A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates.

Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters, but their synthesis and subsequent installation onto metal nanoclusters remains a significant challenge. Herein, two atomically precise silver nanoclusters {Ag[(TC4A)(VO)](CyS)} (Ag14) and {AgS[(TC4A)(VO)](CyS)(PhCOO)Cl(SO)(DMF)·6DMF} (Ag43) are synthesized by controlling reaction temperature (HTC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)(VO)] metalloligand in Ag14 and 1D arcuate [(TC4A)(VO)] metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A as the passivating agent.

RSK2 promotes melanoma cell proliferation and vemurafenib resistance upregulating cyclin D1.

BRAF inhibitors are commonly used in targeted therapies for melanoma patients harboring BRAF mutant. Despite the benefit of vemurafenib therapy, acquired resistance during or after treatment remains a major obstacle in BRAF mutant melanoma. Here we found that RSK2 is overexpressed in melanoma cells and the high expression of RSK2 indicates poor overall survival (OS) in melanoma patients.

HOTTIP polymorphism may affect gastric cancer susceptibility by altering HOTTIP expression.

Background: Non-coding RNA polymorphisms can affect disease risk and prognosis by influencing gene expression. Here, we first investigated the association between single nucleotide polymorphisms (SNPs) of long non-coding RNA (lncRNA) HOTTIP and gastric cancer risk/prognosis.

Methods: A total of five HOTTIP SNPs among 627 gastric cancer cases and 935 controls were tested by Kompetitive Allele Specific PCR (KASP) assay.

Electrospinning Ag-TiO Nanorod-Loaded Air Treatment Filters and Their Applications in Air Purification.

The efficient treatment of the problem of air pollution is a practical issue related to human health. The development of multi-functional air treatment filters, which can remove various kinds of pollutants, including particulate matter (PM) and organic gases, is a tireless pursuit aiming to address the actual needs of humans. Advanced materials and nano-manufacturing technology have brought about the opportunity to change conventional air filters for practical demands, with the aim of achieving the high-efficiency utilization of photons, a strong catalytic ability, and the synergetic degradation of multi-pollutants.

Structural isomerism in gold nanoparticles revealed by X-ray crystallography. [Corrected].

Revealing structural isomerism in nanoparticles using single-crystal X-ray crystallography remains a largely unresolved task, although it has been theoretically predicted with some experimental clues. Here we report a pair of structural isomers, Au38T and Au38Q, as evidenced using electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy, thermogravimetric analysis and indisputable single-crystal X-ray crystallography. The two isomers show different optical and catalytic properties, and differences in stability.

Calix[4]arene-supported mononuclear lanthanide single-molecule magnet.

Three new single paramagnetic lanthanide-based complexes, [Ln(L)(LOEt)] (Ln(3+) = Dy(3+), Tb(3+), and Ho(3+)), are synthesized with the multidentate calix[4]arene ligand H2L (H2L = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-dihydroxy-26,28-dimethoxycalix[4]arene) and Kläui's tripodal ligand LOEt(-) (LOEt(-) = (η(5)-cyclopentadienyl)tris(diethylphosphito-p)cobaltate(III)). All of the complexes have been characterized by single crystal X-ray diffraction analysis, thermal stability, absorption spectra, and magnetization measurements. The magnetic properties and magnetostructural correlation in this seven-coordinated system are investigated.

Enantiopure heterobimetallic single-chain magnets from the chiral Ru(III) building block.

A pair of one-dimensional enantiomers based on the versatile chiral dicyanoruthenate(III) building block have been synthesized and they are chiral single-chain magnets with the effective spin-reversal barrier of 28.2 K.

Seven-coordinate lanthanide sandwich-type complexes with a tetrathiafulvalene-fused Schiff base ligand.

