The synthesis and structural properties of a chlorido-bis-{N-[(4-meth-oxy-phen-yl)imino]-pyrrolidine-1-carboxamide}-zinc(II) (aceto-nitrile)-trichlorido-zincate coordination complex.

The title complex, [ZnCl(C12H15N3O2)2][ZnCl3(CH3CN)], was synthesized and its structure was fully characterized through single-crystal X-ray diffraction analysis. The complex crystallizes in the ortho-rhom-bic system, space group Pbca (61), with a central zinc atom coordinating one chlorine atom and two pyrrolidinyl-4-meth-oxy-phenyl azoformamide ligands in a bidentate manner, utilizing both the nitro-gen and oxygen atoms in a 1,3-heterodiene (N=N-C=O) motif for coordinative bonding, yielding an overall positively (+1) charged complex. The complex is accompanied by a [(CH3CN)ZnCl3]- counter-ion. The crystal data show that the harder oxygen atoms in the heterodiene zinc chelate form bonding inter-actions with distances of 2.002 (3) and 2.012 (3) Å, while nitro-gen atoms are coordinated by the central zinc cation with bond lengths of 2.207 (3) and 2.211 (3) Å. To gain further insight into the inter-molecular inter-actions within the crystal, Hirshfeld surface analysis was performed, along with the calculation of two-dimensional fingerprint plots. This analysis revealed that H⋯H (39.9%), Cl⋯H/H⋯Cl (28.2%) and C⋯H/H⋯C (7.2%) inter-actions are dominant. This unique crystal structure sheds light on arrangement and bonding inter-actions with azo-formamide ligands, and their unique qualities over similar semicarbazone and azo-thio-formamide structures.

Evaluation of azothioformamides and their copper(I) and silver(I) complexes for biological activity.

Redox-active azothioformamides (ATFs) contain an NNCS 1,3-heterodiene motif typically found in other molecular subclasses that exhibit a wide range of cytotoxic and anti-neoplastic effects, either alone or as chelation complexes with various metals. For this study, a small library of ATF compounds was synthesized and tested across a range of microbes, fungi, and cancer cell lines for biological activity, both alone and as metal chelates of copper(I) and silver(I) salts. Alone, the ATF compounds exhibited little antimicrobial activity, but all inhibited the cell growth of A549 lung carcinoma cells (IC50 values of 1-6 µM). As copper(I) and silver(I) coordination complexes, several of the ATFs showed antimicrobial activity against gram positive Staphylococcus aureus and Bacillus subtilis cells (IC50 âˆ¼ 5-20 µM) and the fungi Candida albicans (IC50 âˆ¼ 8-12 µM); as well as cytotoxicity against both lung carcinoma A549 cells and lymphoblastic leukemia K562 cells.

Synthesis of a zwitterionic N-Ser-Ser-C dimethacrylate cross-linker and evaluation in polyampholyte hydrogels.

Polyampholyte hydrogels are attractive materials for tissue engineering scaffolds as they offer a wide variety of features including nonfouling, selective protein delivery, and tunable physical characteristics. However, to improve the potential performance of these materials for in vivo applications, there is a need for a higher diversity of zwitterionic cross-linker species to replace commonly used ethylene glycol (EG) based chemistries. Towards this end, the synthesis of a dipeptide based zwitterionic cross-linker, N-Ser-Ser-C dimethacrylate (S-S) from N-Boc-l-serine is presented. The strategy utilized a convergent coupling of methacrylated serine partners followed by careful global deprotection to yield the zwitterionic cross-linker with good overall yields. This novel cross-linker was incorporated into a polyampholyte hydrogel and its physical properties and biocompatibility were compared against a polyampholyte hydrogel synthesized with an EG-based cross-linker. The S-S cross-linked hydrogel demonstrated excellent nonfouling performance, while promoting enhanced cellular adhesion to fibrinogen delivered from the hydrogel. Therefore, the results suggest that the S-S cross-linker will demonstrate superior future performance for in vivo applications.

The synthesis and crystal structure of bis-[3,3-diethyl-1-(phenyl-imino-κN)thio-urea-κS]silver hexa-fluorido-phosphate.

The structure of the title complex, [Ag(C11H15N3S)2]PF6, has monoclinic (P21/c) symmetry, and the silver atom has a distorted square-planar geometry. The coordination complex crystallized from mixing silver hexa-fluorido-phosphate with a concentrated tetra-hydro-furan solution of N,N-di-ethyl-phenyl-azo-thio-formamide [ATF; systematic name: 3,3-diethyl-1-(phenyl-imino)-thio-urea] under ambient conditions. The resultant coordination complex exhibits a 2:1 ligand-to-metal ratio, with the silver(I) atom having a fourfold AgN2S2 coordination sphere, with a single PF6 counter-ion. In the crystal, however, one sulfur atom from an ATF ligand of a neighboring complex coordinates to the silver atom, with a bond distance of 2.9884 (14) Å. This creates a polymeric zigzag chain propagating along the c-axis direction. The chains are linked by C-H⋯F hydrogen bonds, forming slabs parallel to the ac plane.

Key features and updates for origin 2018.

OriginLab's newest version update to Origin and OriginPro includes ease-of-use features, like Origin Central updates and creation of an App Center, as well as larger changes like the addition of Unicode characters, alteration to how user files are stored and visually searched, and user input formula in cells within worksheets. These features add additional value to an already powerful data analysis and plotting software package.

