two of which are linked together by a BIIM ligand into a [(PNiW11O39)2(BIIM)]10− polyanion supporting two Ni(BIIM)2 2+ units through two terminal oxygen atoms and affording a complicated [{Ni(BIIM)2}2(PNiW11O39)2(BIIM)]6− heteropolyanion. Each of these units is further attached to four surrounding equivalent units by their own Ni(BIIM)2 2+ linkers into a two-dimensional brick wall-like network with (6,3) topology.

The two-dimensional coordination polymer [Ni(bpdc)(bix)1.5 ·H2O]n (H2bpdc = 2,4’-biphenyldicarboxylic acid; bix = 1,4-bis(imidazol-1-ylmethyl)benzene) was hydrothermally synthesized and structurally characterized. In the tile compound, the octahedral coordination environment around the Ni2+ ion is established by two oxygen atoms from two bpdc2− anions, one water molecule and three nitrogen atoms from three bix ligands. One bix ligand in the asymmetric unit lies on an inversion center at 1, 0.5, 0.5, and the other bix molecule resides on a general position. Each of the two bix molecules is coordinated to four Ni2+ ions, forming a 52-membered ring which is further assembled into a one-dimensional tape structure running parallel to the [100] direction. By a combination of the O2 and O4 oxygen atoms of one bpdc2− anion coordinating two Ni2+ ions, adjacent tapes are joined together, forming a layer structure parallel to the (010) plane. A 22-membered ring is formed by means of two bpdc anions binding to two Ni2+ ions.

Transition metal complexes [Mn(L)2] (I) and [Co(L)2] · (ClO4) · H2O (II), where HL = 2-acetylpyridine S-methyldithiocarbazate, have been synthesized. Complex I was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction studies. The manganese(II) atom in complex I adopts a distorted octahedral geometry with the Schiff base coordinated to it as a uninegatively charged tridentate chelating agent via the pyridine and azomethine nitrogen atoms and the thiolate sulfur atom. Biological studies carried out in vitro against K562 leukemia cancer cell line have shown that the free ligand and its metal complexes exhibited significant and different antitumor activity, since they exhibit IC50 values in the μM range.

Transition metal complexes [Zn(L1)2] (I) and [Mn(L2)2] (II), where HL1 = pyridine-2-carboxaldehyde S-methyldithiocarbazate, HL2 = pyridine-2-carboxaldehyde S-benzyldithiocarbazate, have been synthesized. Complex II was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction studies. The manganese(II) atom in complex II adopts a distorted octahedral geometry with the Schiff base coordinated to it as a uninegatively charged tridentate chelating agent via the pyridine and azomethine nitrogen atoms and the thiolate sulfur atom. Biological studies carried out in vitro against selected bacteria, fungi, and K562 leukemia cell line, respectively, have shown that the free ligands and their metal complexes exhibited distinctive differences in the biological properties. Ligand HL1 and complex I have the marked and broad antimicrobial activities compared to HL2 and complex II while only HL1 and complex II show significant antitumor activity against K562 leukemia cell line, since they exhibit IC50 values in the μM range.

Four diorganotin(IV) complexes [(Me)2Sn(L1)(CH3COO)]·CH3CH2OH (1), [(Ph)2Sn(L1)(CH3COO)]·CH3CH2OH (2), [(Me)2Sn(L2)Cl] (3) and [(Ph)2Sn(L2)(CH3COO)] (4) where HL1 = 2-benzoylpyridine N(4)-phenylthiosemicarbazone and HL2 = 2-acetylpyrazine N(4)-phenylthiosemicarbazone have been synthesized and characterized by elemental analysis, IR MS, 1H NMR and single-crystal X-ray diffraction studies. Schiff bases in their deprotonated forms coordinate to tin(IV) via pyridine/pyrazine nitrogen atom and the nitrogen atom and sulfur atoms of the thiosemicarbazone moiety. The tin atom is seven-coordinated in 1, 2 and 4 containing one acetato group, respectively, and six-coordinated in 3 containing one chloride ion. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cells, respectively, have shown that different substituted groups attached at the thiosemicarbazone moieties and different diorganotin(IV) groups showed distinctive differences in the biological property.