Three seven-coordinate lanthanide(III) sandwich-type mononuclear complexes with π-conjugated TTF-Schiff base ligand H2L (L(2-) = 2,2'-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole-5,6-diyl)bis(nitrilomethylidyne)bis(4-chlorophenolate)) and the tripodal ligand L(OEt)(-) (L(OEt)(-) = [(η(5)-C5H5)Co(P(═O)(OEt)2)3](-)), [(L(OEt))Ln(L)]·0.25H2O (Ln(3+) = Dy(3+), 1; Tb(3+), 2; Ho(3+), 3), have been synthesized and structurally characterized. All of the complexes are also characterized by absorption spectra and electrochemical, spectroelectrochemical, and magnetic studies.

A sandwich-type triple-decker lanthanide complex with mixed phthalocyanine and Schiff base ligands.

A new triple-decker dinuclear sandwich-type dysprosium complex based on both the phthalocyanine ligand and the tetradentate Schiff base ligand was synthesized, which is of interest for synthetic chemistry and also shows single-molecule magnetic behaviour.

Syntheses, structures, and magnetic properties of seven-coordinate lanthanide porphyrinate or phthalocyaninate complexes with Kläui's tripodal ligand.

A series of seven-coordinate mononuclear lanthanide(III) complexes of the general formula [(TPP)Ln(L(OEt))]·0.25H2O and [(Pc)Ln(L(OEt))] (Ln(3+) = Dy(3+), Tb(3+), Ho(3+), and Gd(3+); TPP = 5,10,15,20-tetraphenylporphyrinate; Pc = phthalocyaninate; L(OEt)(-) = [(η(5)-C5H5)Co(P(=O)(OEt)2)3](-)) are synthesized on the basis of the tripodal ligand L(OEt)(-) and either porphyrin or phthalocyanine ligands. All of the complexes are characterized by X-ray crystallography and by static and dynamic magnetic measurements.

A giant metallo-supramolecular cage encapsulating a single-molecule magnet.

A giant metallo-supramolecular cage encapsulating a single-molecule magnet, [Ag42{Ho(W5O18)2}(t-BuC≡C)28Cl4]OH, is prepared and structurally characterized. It shows an interesting "peanut-like" structure and remains intact in solution as demonstrated by NMR studies.

Self-assembly of metallomacrocycles with dipyrazole ligands and anion sensing of [Pd4Fe2] macrocycle with ferrocene-based dipyrazole ligand.

By employing dipalladium corners [(bpy)(2)Pd(2)(NO(3))(2)](NO(3))(2) or [(phen)(2)Pd(2)(NO(3))(2)](NO(3))(2) (where bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline) to bridge ferrocene-based dipyrazole ligand (L(1)) and m-phenylene-based dipyrazole ligands (L(2-3)) in aqueous solution, a series of positively-charged [M(4)L(2)](4+) metallomacrocycles were obtained. Their structures were characterized by (1)H NMR, electrospray ionization mass spectrometry (ESI-MS), elemental analysis, and single crystal X-ray diffraction analysis for 1·4NO(3) ({[(bpy)Pd](4)L(1)(2)}(NO(3))(4)) and 4·4NO(3) ({[(phen)Pd](4)L(2)(2)}(NO(3))(4)). In their single crystal structures, NO(3)(-) anions are located at the dipalladium corners by C-H.

Chiral one-dimensional O-P-O bridged Mn(III)-Schiff base complexes.

Two couples of enantiomerically pure metal phosphonates are successfully synthesized by using chiral Mn(III)-Schiff base mononuclear precursors. Compounds [Mn((R,R)-5-Brsalcy)(2-FC(6)H(4)PO(3)H)]·3H(2)O (1) and [Mn((R,R)-5-Brsalcy)(4-CH(3)C(6)H(4)PO(3)H)]·CH(3)OH·H(2)O (3) [5-Brsalcy = N,N'-(1,2-cyclohexanediylethylene)bis(5-bromosalicylideneiminato) dianion] are isostructural and show similar one-dimensional chain structures where the Mn((R,R)-5-Brsalcy)(+) species are bridged by O-P-O units. Compounds 2 and 4 are (S,S)-enantiomers of 1 and 3, respectively.