Deconvoluting the Innocent vs. Non-innocent Behavior of N,N-diethylphenylazothioformamide Ligands with Copper Sources.

Redox-active ligands lead to ambiguity in often clearly defined oxidation states of both the metal centre and the ligand. The arylazothioformamide (ATF) ligand class represents a redox-active ligand with three possible redox states (neutral, singly reduced, and doubly reduced). ATF-metal interactions result in strong colorimetric transitions allowing for the use of ATFs in metal detection and/or separations. While previous reports have discussed dissolution of zerovalent metals, the resulting oxidation states of coordination complexes have proved difficult to interpret through X-ray crystallographic analysis alone. This report describes the X-ray crystallographic analysis combined with computational modelling of the ATF ligand and metal complexes to deconvolute the metal and ligand oxidation state of metal-ATF complexes. Metal(ATF)2 complexes that originated from zerovalent metals were found to exist as dicationic metal centers containing two singly reduced ATF ligands. When employing Cu(I) salts instead of Cu(0) to generate copper-ATF complexes, the resulting complexes remained Cu(I) and the ATF ligand remained "innocent", existing in its neutral state. Although the use of CuX (where X = Br or I) or [Cu(NCMe)4]Y (where Y = BF4 or PF6) generated species of the type: [(ATF)Cu(µ-X)]2 and [Cu(ATF)2]Y, respectively, the ATF ligand remained in its neutral state for each species type.

Autonomic molecular transport by polymer films containing programmed chemical potential gradients.

Materials which induce molecular motion without external input offer unique opportunities for spatial manipulation of molecules. Here, we present the use of polyacrylamide hydrogel films containing built-in chemical gradients (enthalpic gradients) to direct molecular transport. Using a cationic tertiary amine gradient, anionic molecules were directionally transported up to several millimeters. A 40-fold concentration of anionic molecules dosed in aerosol form on a substrate to a small region at the center of a radially symmetric cationic gradient was observed. The separation of mixtures of charged dye molecules was demonstrated using a boronic acid-to-cationic gradient where one molecule was attracted to the boronic acid end of the gradient, and the other to the cationic end of the gradient. Theoretical and computational analysis provides a quantitative description of such anisotropic molecular transport, and reveals that the gradient-imposed drift velocity is in the range of hundreds of nanometers per second, comparable to the transport velocities of biomolecular motors. This general concept of enthalpy gradient-directed molecular transport should enable the autonomous processing of a diversity of chemical species.

Polymer brushes patterned with micrometer-scale chemical gradients using laminar co-flow.

We present a facile microfluidic method for forming narrow chemical gradients in polymer brushes. Co-flow of an alkylating agent solution and a neat solvent in a microfluidic channel forms a diffusion-driven concentration gradient, and thus a gradient in reaction rate at the interface of the two flows, leading to a quaternization gradient in the underlying poly(2-(dimethylamino)ethyl methacrylate) polymer brush. The spatial distribution of the quaternized polymer brush is characterized by confocal Raman microscopy. The quaternization gradient length in the polymer brush can be varied with the injection flow rate and the distance from the co-flow junction. A chemical gradient in the polymer brush as narrow as 5 µm was created by controlling these parameters. The chemical gradient by laminar co-flow is compared with numerical calculations that include only one adjustable parameter: the reaction rate constant of the polymer brush quaternization. The calculated chemical gradient agrees with the experimental data, which validates the numerical procedures established in this study. Flow of multiple laminar streams of reactive agent solutions enables single-run fabrication of brush gradients with more than one chemical property. As one example, four laminar streams-neat solvent/benzyl bromide solution/propargyl bromide solution/neat solvent-generate multistep gradients of aromatic and alkyne groups. Because the alkyne functional group is a click-reaction available site, the alkyne gradient could allow small gradient formation with a wide variety of chemical properties in a polymer brush.

Synthesis of ß-C-GlcNAc Ser from ß-C-Glc Ser.

The glycosylation of proteins, specifically installation of O-GlcNAc on Ser/Thr residues, is a dynamic control element for transcription repression, protein degradation, and nutrient sensing. To provide homogeneous and stable structures with this motif, the synthesis of a C-linked mimic, C-GlcNAc Ser, has been prepared from the C-Glc Ser by a double inversion strategy using azide to insert the C-2 nitrogen functionality. The C-Glc Ser was available by a ring-closing metathesis and hydroalkoxylation route.

Synthesis of benzocycloheptanones through coupling of δ,ε-unsaturated chromium carbene complexes and 2-alkynylbenzoyl derivatives.

The coupling of pentenylcarbene complexes and 2-alkynylbenzoyl derivatives affords naphthocycloheptanones in a single step involving simultaneous construction of both the seven-membered ring and one of the aromatic rings. Aryl tethered systems undergo intramolecular cyclopropanation.

Synthesis and structural characterization of a fused bispyrone and preparation of the first metal bispyrylium complexes.

Dehydroacetic acid reacts with acetic anhydride in the presence of perchloric acid to give a salt which upon careful neutralization affords a fused bis-gamma-pyrone. The bis-gamma-pyrone forms stable metal complexes with Li, Mg, Cu(II), Ni(II), Zn, Fe(II), Co(II) and Ba perchlorates whose crystal structures reveal that the ligand possesses significant bispyrylium character while the metal is coordinated at the negatively charged edge of the structure.