2-Acetylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its manganese(II) and nickel(II) complexes formulated as [Mn(L)2] (1) and [Ni(L)2] (2) have been synthesized and characterized by elemental analysis, infrared spectra, mass spectra, and single-crystal X-ray diffraction studies. In the two complexes, the coordination polyhedron approaches an octahedron, where the two ligands coordinate to the metal via the pyridine nitrogen atom and the nitrogen and sulfur donors of the thiosemicarbazide moiety. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cell line, respectively, have shown that the free ligand and its complexes exhibited distinct differences in the biological activities.

In the title salt, (C(6)H(8)N(4))[Mn(C(14)H(8)O(4))(2)(C(6)H(6)N(4))(2)]·6H(2)O, the Mn(II) atom lies on an inversion centre and is coordinated by four N atoms from two 2,2'-biimidazole (biim) ligands and two O atoms from two biphenyl-2,4'-dicarboxylate (bpdc) anions to give a slightly distorted octahedral coordination, while the cation lies about another inversion centre. Adjacent [Mn(bpdc)(2)(biim)(2)](2-) anions are linked via two pairs of N-H...O hydrogen bonds, leading to an infinite chain along the [100] direction. The protonated [H(2)biim](2+) moiety acts as a charge-compensating cation and space-filling structural subunit. It bridges two [Mn(bpdc)(2)(biim)(2)](2-) anions through two pairs of N-H...O hydrogen bonds, constructing two R(2)(2)(9) rings, leading to a zigzag chain in the [2-1-1] direction, which gives rise to a ruffled set of [H(2)biim](2+)[Mn(bpdc)(2)(biim)(2)](2-) moieties in the [01-1] plane. The water molecules give rise to a chain structure in which O-H...O hydrogen bonds generate a chain of alternating four- and six-membered water-oxygen R(4)(2)(8) and R(6)(6)(12) rings, each lying about independent inversion centres giving rise to a chain along the [100] direction. Within the water chain, the (H(2)O)(6) water rings are hydrogen bonded to two O atoms from two [Mn(bpdc)(2)(biim)(2)](2-) anions, giving rise to a three-dimensional framework.

2-Thiophene N(4)-methylthiosemicarbazone (HL) and its Ag(I) complex of formula [Ag6(L)6⋅ 4DMF] 1 have been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction studies. The silver(I) complex 1 with a 1:1 metal–ligand molar ratio is an unusual hexanuclear cluster with 6 silver atoms in different environments: four silver atoms of them are considered to be 3-coordinate form, which are coordinated by two thiolate sulfur atoms and one imine nitrogen and the other two silver atoms are considered to be 4-coordinate form, which are coordinated by three thiolate sulfur atoms and one imine nitrogen, with four thiolate sulfur bridging two silver atoms and two thiolate sulfur bridging three silver atoms. Biological studies, carried out in vitro against bacteria, fungi and SMMC-7721 liver cancer cell line, respectively, have shown that the free ligand and the title complex show distinct difference in the biological property.

The first hyperpolarizabilities β and ultraviolet spectra of two-dimensional charge transfer (2DCT) donor/acceptor-functionalized trigonal dehydrobenzoannulenes (compounds 2–7) have been calculated by using ab initio quantum chemistry methods. It is found that these multiple substituted chromophores possess large β values, where both diagonal and off-diagonal terms play important roles in β . This is different from the typical one-dimensional charge transfer (1DCT) compounds, where β is dominated by the diagonal terms. It is worth noting that a good nonlinearity-transparency trade-off is achieved for compounds 2–7 which exhibit larger β values coupled with enhanced transparency in the visible region. Moreover, the contributions of dipolar components to β are larger than that of octupolar components for compounds 2–7.

In this article, a study was presented on the adsorption activity of a new nanocomposite particle Fe3O4@1, which was synthesized by combining [Cu(HL)2]2H2[P2Mo5O23]&middot, 10H2O (1) (HL = 2-acetylpyridine semicarbazone) and Fe3O4 nanoparticles. Transmission electron microscopy and X-ray powder diffraction analyses revealed that Fe3O4@1 possessed high crystallinity with an average particle size of 19.1 nm. The adsorption activity of the as-prepared Fe3O4@1 was investigated by photometrically monitoring the removal of methylene blue, rhodamine B, safranine T, gentian violet, fuchsin basic, and methyl orange from aqueous solutions. Significantly, we could easily separate Fe3O4@1 from the reaction media by applying an external magnet. Furthermore, the recycling performance was observed using methylene blue, revealing the recyclability and high stability of Fe3O4@1. It was shown that Fe3O4@1 is a promising candidate material for adsorbing cationic dyes in aqueous media.