Field-induced slow magnetic relaxation in chiral seven-coordinated mononuclear lanthanide complexes.

Four couples of enantiomerically pure chiral seven-coordinated mononuclear lanthanide complexes, [(L(OEt))Dy((R,R)-Salphen)](2)·3H(2)O (1, L(OEt) = [(Cp)Co(P(O)(OEt)(2))(3)], Cp = cyclopentadiene, Salphen = N,N'-1,2-diphenylethylenebis(salicylideneiminato) dianion), [(L(OEt))Dy((S,S)-Salphen)](2)·3H(2)O (2), [(L(OEt))Dy((R,R)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (3, Salcy = N,N'-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [(L(OEt))Dy((S,S)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (4), [(L(OEt))Tb((R,R)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (5), [(L(OEt))Tb((S,S)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (6), [(L(OEt))Ho((R,R)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (7) and [(L(OEt))Ho((S,S)-5-Cl-Salcy)]·CH(3)OH·1/8H(2)O (8), have been successfully synthesized by using tetradentate chiral salen-type ligands and the Kläui's tripodal ligand of L(OEt). Structural analyses reveal that all compounds have a typical double-decker sandwich structure, and the Ln(iii) ions exhibit a rare seven-coordinated mode, situating in a distorted monocapped triangular prism polyhedron. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes and demonstrate that the chirality is successfully transferred from the ligand to the coordination environment of the Ln(iii) ions.

Formation of stable iron/cobalt NHC complexes via unexpected ring opening and in situ generation of a tridentate ligand.

The reactions of FeCl(2) and CoCl(2) with a bistriazolium salt yields the NHC complexes [Fe(III)(L1)(2)]I·H(2)O, [Fe(III)(L2)(2)]PF(6)·CH(3)CN and [Co(III)(L1)(2)]I·0.5CH(3)CN, through an unusual ring opening of one of the triazoyl rings, which leads to the formation of C,N,O tridentate ligands L1 or L2. Furthermore, a Fe(ii) species [Fe(II)(L1)(2)]·CH(2)Cl(2) was also obtained.

A racemic polar cobalt phosphonate with weak ferromagnetism.

Comfortably nemp: A novel polar compound [Co(2)(nemp)(2)(H(2)O)(2) ] incorporating racemic [1-(1-naphthyl)ethylamino]methylphosphonate (nemp(2-)) as a ligand is reported (see packing structure). This compound shows nonlinear optical properties at room temperature and weak ferromagnetism below 2 K.

Solvent-induced single-crystal-to-single-crystal transformation in multifunctional chiral dysprosium(III) compounds.

Two new enantiomeric ionic chiral dysprosium(III) compounds were designed and synthesized. These compounds show simultaneously the optical activity, ferroelectric effects, nonlinear-optical effects, and slow magnetic relaxation behavior. More interestingly, these compounds exhibit reversible single-crystal-to-single-crystal transformations associated with the release or absorption of solvent molecules.

Lanthanide-ion-tuned magnetic properties in a series of three-dimensional cyano-bridged Ln(III)W(V) assemblies.

The reaction of [W(CN)(8)](3-) with Ln(3+) and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H(2)O)(4)(pyrazine)(0.5)W(CN)(8) (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(III) and W(V) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks.

Vibrational and electronic circular dichroism monitoring of copper(II) coordination with a chiral ligand.

Novel copper(II) coordination compounds with chiral macrocyclic imine ligands derived from R-/S-camphor were asymmetrically synthesized and characterized with the aid of chiroptical spectroscopies. Crystal structures of both enantiomers were determined by single crystal X-ray diffraction analysis. Circular dichroism (CD) spectra were analyzed using a simplified exciton model as well as quantum chemical computations.

Metal-organic frameworks constructed from versatile [WS4Cu(x)](x-2) units: micropores in highly interpenetrated systems.

