Mixture Of Ligands Research Articles

Stabilization and Encapsulation of Gold Nanostars Mediated by Dithiols.

Surface chemistry plays a pivotal role in regulating the morphology of nanoparticles, maintaining colloidal stability, and mediating the interaction with target analytes toward practical applications such as surface-enhanced Raman scattering (SERS)-based sensing and imaging. The use of a binary ligand mixture composed of 1,4-benzenedithiol (BDT) and hexadecyltrimethylammonium chloride (CTAC) to provide gold nanostars with long-term stability is reported. This is despite BDT being a bifunctional ligand, which usually leads to bridging and loss of colloidal stability. It is found however that neither BDT nor CTAC alone are able to provide sufficient colloidal and chemical stability. BDT-coated Au nanostars are additionally used as seeds to direct the encapsulation with a gold outer shell, leading to the formation of unusual nanostructures including semishell-coated gold nanostars, which are characterized by high-resolution electron microscopy and electron tomography. Finally, BDT is exploited as a probe to reveal the enhanced local electric fields in the different nanostructures, showing that the semishell configuration provides significantly high SERS signals as compared to other core-shell configurations obtained during seeded growth, including full shells.

Conformational Switching of a Foldamer in a Multicomponent System by pH-Filtered Selection between Competing Noncovalent Interactions.

Biomolecular systems are able to respond to their chemical environment through reversible, selective, noncovalent intermolecular interactions. Typically, these interactions induce conformational changes that initiate a signaling cascade, allowing the regulation of biochemical pathways. In this work, we describe an artificial molecular system that mimics this ability to translate selective noncovalent interactions into reversible conformational changes. An achiral but helical foldamer carrying a basic binding site interacts selectively with the most acidic member of a suite of chiral ligands. As a consequence of this noncovalent interaction, a global absolute screw sense preference, detectable by 13C NMR, is induced in the foldamer. Addition of base, or acid, to the mixture of ligands competitively modulates their interaction with the binding site, and reversibly switches the foldamer chain between its left and right-handed conformations. As a result, the foldamer–ligand mixture behaves as a biomimetic chemical system with emergent properties, functioning as a “proton-counting” molecular device capable of providing a tunable, pH-dependent conformational response to its environment.

Indium Tin Oxide and Silicon Nanocrystal Nanocomposite Grown By Aerosol Assisted Chemical Vapour Deposition

Nanocomposite films were successfully grown by aerosol-assisted chemical vapour deposition (CVD) in a single deposition step using a mixture of Indium Tin neodecanoate and ligand stabilised silicon nanocrystals. Samples were analysed by HRTEM and silicon nanocrystals with a density of 1.2 × 1012 cm-2 were observed. From the reconstructed 3D tomogram, the averaged distance between the nearest nanoparticles is 8.3 nm and the 3D density of nanoparticles is 1.6 × 1018 cm-3. An animation of the 3D reconstruction is supplied in the supporting information. These data show the versatility of aerosol assisted CVD in achieving a nanocomposite with such a density of silicon nanocrystals, of carefully controlled size and shape, within a polycrystalline host matrix. Therefore, meeting the density and size distribution requirements of particle inclusion in active nanocomposites for photovoltaic structures

Development of Experiment and Theory to Detect and Predict Ligand Phase Separation on Silver Nanoparticles

AbstractMALDI mass‐spectrometry measurements are combined with self‐consistent mean‐field (SCF) calculations to detect and predict ligand phase separation on Ag nanoparticles. The experimental and theoretical techniques complement each other by enabling quantification of the nearest‐neighbor distribution of a ligand mixture in a monolayer shell. By tracking a characteristic metallic fragment family, analysis of a MALDI spectrum produces a frequency distribution corresponding to specific ligand patterning. Inherent to the SCF calculation is the enumeration of local interactions that dictate ligand assembly. Interweaving MALDI and SCF facilitates a comparison between the experimentally and theoretically derived frequency distributions as well as their deviation from a well‐mixed state. Thus, we combine these techniques to detect and predict phase separation in monolayers that mix uniformly or experience varying degrees of de‐mixing, including microphase separation and stripe formation. Definition of MALDI removed as this is a commonly recognized technique.