Nickel complex formulated as Ni(L)2 (L = monodeprotonated ligand corresponding to 2-acetylpyridine N(4)-methylthiosemicarbazone, HL) has been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The complex consists of discrete monomeric molecules with octahedral nickel(II) with two anionic 2-acetylpyridine N(4)-methylthiosemicarbazones as NNS tridentate ligands coordinated to nickel via the pyridine nitrogen, azomethine nitrogen, and sulfur. Hydrogen bonds link the different components to stabilize the crystal structure. Biological studies, carried out in vitro against bacteria, fungi, and the K562 leukemic cell line have shown that the free ligand and complex show distinct differences in biological activity.

Transition metal complexes [Fe(HL)2]Cl3 ⋅ 1.5H2O (1), [Co(L)2] ⋅ ClO4 ⋅ H2O (2), Ni(HL)2(ClO4)2 ⋅ 2H2O (3), Zn(HL)L ⋅ BF4 ⋅ 2H2O (4), and Cd(HL)2(ClO4)2 ⋅ 2H2O (5), where HL = C7H9N5S, 2-acetylpyrazine thiosemicarbazone, have been synthesized. Complex 2 was characterized by elemental analysis, infrared spectra, mass spectra, and single-crystal X-ray diffraction. Preliminary in vitro screening showed that 1, 4, and 5 exhibit higher antitumor activity than 2 and 3 against K562 leucocythemia cancer cell line.

Two 2:2 types of monolanthanide substituted polyoxometalates [{(α-PW11O39H)Ln(H2O)3}2]6− (Ln = NdIII for 1 and GdIII for 2) and [{(α-PW11O39)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10− (Ln = SmIII for 3, EuIII for 4, GdIII for 5, TbIII for 6, HoIII for 7 and ErIII for 8) have been synthesized in aqueous solution and characterized by elemental analyses, IR spectra, UV−vis−NIR spectra, thermogravimatric analyses and single-crystal X-ray diffraction. The common structural features are that they are constructed from monovacant Keggin-type polyoxoanions [α-PW11O39]7− and trivalent lanthanide cations. Both 1 and 2 are essentially isomorphous, and the molecular structure is built by two symmetrically related monolanthanide substituted Keggin units [α-PW11O39Ln(H2O)3]4− linked via two Ln−O−W bridges, representing the first monovacant Keggin polyoxotungstate dimers constituted by two [α-PW11O39]7− polyoxoanions and two lanthanide cations in polyoxometalate chemistry. 3−8 are also isostructural and display another dimeric struc...

The effects of solvent polarity on the geometry and static first hyperpolarizability of one- and two-dimensional charge transfer molecules based on para-nitroaniline (PNA) and 1,3-diamino-4,6-dinitrobenzene (DADB) were studied using a polarizable continuum model (PCM) at the B3LYP/6-31+G(d,p) level of theory. The inclusion of solvent does not change the geometry significantly, but produces a change in the calculated results of the electronic structures and nonlinear optical properties. It is found that solvent polarity has an important influence on the first hyperpolarizability, whereas its influence is negligible on the nonlinearity anisotropy parameter both for PNA and DADB, due to the fact that the off-diagonal component and the diagonal component of the first hyperpolarizability possess similar solvent effect characteristics.

The frequency-dependent first hyperpolarizabilities β(−2ω; ω, ω) and β(−ω; ω, 0) of the hemicyanine derivative, 4-N,N-dimethylamino-4′-N′-methyl stilbazolium (DAS), have been theoretically investigated by using ab initio and semi-empirical methods at the near-infrared region, respectively. Theoretical results indicate that the first hyperpolarizabilities, dominated by the contribution of the first excited state, show strong frequency dependence on the incident light. With the increase of the incident light frequency in infrared region, the values of β(−2ω; ω, ω) and β(−ω; ω, 0) increase, but β(−2ω; ω, ω) increases more significantly in near-infrared range (λ

[Fe(HL)2]Cl3 · 1.5H2O (1), where HL = C7H9N5S, 2-acetylpyrazine thiosemicarbazone, was obtained and fully characterized. X-ray diffraction studies show that complex 1 crystallizes in monoclinic lattice, space group P21 /n, with a = 11.342(6), b = 12.547(6), c = 17.056(9) A, β = 103.551(7)°, V = 2360(2) A3, Z = 2, Mr = 1159.46, D Calcd = 1.632 g cm−3, μ(Mo-Kα) = 1.188 mm−1, F(000) = 1184, the final R 1 = 0.0955 and wR 2 = 0.2626. The 2-acetylpyrazine thiosemicarbazone is a tridentate ligand and binds to the metal through the pyrazine nitrogen, the imine nitrogen and the sulfur in the neutral thione form yielding an octahedral geometry. The title iron complex showed significant antitumor activity against the Ec9706 human esophagus cancer cell line with an IC50 value (10.50 µM) in a micromolar range similar to cisplatin.

