The design of molecular sensing interfaces with lipid-bilayer assemblies

We describe the current status of techniques for preparing planar lipid bilayers, the fusion of sensory elements and the design of bilayer interfaces for analytical applications. Advances in bilayer fabrication have allowed preparation of lipid bilayers with membrane resistance of >1 GΩ (“gigaseal”) in flow, microfluidic and array formats, which have enabled single-channel and multi-channel recording. Not only biological but also engineered channels have been adopted as sensory elements for lipid-bilayer-based biosensors. Synthetic and inorganic channels are also emerging for designing membranes for lipid-bilayer sensors. We discuss the potential of lipid bilayers containing biological, engineered or synthetic channels for the design of biosensors, including drug-screening biosensors.     

Variation in the chromatographic,material, and chemical characteristics of methacrylate‐based polymer monoliths during photoinitiated low‐temperature polymerization

Both the separation behavior and the structure of a polymer monolith column depends on both the reaction solution composition and the polymerization conditions. In photoinitiated low‐temperature polymerization, polymerization temperature, irradiation intensity, and polymerization time were key factors to control the monolith characteristics. In this study, the effect of polymerization time on the chromatographic, material, and chemical characteristics of poly(butyl methacrylate‐co‐ethylene dimethacrylate) monoliths was studied using pyrolysis‐gas chromatography, Raman spectroscopy, inverse size exclusion chromatography, scanning electron microscopy, and chromatographic methods. Both butyl methacrylate and ethylene dimethacrylate monomers were incorporated into the monolith as the polymerization time increased, and it resulted in increases in both the flow resistance (decrease in both permeability and total/through pore porosities) and retention factors. The longer polymerization time led to lower relative amounts of free methacrylate functional groups in the monolith, i.e. cross‐linking was enhanced. The increase of the polymerization time from 8 to 12 min significantly reduced the separation efficiency for the retained analyte, whereas an increase in the fraction of the mesoporosity was observed.     

Diastereomer-specific effects of double-stranded peptides conjugated with -L-Tyr-L-Phe- or -L-Tyr-D-Phe- residues on tyrosine phosphorylation and inhibition of src(ts)NRK, A431, MCF-7, and DU145 cell growth

The interaction between growth inhibition and chirality, especially of diastereomers, has an important modifying effect on cancer cell proliferation. Previously, we have reported on the design, synthesis, and chemical properties of a series of novel, double-stranded peptides, (y-AA-x-AA)(2)-(CH(2))(12), with -y-AA-x-AA- and -z-AA-y-AA-x-AA- sequences conjugated to the spacer. Here, we extend those results by showing that (D-, L-) and (L-, D-) diastereomers are more potent inhibitors of tyrosine phosphorylation than (L-, L-). Although the replacement of the L-Phe-L-Phe sequence with L-Tyr-L-Phe produces a less active inhibitor, the double-stranded peptide conjugated with L-Tyr-D-Phe is more active than that conjugated with L-Tyr-L-Phe. In addition, we show that SDS-PAGE gel profiles of tyrosine phosphorylation following treatment with bis(y-Tyr-x-Phe)-N,N-dodecane-1,12-diamine appear very similar to profiles of tyrosine phosphorylation following treatment with an analog of the tyrosine kinase inhibitor, erbstatin. Moreover, the level of autophosphorylation of the epidermal growth factor receptor kinase domain (EGFRKD) treated with bis(L-Tyr-D-Phe)-N,N-dodecane-1,12-diamine was lower than that seen following treatment with bis(L-Phe-D-Phe)-N,N-dodecane-1,12-diamine. These data provide new insights for the control of cancer cell proliferation through drug designs which replace the less active -L-Phe-L-Phe- (and -D-Phe-L-Phe-) with the more active -L-Tyr-L-Phe- (and -L-Tyr-D-Phe-) sequence.     