Development of experiment and theory to detect and predict ligand phase separation on silver nanoparticles.

MALDI mass-spectrometry measurements are combined with self-consistent mean-field (SCF) calculations to detect and predict ligand phase separation on Ag nanoparticles. The experimental and theoretical techniques complement each other by enabling quantification of the nearest-neighbor distribution of a ligand mixture in a monolayer shell. By tracking a characteristic metallic fragment family, analysis of a MALDI spectrum produces a frequency distribution corresponding to specific ligand patterning. Inherent to the SCF calculation is the enumeration of local interactions that dictate ligand assembly. Interweaving MALDI and SCF facilitates a comparison between the experimentally and theoretically derived frequency distributions as well as their deviation from a well-mixed state. Thus, we combine these techniques to detect and predict phase separation in monolayers that mix uniformly or experience varying degrees of de-mixing, including microphase separation and stripe formation. Definition of MALDI removed as this is a commonly recognized technique.

ChemInform Abstract: Palladium Catalyzed Heck‐Mizoroki and Suzuki‐Miyaura Coupling Reactions (Review)

AbstractReview: 145 refs.

Activation of the mouse odorant receptor 37 subsystem coincides with a reduction of novel environment-induced activity within the paraventricular nucleus of the hypothalamus.

Within the main olfactory system of mammals, a unique subsystem exists that is comprised of sensory neurons expressing odorant receptors (ORs) of the OR37 subfamily. These receptors are exclusive for mammals and are highly conserved across species. The mouse OR37 receptor subtypes A, B and C were shown to be activated by the long-chain aliphatic aldehydes pentadecanal, hexadecanal and heptadecanal, respectively. The search for biological sources of these compounds showed that bodily secretions from conspecifics activated the OR37A, B and C glomerulus. At the same time, the activity of cells in a target region of projection neurons from OR37 glomeruli, the paraventricular nucleus of the hypothalamus (PVN), was reduced compared with controls (clean test box). A large number of the activated cells in the PVN of mice that were placed into a clean test box were corticotropin-releasing hormone cells, indicating an induction of the stress axis due to the novel environment. The much lower number of activated cells of mice in a box enriched with bodily secretions from conspecifics indicated a reduced stress response. As bodily secretions from conspecifics activated the OR37 system and simultaneously reduced stress-induced activation of the PVN, it was tested whether the ligands for OR37 receptors could induce this effect. Indeed, a similarly reduced activity in the PVN was found in mice kept in a clean test box and exposed to a mixture of the OR37 ligands delivered via an air stream. These data indicate that the OR37 system may play a role in mediating a phenomenon called social buffering.

Indium tin oxide–silicon nanocrystal nanocomposite grown by aerosol assisted chemical vapour deposition

Nanocomposite films were successfully grown by aerosol-assisted chemical vapour deposition (CVD) in a single deposition step using a mixture of indium tin neodecanoate and ligand stabilised silicon nanocrystals. Samples were analysed by HRTEM and silicon nanocrystals with a density of 1.2 × 1012 cm−2 were observed. From the reconstructed 3D tomogram, the averaged distance between the nearest nanoparticles is 8.3 nm and the 3D density of nanoparticles is 1.6 × 1018 cm−3. An animation of the 3D reconstruction is supplied in the supporting information. These data show the versatility of aerosol assisted CVD in achieving a nanocomposite with such a density of silicon nanocrystals, of carefully controlled size and shape, within a polycrystalline host matrix. Therefore, meeting the density and size distribution requirements of particle inclusion in active nanocomposites for photovoltaic structures. ITO–silicon nanocrystal nanocomposite samples were analysed by HRTEM and silicon nanocrystals with a density of 1.2 × 1012 cm−2 were observed. From the reconstructed 3D tomogram, the averaged distance between the nearest nanoparticles is 8.3 nm and the 3D density of nanoparticles is 1.6 × 1018 cm−3.

