Syntheses and structures of N-polyfluorophenyl- and N,N′-bis(polyfluorophenyl)ethane-1,2-diaminato(1- or 2-)platinum(II) complexes

The reaction of [PtX₂(L)] (X = Cl, Br, I; L = NH₂CH₂CH₂NY₂; Y = Et, Me) with thallium(I) carbonate and a polyfluorobenzene (RF) in pyridine (py) yields the platinum(II) complexes, [Pt{N(R)CH₂CH₂NY₂}X(py)] (R = C₆F₅, 4-HC₆F₄, 4-BrC₆F₄, or 4-IC₆F₄, Y = Et (1), Me (2), X = Cl, Br or I) in an improved synthesis. From the reaction of [PtCl₂(H₂NCH₂)₂)] with Tl₂CO₃ and 1,2,3,4-tetrafluorobenzene or 2-bromo-1,3,4,5-tetrafluorobenzene in py, the new complexes [Pt(NRCH₂)₂(py)₂] (3) (R = C₆H₂F₃-2,3,6 and C₆HBrF₃-2,3,5,6) have been isolated but the latter preparation also gave product(s) with a 4-bromo-2,3,5-trifluorophenyl group. From an analogous preparation in 4-ethylpyridine (etpy), [Pt(N(4-HC₆F₄)CH₂)₂(etpy)₂] (4) was obtained. The X-ray crystal structures of (3) (R = C₆HBrF₃-2,3,5,6) and (4) were determined as well as that of the previously prepared (3) (R = 4-BrC₆F₄) and a more precise structure of (3) (R = 4-HC₆F₄) has been obtained.     

Performance of a biomimetic oxidation catalyst immobilized on silicon wafers: comparison with its gold congener

With the aim of extending the usefulness of an existing biomimetic catalytic system, cobalt porphyrin catalytic units with thiol linkers were heterogenized via chemical grafting to silicon wafers and utilized for the catalytic oxidation of hydroquinone to p-benzoquinone. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to analyze the morphology and composition of the heterogeneous catalyst. The results of the catalytic oxidation of hydroquinone obtained with porphyrins grafted on silicon were compared with those obtained earlier with the same catalyst in homogeneous phase and immobilized on gold. It was found that the catalysis could run over 400 h, without showing any sign of deactivation. The measured catalytic activity is at least 10 times higher than that measured under homogeneous conditions, but also 10 times lower than that observed with the catalytic unit immobilized on gold. The reasons of this discrepancy are discussed in term of substrate influence and overlayer organization. The silicon-immobilized catalyst has potential as an advanced functional material with applications in oxidative heterogeneous catalysis of organic reactions, as it combines long-term relatively high activity with low cost.     

Mechanical Properties of Dense Zeolitic Imidazolate Frameworks (ZIFs): A High‐Pressure X‐ray Diffraction,Nanoindentation and Computational Study of the Zinc Framework Zn(Im)2, and its Lithium?Boron Analogue,LiB(Im)4

The dense, anhydrous zeolitic imidazolate frameworks (ZIFs), Zn(Im)₂ ( 1 ) and LiB(Im)₄ ( 2 ), adopt the same zni topology and differ only in terms of the inorganic species present in their structures. Their mechanical properties (specifically the Young’s and bulk moduli, along with the hardness) have been elucidated by using high pressure, synchrotron X‐ray diffraction, density functional calculations and nanoindentation studies. Under hydrostatic pressure, framework 2 undergoes a phase transition at 1.69 GPa, which is somewhat higher than the transition previously reported in 1 . The Young’s modulus (E) and hardness (H) of 1 (E≈8.5, H≈1 GPa) is substantially higher than that of 2 (E≈3, H≈0.1 GPa), whilst its bulk modulus is relatively lower (≈14 GPa cf. ≈16.6 GPa). The heavier, zinc‐containing material was also found to be significantly harder than its light analogue. The differential behaviour of the two materials is discussed in terms of the smaller pore volume of 2 and the greater flexibility of the LiN₄ tetrathedron compared with the ZnN₄ and BN₄ units.     

Design and operation of microelectrochemical gates and integrated circuits

Here we report a simple design philosophy, based on the principles of bipolar electrochemistry, for the operation of microelectrochemical integrated circuits. The inputs for these systems are simple voltage sources, but because they do not require much power they could be activated by chemical or biological reactions. Device output is an optical signal arising from electrogenerated chemiluminescence. Individual microelectrochemical logic gates are described first, and then multiple logic circuits are integrated into a single microfluidic channel to yield an integrated circuit that can perform parallel logic functions. AND, OR, NOR, and NAND gates are described. Eventually, systems such as those described here could provide on-chip data processing functions for lab-on-a-chip devices.     

