Diverse evolution of [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 2, 3) metalloligands in CH(2)Cl(2)

The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment.     

Synthesis, characterization, and tautomerism of four novel copper(I) complexes from 3-hydroxy-3-(p-R-phenyl)-2-propenedithioic acids

The paper describes the synthesis and structural characterization of four novel copper(I) complexes [CuL(PPh(3))(2)] (L = 3-hydroxy-3-(p-R-phenyl)-2-propenedithioate). In addition, a tautomeric equilibrium in solution was found and Hammett correlations with (13)C NMR parameters were studied. The structure of one complex was fully established by X-ray diffraction analysis.     

CRDOCK: An Ultrafast Multipurpose Protein-Ligand Docking Tool

An ultrafast docking and virtual screening program, CRDOCK, is presented that contains (1) a search engine that can use a variety of sampling methods and an initial energy evaluation function, (2) several energy minimization algorithms for fine tuning the binding poses, and (3) different scoring functions. This modularity ensures the easy configuration of custom-made protocols that can be optimized depending on the problem in hand. CRDOCK employs a precomputed library of ligand conformations that are initially generated from one-dimensional SMILES strings. Testing CRDOCK on two widely used benchmarks, the ASTEX diverse set and the Directory of Useful Decoys, yielded a success rate of ～75% in pose prediction and an average AUC of 0.66. A typical ligand can be docked, on average, in just ～13 s. Extension to a representative group of pharmacologically relevant G protein-coupled receptors that have been recently cocrystallized with some selective ligands allowed us to demonstrate the utility of this tool and also highlight some current limitations. CRDOCK is now included within VSDMIP, our integrated platform for drug discovery.     

Electrochemically Generated Nanoparticles of Halogen‐Bridged Mixed‐Valence Binuclear Metal Complex Chains

Spherical nanoparticles composed of MMX chains can be made by a polymerization strategy driven by electrochemical processes. In particular, the [Pt₂(MeCS₂)₄I₂] (MMI₂) dimetal subunit is employed as a monomer for the formation of [Pt₂(MeCS₂)₄I]_n spherical nanostructures on surfaces. We have paid particular attention to elucidating the general mechanism of the deposition process on the basis of in situ electrochemical measurements. The reduction of MMI₂ to give the electrodeposition of nanostructures agrees well with formation of the reduced [MMI₂]^? species followed by a disproportionation mechanism mediated by iodide anions. The chemical composition of the particles was determined by energy‐dispersive X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS) to reveal the MMI₂ polymer.     

In vitro studies of carbon fiber microbiosensor for dopamine neurotransmitter supported by copper-graphene oxide composite

A composite was prepared from copper and graphene oxide (Cu-GO) by in-situ chemical reduction of a mixture containing GO and Cu(II) ions with potassium borohydride. The morphology and structure of the composite were confirmed by various physicochemical techniques. The materials were used in a tyrosinase-based microbiosensor where the enzyme is immobilized in a biocompatible matrix consisting of poly(ortho-phenylene diamine) and Cu-GO. The composite was deposited on the surface of an 8-μm thick carbon fiber microelectrode. The role of each component in the sensing layer was systematically investigated with respect to the analytical performance of the system. In its optimal configuration, the biosensor demonstrated (a) a sensitivity of 6.1?±?3 nA mM^-1 dopamine (DA), (b) a linear response to DA (with a Michaelis-Menten constant of 0.29?±?0.03 mM), (c) good selectivity over ascorbic acid and uric acid, and (d) a high blocking capacity (112.2?±?2 mM) for ascorbic acid.

Study of the Interaction Between Promazine Hydrochloride and Surfactant (Conventional/Gemini) Mixtures at Different Temperatures

In the present paper, the micellization of an amphiphilic drug, promazine hydrochloride, and gemini surfactants (16-s-16) with s = 4–6 and the monomeric hexadecyltrimethylammonium bromide (CTAB) counterparts has been examined conductometrically in the pure and mixed states in aqueous solutions at different compositions and temperatures (298.15–308.15 K). Dicationic gemini surfactants provide much better environment for the micellization behavior than the corresponding monocationic counterpart CTAB. The critical micelle concentration (cmc) values are lower than the cmc for ideal mixing, cmc ^id, suggesting attractive interactions between the two components in mixed micelles. The micellar mole fractions of surfactants, evaluated by different models, show greater contributions of surfactants in mixed micelles and increase with increasing concentrations of these surfactants. The negative values of β suggest synergism in the mixtures, which is highly beneficial as it reduces the total amount of surfactants required in a particular application, leading to reductions of cost and environmental impact. Activity coefficients (f ₁ and f ₂) are always less than unity showing nonideality in the systems. The data have been also used for evaluation of thermodynamic parameters.     

Cytochrome P450 Catalyzed Oxidative Hydroxylation of Achiral Organic Compounds with Simultaneous Creation of Two Chirality Centers in a Single CH Activation Step

Regio‐ and stereoselective oxidative hydroxylation of achiral or chiral organic compounds mediated by synthetic reagents, catalysts, or enzymes generally leads to the formation of one new chiral center that appears in the respective enantiomeric or diastereomeric alcohols. By contrast, when subjecting appropriate achiral compounds to this type of C? H activation, the simultaneous creation of two chiral centers with a defined relative and absolute configuration may result, provided that control of the regio‐, diastereo‐, and enantioselectivity is ensured. The present study demonstrates that such control is possible by using wild type or mutant forms of the monooxygenase cytochrome P450 BM3 as catalysts in the oxidative hydroxylation of methylcyclohexane and seven other monosubstituted cyclohexane derivatives.     

Zinc‐Catalyzed Functionalization of SiH Bonds with 2‐Furyl Carbenoids through Three‐Component Coupling

A three‐component coupling of alk‐2‐ynals, 1,3‐dicarbonyls and silanes is reported. ZnCl₂ serves as an inexpensive and low‐toxic catalyst for the overall transformation, which involves Knoevenagel condensation, cyclization, and carbene Si?H bond insertion. The process takes place with high atom economy in the absence of organic solvents and shows a broad scope. This reaction is also applicable to the functionalization of oligomeric siloxanes.     

Direct On‐Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature

We report herein an efficient, fast, and simple synthesis of an imine‐based covalent organic framework (COF) at room temperature (hereafter, RT‐COF‐1 ). RT‐COF‐1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N₂ and CO₂. The room‐temperature synthesis has enabled us to fabricate and position low‐cost micro‐ and submicropatterns of RT‐COF‐1 on several surfaces, including solid SiO₂ substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink‐jet printing.     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.