The role of PEG conformation in mixed layers: from protein corona substrate to steric stabilization avoiding protein adsorption

Abstract Although nanoparticles (NPs) have been traditionally modified with a single ligand layer, mixture of ligands might help to combine different functionalities and to further engineer the NP surface. A detailed study of the competition between an alkanethiol (11-mercaptoundecanoic acid) and SH-PEG for the surface of AuNPs and the resultant behaviors of this model nanoconjugate is presented here. As a result, the physicochemical properties of these conjugates can be progressively tuned by controlling the composition and especially the conformation of the mixed monolayer. This has implications in the physiological stability. The controlled changes on the SH-PEG conformation rather than its concentration induce a change in the stabilization mechanism from electrostatic repulsion to steric hindrance, which changes the biological fate of NPs. Importantly, the adsorption of proteins on the conjugates can be tailored by tuning the composition and conformation of the mixed layer.

Identifying lead hits in catalyst discovery by screening and deconvoluting complex mixtures of catalyst components.

A reaction-economic combinatorial strategy is described for lead hit identification in catalyst discovery efforts directed towards a specific transformation. Complex mixtures of rationally chosen precatalysts and ligands are screened against various reaction parameters to identify lead conditions in a small number of reactions. Iterative deconvolution of the resulting hits identifies which components contribute to the lead in situ generated catalyst. Application of this strategy rapidly uncovered a new mild in situ generated catalyst for the dehydrative Friedel-Crafts reaction as well as conditions for selective monoarylation in catalytic ortho-C-H arylation of unsubstituted N-(quinolin-8-yl)benzamide.

Utilization of mixtures of aromatic N-donor ligands of different coordination ability for the solvothermal synthesis of thiostannate containing molecules.

Utilization of mixtures of differently coordinating aromatic N-donor ligands leads to the formation of the two new compounds {[Ni(phen)2]2Sn2S6}·4,4'-bipy·½H2O I and {[Ni(phen)2]2Sn2S6}·2,2'-bipy II that could be prepared under solvothermal conditions (4,4'-bipy = 4,4'-bipyridine, C10H8N2; phen = 1,10-phenanthroline, C12H8N2; 2,2'-bipy = 2,2'-bipyridine, C10H8N2). In the structures of both compounds Ni-S bond formation is observed which is highly unusual when only bidentate N-donor ligands are applied in the reaction mixture. The detailed analysis of the crystal structure indicates that the presence of 4,4'-bipy and 2,2'-bipy molecules are essential for the stabilization of the arrangement of the constituents. The main structural motif {[Ni(phen)2]2Sn2S6} is arranged generating off center parallel stacking of the phen ligands. The empty spaces between the {[Ni(phen)2]2Sn2S6} moieties are occupied by either 2,2'-bipy (I) or 4,4'-bipy (II) molecules which are oriented towards the phen ligands to form intermolecular π-π interactions.

ChemInform Abstract: Cobalt‐Catalyzed Hydrogenation of β‐Enamino Esters Using an Internal Mixture Of bidentate and Monodentate Ligands.

Abstract Different β-amino esters have been obtained in good yields by means of octacarbonyldicobalt-catalyzed hydrogenation of β-enamine esters in the presence of mixture of a bidentate phosphine chiral (R-BINAP) and a monodentate phosphine achiral (PPh3). Likewise, a non-symmetric Co/BINAP/PPh3 complex was isolated. This new compound was used in the hydrogenation reaction under different conditions and the results suggest that this heterocombination could be responsible for improving enantiomeric excess in the reduction products.

As-stereogenic C2-symmetric organoarsines: synthesis and enantioselective self-assembly into a dinuclear triple-stranded helicate with copper iodide

As-stereogenic C2-symmetric 2,5-diaryl-cis-1,4-dihydro-1,4-diarsinines (2,5-diaryl-cis-DHDAs) were synthesized without volatile precursors. A racemic mixture of the ligands enantioselectively self-assembled into a dinuclear triple-stranded helicate with copper iodide in quantitative yield. In the helicate, two metals were bridged via three enantiomerically pure ligands.

Relative binding affinities of integrin antagonists by equilibrium dialysis and liquid chromatography-mass spectrometry.