Electrospun Functionalized Polyaniline Copolymer‐Based Nanofibers with Potential Application in Tissue Engineering

Nanofibrous blends of HCl‐doped poly(aniline‐co‐3‐aminobenzoic acid) (3ABAPANI) copolymer and poly(lactic acid) (PLA) were fabricated by electrospinning solutions of the polymers, in varying relative proportions, in dimethyl sulfoxide/tetrahydrofuran mixture. The morphology, mechanical and electrical properties of the nanofibers were characterized and an assessment of their bioactivity performed. To assess cell morphology and biocompatibility, pure PLA and 3ABAPANI‐PLA nanofibrous mats were deposited in the form of three‐dimensional networks with a high degree of connectivity, on glass substrates, and their ability to promote proliferation of COS‐1 fibroblast cells was determined. The nanofibrous electrospun 3ABAPANI‐PLA blends gave enhanced cell growth, potent antimicrobial capability against Staphylococcus aureus and electrical conductivity. This new class of nanofibrous blends can potentially be employed as tissue engineering scaffolds, and in particular have showed promise as the basis of a new generation of functional wound dressings that may eliminate deficiencies of currently available antimicrobial dressings.

     

Direct O-glycosidation of resin bound thioglycosides

The application of the safety-catch linker concept to solid-phase glycoconjugate synthesis is described. The process allows for direct conjugation of resin bound glycans to complex aglycones during cleavage. Large excesses of either coupling partner are not required, and even very hindered alcohols serve as acceptors in the reaction.     

Reaction‐Based Colorimetric and Ratiometric Fluorescence Sensor for Detection of Cyanide in Aqueous Media

A stilbene‐based compound ( 1 ) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F^?, Cl^?, Br^?, I^?, ClO₄^?, H₂PO₄^?, HSO₄^?, NO₃^?, and CH₃CO₂^?. A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron‐deficient cyanoacrylate group of 1 . The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge‐transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.     

Subfrequency noise signal extraction in fiber-optic strain sensors using postprocessing

Laser frequency fluctuations typically limit the performance of high-resolution interferometric fiber strain sensors. Using time delay interferometry, we demonstrate a frequency noise immune fiber sensing system, where strain signals were extracted well below the noise floor normally imposed by the frequency fluctuations of the laser. Initial measurements show a reduction in the noise floor by a factor of 30, with strain sensitivities of a nanostrain/Hz at 100 mHz and reaching 100 ps/Hz at 1 Hz. Further characterization of the system indicates the potential for at least 4.5 orders of magnitude frequency fluctuation rejection.     

Exceptionally low shear modulus in a prototypical imidazole-based metal-organic framework

Using Brillouin scattering, we measured the single-crystal elastic constants (C(ij)'s) of a prototypical metal-organic framework (MOF): zeolitic imidazolate framework (ZIF)-8 [Zn(2-methylimidazolate)(2)], which adopts a zeolitic sodalite topology and exhibits large porosity. Its C(ij)'s under ambient conditions are (in GPa) C(11)=9.522(7), C(12)=6.865(14), and C(44)=0.967(4). Tensorial analysis of the C(ij)'s reveals the complete picture of the anisotropic elasticity in cubic ZIF-8. We show that ZIF-8 has a remarkably low shear modulus G(min) < or approximately 1 GPa, which is the lowest yet reported for a single-crystalline extended solid. Using ab initio calculations, we demonstrate that ZIF-8's C(ij)'s can be reliably predicted, and its elastic deformation mechanism is linked to the pliant ZnN(4) tetrahedra. Our results shed new light on the role of elastic constants in establishing the structural stability of MOF materials and thus their suitability for practical applications.     

Supramolecular Polymeric Chemosensor for Biomedical Applications: Design and Synthesis of a Luminescent Zinc Metallopolymer as a Chemosensor for Adenine Detection

Adenine is an important bio-molecule that plays many crucial roles in food safety and biomedical diagnostics. Differentiating adenine from a mixture of adenosine and other nucleic bases (guanine, thymine, cytosine, and uracil) is particularly important for both biological and clinical applications. A neutral Zn^II metallosupramolecular polymer based on acyl hydrazone derived coordination centres (P1) were generated through self-assembly polymerization. It is a linear coordination polymer that behaves like self-standing film. The synthesis, ¹H-NMR characterization, and spectroscopic properties of this supramolecular material are reported. P1 was found to be a chemosensor specific to adenine, with a luminescent enhancement. The binding properties of P1 with common nucleic bases and nucleosides reveal that this supramolecular polymer is very selective to adenine molecules (~20 to 420 times more selectivity than other nucleic bases). The formation constant (K) of P1 to adenine was found to be log K?=?4.10?±?0.02. This polymeric chemosensor produces a specific response to adenine down to 90?ppb. Spectrofluorimetric and ¹H-NMR titration studies showed that the P1 polymer allows each Zn^II coordination centre to bind to two adenine molecules through hydrogen bonding with their imine and hydrazone protons.