The title complex [Fe(C8H10N5S)2] · Cl has been synthesized from 2-acetylpyrazine N(4)-methylthiosemicarbazone and FeCl3 · 6H2O and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The complex consists of discrete monomeric molecules with octahedrally hexacoordinated iron(III) ions, in which two 2-acetylpyrazine 4-methylthiosemicarbazone units act as meridional NNS tridentate ligands coordinated to the central iron atom via the pyrazine nitrogen, azomethine nitrogen and sulfur atoms. Hydrogen bonds link the complex components to stabilize the crystal structure. The antitumor activity of the title complex was tested against K562 leucocythemia and BEL7402 liver cancer cell lines. The complex exhibits higher antitumor activity as compared to the free ligand.

A new organic-inorganic hybrid compound constructed from Keggin-type polyanion clusters and transition metal complexes, [Co(2,2′-bipy)3]1.5[SiWVWVI 11O40Co(2,2′-bipy)2(H2O)] · 0.5H2O (1), has been hydrothermally prepared and characterized by elemental analysis, IR, UV–Vis, TG-DTA and single crystal X-ray diffraction. Compound 1 crystallized in the monoclinic system, space group C2/c, a = 46.995(15), b = 14.487(5), c = 26.205(9)A, β = 90.000(0)°, V = 17841(10)A3, Z = 4. Compound 1 contains a [SiWVWVI 11O40Co(2,2′-bipy)2(H2O)]3− polyoxoanion in which [Co(2,2′-bipy)2(H2O)]2+ is covalently bonded to the α-Keggin-type heteropolyanion [SiWVWVI 11O40]5− via a terminal oxygen.

Two supra-molecular compounds: (1,1′-biphenyl)-4,4′-diammonium bis(3,5-dinitrobenzoate) (1) and 4,4′-methylene bis(benzenammonium) bis(3,5-dinitrobenzoate) monohydrate (2) were synthesized and characterized by IR spectrum, UV spectrum and element analysis. The single crystal structure analysis indicates that these compositions in two compounds are linked through N–H⋯O and O–H⋯O hydrogen bonds into infinite two-dimensional structure. Moreover, theoretical investigation was performed by using RHF/6-31G(d) method, and their stabilities, frontier molecular orbital composition and Mulliken charge distribution were discussed.

A zinc complex of the 2-benzoylpyridine thiosemicarbazone (Hbpt) ligand, Zn(bpt)2 · DMF, has been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. The molecular structure has a Zn2+ cation bonded to two perpendicular bpt ligands in a distorted octahedral geometry through two sulfur and four nitrogen atoms. The crystal contains a disordered DMF solvate molecule. Adjacent molecules are interconnected by means of hydrogen bonding generating a 1-D chain structure. The cytotoxic activity measurement indicates that the complex exhibits higher antitumor activity against lung cancer A549 cell lines than the free ligand.

A Keggin-type arsenotungstate anion-supported iron-bipyridine complex, [Fe(2,2'-bipy)3]1.5- [AsWVI 10WV 2O40Fe(2,2'-bipy)2(H2O)] · 0.25H2O, has been hydrothermally synthesized and characterized by IR and ESR spectra, TG-DTA analysis, and single crystal X-ray diffraction. Each structural unit of the title compound consists of one [AsWVI 10WV 2O40Fe(2,2'-bipy)2(H2O)]3− heteropolyanion, one and a half [Fe(2,2'-bipy)3]2+ cations, and a quarter of an H2O molecule. In the heteropolyanion the [Fe(2,2'-bipy)2(H2O)]2+ unit is covalently bonded to the reduced Keggin polyoxoanion [AsWVI 10WV 2O40]5−. The complex ismonoclinic, space group C2/c with a = 46.8079(13), b = 14.3990(4), c = 26.1085(8) Å , β = 90.00(5)°, Z = 8, Dc = 3.10 g/cm3