The integrin αvβ6 is a potential target for treatment of idiopathic pulmonary fibrosis (IPF). Equilibrium dialysis (ED) was investigated for its ability to report ligand binding in an αvβ6 inhibitor screening assay. As a preliminary experiment, an established peptidomimetic inhibitor of the integrin was dialyzed against αvβ6, and the fraction bound (f b) and percentage saturation determined by liquid chromatography-mass spectrometry (LC-MS) analysis. Quantitation of the inhibitor in the two chambers of the ED cartridge revealed an uneven distribution in the presence of αvβ6, corresponding to near saturation binding to the protein (93 ± 3%), while the control (without integrin) showed an equal partitioning of the inhibitor on either side of the dialysis membrane. A competitive ED assay with a 12 component mixture of antagonists was conducted, and the results compared with an established cell adhesion assay for quantifying αvβ6 inhibition of individual antagonists. Compounds clustered into three groupings: those with pIC 50 values between ca. 5.0 and 5.5, which possessed ED f b values indistinguishable from the controls, those with pIC 50s of 6.5 ± 0.2, which exhibited detectable integrin binding (f b 13-25%) in the ED assay, and a single compound of pIC 50 7.2 possessing an f b value of 38%. A good correlation between ED-derived f b and pIC 50 was observed despite the two assays utilizing quite different outputs. These results demonstrate that ED with LC-MS detection shows promise as a rapid αvβ6 integrin antagonist screening assay for mixtures of putative ligands.

Tuning the Dimensionality of Polyoxometalate-Based Materials by Using a Mixture of Ligands

Five molecular one-, two-, or three-dimensional (1D, 2D, or 3D) organic–inorganic hybrid polyoxometalates (POMs) based on the {ε-PMoV8MoVI4O40Zn4} (εZn) Keggin unit have been synthesized under hydrothermal conditions using a mixture of O- and N-donor ligands. (TBA)6[PMoV8MoVI4O37(OH)3Zn4]2(C14H8O4)3·6H2O (ε2(biphen)3) is a 3D material with two interpenetrated networks built from dimeric (εZn)2 POMs linked by 4,4′-biphenyldicarboxylate (biphen) ligands. (TBA)2[PMoV8MoVI4O38(OH)2Zn4](C7H6N2)3(C14H8O4)1/2·H2O (ε(bim)3(biphen)1/2), (TBA)3[PMoV8MoVI4O38(OH)2Zn4](C7H6N2)2(C8H4O4)·6H2O (ε(bim)2(isop)), (TBA)7/3[PMoV8MoVI4O38(OH)2Zn4](C7H6N2)8/3(C8H4O4)2/3 (ε(bim)8/3(bdc)2/3), and (TBA)3[PMoV8MoVI4O38(OH)2Zn4](C7H6N2)2(C9H3O6)2/3·6H2O (ε(bim)2(trim)2/3) all consist of monomeric εZn units bound to two types of organic ligands: benzimidazole (bim) and one of the following carboxylate ligands: biphen, 1,3-benzenedicarboxylate (isop), 1,4-benzenedicarboxylate (bdc), or 1,3,5-benzenetricarboxylate (trim) ligands. While ε(bim)3(biphen)1/2 is a molecular complex, ε(bim)2(isop) and ε(bim)8/3(bdc)2/3 adopt a chain arrangement, and ε(bim)2(trim)2/3 is a 2D compound. In these materials, the limitation of the dimensionality is a direct consequence of the protonation of the nitrogen atom of the bim ligands. The electrocatalytic activity for the hydrogen evolution reaction (HER) of these five new POM-based coordination polymers has been studied, showing that their performance depends mainly on the presence of the εZn Keggin units but also on their structure. Modified electrodes fabricated with ε(bim)2(trim)2/3 entrapped in a carbon paste revealed that this hybrid is the most efficient electrocatalyst of the series, being stable and catalyzing the HER in the pH 1–5 range.