Five metal-organic frameworks (MOFs) formed by [WS(4)Cu(x)](x-2) secondary building units (SBUs) and multi-pyridyl ligands are presented. The [WS(4)Cu(x)](x-2) SBUs function as network vertexes showing various geometries and connectivities. Compound 1 contains one-dimensional channels formed in fourfold interpenetrating diamondoid networks with a hexanuclear [WS(4)Cu(5)](3+) unit as SBU, which shows square-pyramidal geometry and acts as a tetrahedral node.

Chiral cyanide-bridged Cr(III)-Mn(III) heterobimetallic chains based on [(Tp)Cr(CN)3]-: synthesis, structures, and magnetic properties.

By the reactions of Mn(III) Schiff-base complexes with the tricyanometalate building block, [(Tp)Cr(CN)(3)](-) (Tp = Tris(pyrazolyl) hydroborate), two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes, [Mn((R,R)-Salcy)Cr(Tp)(CN)(3)·1/4H(2)O·1/2CH(2)Cl(2)](n) (1) and [Mn((S,S)-Salcy)Cr(Tp)(CN)(3)·1/4H(2)O·1/2CH(2)Cl(2)](n) (2) (Salcy = N,N'-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [Mn((R,R)-Salphen)Cr(Tp)(CN)(3)](n) (3) and [Mn((S,S)-Salphen)Cr(Tp)(CN)(3)](n) (4) (Salphen = N,N'-1,2-diphenylethylene-bis(salicylideneiminato) dianion), have been successfully synthesized. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Structural analyses reveal the formation of neutral cyano-bridged zigzag single chains in 1 and 2, and neutral cyano-bridged zigzag double chains in 3 and 4.

Three self-penetrated, interlocked, and polycatenated supramolecular isomers via one-pot synthesis and crystallization.

Three supramolecular isomers, {[Cd(2)(TPOM)(hfipbb)(2)]·x/y/zsolvent}(n) (1-3), have been synthesized and characterized by one-pot reaction. Even though the compositions of 1-3 are the same, they generate different structures. Reactions over various time periods were found to influence the formation of supramolecular isomers, and there is little influence on this system under other conditions.

Poly[[hexa-kis-(μ-benzene-1,4-dicarboxyl-ato)octa-kis-(N,N-dimethyl-acetamide)-hexa-manganese(II)] monohydrate].

In the title compound, {[Mn(6)(C(8)H(4)O(4))(6)(C(4)H(9)NO)(8)]·H(2)O}(n), two of the Mn atoms are six-coordinated by six O atoms from three benzene-1,4-dicarboxyl-ate (bdc) ligands and two trans DMA (dimethyl-acetamide) mol-ecules, whereas two other Mn atoms, located on inversion centers, are both in octa-hedral coordinations by six bdc O atoms. The discrete trinuclear manganese secondary building units (SBU) of Mn(3)(O(2)CR)(6) ({-Mn-Mn-Mn-}) are linked through bdc ligands, forming a chain, while the discrete trinuclear SBU of {-Mn-Mn-Mn-} are bridged, forming another chain]. The two types of chains are linked through bdc ligands, resulting in the formation of a layer with 3(6) topology.

Poly[[aqua-tris-(μ-benzene-1,4-dicarboxyl-ato)tricobalt(II)] methanol monosolvate monohydrate].

The asymmetric unit of the title compound, {[Co(3)(C(8)H(4)O(4))(3)(H(2)O)]·CH(3)OH·H(2)O}(n), consists of four crystallographically independent Co cations, four benzene-1,4-dicarboxyl-ate (bdc) anions, two water and one methanol solvent mol-ecule. Two of the Co cations and two of the bdc anions are located on centres of inversion, whereas all other atoms are located in general positions. In the crystal, two Co atoms are only fourfold coordinated by three O atoms from three bdc ligands and by one O atom from one coordinated water mol-ecule, while a third Co atom is coordinated by four O atoms from four bdc ligands within a strongly distorted tetra-hedral geometry.