The title complex [Co(C7H8N5S)2]·2H2O has been synthesized and characterized by IR and UV spectral studies. The structure of the compound has been determined by single-crystal X-ray diffraction. The complex consists of discrete monomeric molecules with octahedrally hexacoordinate cobalt(II) ions, where two acetylpyrazine thiosemicarbazones act as NNS tridentate ligands coordinated to the central cobalt atom via the pyrazine nitrogen, azomethine nitrogen and sulfur atoms. Hydrogen bonds link the different components to stabilize the crystal structure. The antitumor activity of the title complex was tested against A549 lung cancer cell line. The complex exhibited lower antitumor activity, as compared to the free ligand.

In the presence of NBu4nBr acting as phase-transfer reagent, organosilicon trichloride RSiCl3 reacts in acetonitrile with the trivacant tungstophosphate sodium salt β-A-Na8H[PW9O34]·24 H2O to give hybrid organosilyl polyoxotungstate derivatives α-A-[NBu4n]3[PW9O34(RSiO)3(RSi)] (R=C2H3 (1), CH3 (2)). These compounds are characterized by X-ray crystallography. Each of the two hybrid anions consists of one α-A-PW9O349− framework on which is grafted by three RSiO groups through six SiOW bridges, each of which is attached to the fourth RSi through three SiOSi bridges. Both hybrid anions become saturated, close cage structure and display C3v symmetry.

The heteropoly tungstogallate acid H5GaW12O40 has been synthesized and characterized. Colorless octahedral crystals of the title compound were crystallized from acetonitrile with formula H5GaW12O40. The single crystal X-ray structure analysis of the title compound revealed that it crystallized in monoclinic system, space group Cm with a = 17.691 (4) A, b = 25.065 (5) A, c = 15.315 (3) A, β = 125.21 (3)°, V= 5548.5 (19) A3, and Z = 2. The crystal consists of the heteropolyanion GaW12O405− and H+ cations. The heteropolyanion GaW12O405− is an independent unit and assumed to have the Keggin structure.

Up to now, the metal complexes with thiocarbonohydrazones have been comparatively rare. Herein, three main group monometallic complexes formulated as [Bi(HL)(NO3)2(H2O)] (1), [Ga(HL)2]OAc·EtOH (2) and [(Ph)2Sn(HL)(OAc)]·DMF (3), where H2L = bis(2-acetylpyrazine)thiocarbonohydrazone, have been synthesized and characterized. The crystal structures of complexes 2 and 3 have been determined by single-crystal X-ray diffraction. Growth inhibition assays have indicated that both the free ligand and the title complexes are capable of inhibiting cell proliferation growth and could slightly distinguish the human hepatocellular carcinoma HepG2 cells from normal hepatocyte QSG7701 cells. Of particular note is the fact that the bismuth(III) complex 1 is the most active compound of this study and is 14-fold more cytotoxic than H2L with an IC50 value of 2.96 ± 0.25 μM. Its possible apoptotic mechanism has been evaluated in HepG2 cells. Complex 1 promotes a dose-dependent apoptosis in HepG2 cells and the apoptosis is associated with an increase in intracellular reactive oxygen species (ROS) production and reduction of mitochondrial membrane potential (MMP).

The asymmetric unit of the title two-dimensional coordination polymer, [Co(2)(C(16)H(6)O(8))(C(14)H(14)N(4))(2)](n), contains one Co(2+) ion, half of a biphenyl-3,3',4,4'-tetracarboxylate (bptc) anion lying about an inversion centre and one 1,4-bis(imidazol-1-ylmethyl)benzene (bix) ligand. The Co(II) atom is coordinated by three carboxylate O atoms from two different bptc ligands and two N atoms from two bix ligands constructing a distorted square pyramid. Each Co(2+) ion is interlinked by two bptc anions, while each bptc anion coordinates to four Co atoms as a hexadentate ligand so that four Co(II) atoms and four bptc anions afford a larger 38-membered ring. These inorganic rings are further extended into a two-dimensional undulated network in the (101) plane. Two Co(II) atoms in adjacent 38-membered rings are joined together by pairs of bix ligands forming a 26-membered [Co(2)(bix)(2)] ring that is penetrated by a bptc anion; these components share a common inversion centre.