Sonochemical synthesis and characterization of new one-dimensional manganese(II) coordination polymer nanostructures

A new Mn(II) coordination polymer, [Mn (L1)2(NCS)2]n (1) [L1=3,4-bis(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole] was synthesized by the reaction of ligand L1 and mixtures of manganese(II) acetate and potassium thiocyanate using the heat gradient method. Compound 1 has been characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The crystal structure of compound 1 was determined by single-crystal X-ray diffraction and shows a new interesting one-dimensional coordination polymer. Nanostructures of compound 1 have been synthesized by sonochemical method. The products were characterized by X-ray powder diffraction, scanning electron microscopy (SEM), and IR spectroscopy. The thermal stability of nano particles of compound 1 was studied by thermal gravimetric and differential thermal analyses.

Synthesis, characterization and application of iron N-substituted imidazole complexes with the motif ClFeL4OFeCl3

The activation of molecular oxygen was investigated applying a mixture of iron(II) chloride and N-substituted imidazole ligands. The resulting complexes were characterized and investigated by various techniques, pointing out bimetallic complexes with the general Cl(imidazole)4FeOFeCl3 motif. The complexes contain two different iron centers, on the one hand iron with an octahedral geometry and on the other hand iron with a tetrahedral geometry were observed. Both units are connected via a bridging oxido-ligand. Moreover, the complexes have been applied as precatalyst in iron-catalyzed epoxidation of stilbene.

Palladium catalyzed Heck-Mizoroki and Suzuki-Miyaura coupling reactions (Review)

This article is about the progress of palladium compounds as a catalyst for Heck-Mizoroki and Suzuki-Miyaura coupling reactions. Industrial catalysts with broad applicability need continuous catalyst development process through modification of ligand design, geometry and functionality. Recently catalysts have been synthesized through attachment of the activated palladium complexes on the surface of polymer support, particularly, insoluble in reaction medium. An appropriate mixture of palladium salt and ligand is also used as an important modification in some cases to get better results. We surveyed the important palladium compounds synthesized up to early 2014 for Heck-Mizoroki and Suzuki-Miyaura coupling reactions and summarize their progress in terms of ligand modification and other associated parameters.

ChemInform Abstract: Polynuclear Heterometallic Complexes from Metal Powders: The “Direct Synthesis” Approach

AbstractReview: [51 refs.

Synthesis and crystal structure of 1D Cd-amine coordination polymer and its luminescent properties

A novel one dimension(1D) cadmium coordination polymer {[Cd(mpda)3]·2(NO3)} n (1) was synthesized via refluxing a mixture of tetradentate Schiff base ligand N,N′-bis(2-pyridinylethylidene)phenylene-1,3-diamine(L) and Cd(NO3)2 in acetonitrile, whose structure was characterized by means of single crystal X-ray diffraction, FTIR spectroscopy, elemental analysis and proton nuclear magnetic resonance(1H NMR). Center metal Cd(II) ion is six-coordinated by six nitrogen atoms from six different m-phenylenediamine(mpda), giving rise to a [CdN6] octahedral coordination environment. The two adjacent cadmium centers are linked by three mpda molecules leading to the construction of 1D chain structure. The crystal structure is stabilized by N—H…O hydrogen bonds to form three-dimension supramolecule. Compound 1 exhibits intense yellow luminescence in solid state at 298 K(λ em=554 nm), which shows a blue shift at 77 K(ca. 147 nm). Additionally, fluorescence characteristics of compound 1 were investigated in different solvents(polarity: DMSO>CH3CN>CH3OH>CHCl3>toluene) at 298 and 77 K. The results show that the emission peak of compound 1 in solvent exhibits a slight bathochromic shift. However, the emission peaks of compound 1 in CH3OH and CHCl3 are red shift compared with that in CH3CN. It is revealed that the luminescence behavior of compound 1 depends on not only the polarity of solvent but also the hydrogen bonding properties between solvent and solute. In addition, the emission peak of compound 1 in solution shows a red shift obviously at 77 K than that at 298 K(ca. 144–159 nm), with the fluorescence lifetime increased at 77 K. The lifetime in DMSO at 77 K(τ=12.470 μs) was the longest one. The quantum yield of compoud 1 increases with increasing the polarity of solvent within a range of 1.8%–8.3 %.