Single-molecule magnet behavior in heterometallic M(II)-Mn(III)(2)-M(II) tetramers (M(II) = Cu, Ni) containing Mn(III) salen-type dinuclear core

The linear-type heterometallic tetramers, [Mn(III)(2)(5-MeOsaltmen)(2)M(II)(2)(L)(2)](CF(3)SO(3))(2) x 2H(2)O (MII = Cu, 1a; Ni, 2a), where 5-MeOsaltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene) bis(5-methoxysalicylideneiminate), and H(2)L = 3-{2-[(2-hydroxy-benzylidene)-amino]-2-methyl-propylimino}-butan-2-one oxime, have been synthesized and characterized from structural and magnetic points of view. These two compounds are isostructural and crystallize in the same monoclinic P2(1)/n space group. The structure has a [M(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-M(II)] skeleton, where -NO- is a linking oximato group derived from the non-symmetrical Schiff-base complex [M(II)(L)] and -(O)(2)- is a biphenolato bridge in the out-of-plane [Mn(2)(5-MeOsaltmen)(2)](2+) dimer. The solvent-free compounds, 1b and 2b, have also been prepared by drying of the parent compounds, 1a and 2a, respectively, at 100 degrees C under dried nitrogen. After this treatment, the crystallinity is preserved, and 1b and 2b crystallize in a monoclinic P2(1)/c space group without significant changes in their structures in comparison to 1a and 2a. Magnetic measurements on 1a and 1b revealed antiferromagnetic Mn(III)---Cu(II) interactions via the oximato group and weak ferromagnetic Mn(III)---Mn(III) interactions via the biphenolato bridge leading to an S(T) = 3 ground state. On the other hand, the diamagnetic nature of the square planar Ni(II) center generates an S(T) = 4 ground state for 2a and 2b. At low temperature, these solvated (a) and desolvated (b) compounds display single-molecule magnet behavior modulated by their spin ground state.     

Study of pyrolysis kinetic of green corn husk

In this paper, it was suggested the use of green corn husk, which is a biomass from agro-industry, as an alternative source of energy through its pyrolysis. Green corn husk characterization was done through immediate and elemental analysis of its components: cellulose, hemicelluloses, and lignin. It was also measured its higher calorific value. The pyrolysis study of green corn husk was done by the isoconversion and the Master plots method. Thermogravimetric plots were obtained at heating rates of 5, 10, 15, and 20 °C min^?1. The pyrolysis kinetics parameters were studied through the Flynn–Wall–Ozawa (FWO), Kissinger, and Friedman models. The Master plots method was used to determine the pyrolysis reaction order. The results of the reaction energy activation were found to be in the range 105.21–157.46 kJ mol^?1 by the FWO method, 150.50 kJ mol^?1 by the Kissinger method, and ranged 120.66–163.81 kJ mol^?1 by the Friedman method. The Master plots method showed a three-way-transport diffusional kinetics for the biomass de-volatilization process. The higher calorific value found for green corn husk was 16.14 MJ kg^?1. The simulation showed correlation between the experimental data and the proposed model for conversion values up to 0.8.

     

Salviskinone A, a diterpene with a new skeleton from Salvia przewalskii

A novel compound, named salviskinone A (1), was isolated from Salvia przewarskii. The compound has a rearranged carbon skeleton with a methyl unit at C-5 from abietane-type diterpene. Its structure and relative stereochemistry were elucidated by detailed spectroscopic analysis, including HREIMS and 2DNMR (COSY, HSQC, HMBC, and NOESY) spectra.     

A high voltage organic-inorganic hybrid photovoltaic cell sensitized with metal-ligand interfacial complexes

A thin solid-state photovoltaic cell of organic-inorganic hetero junctions was fabricated by forming a dye-metal charge-transfer complex as the sensitizer monolayer at the interface of crystalline state organic and inorganic semiconductors. The organic-inorganic hybrid thin-film photocell generates a high photovoltage of 1.2 V, yielding an energy conversion efficiency of up to 1.5%.     

A Ru(I) metalloradical that catalyzes nitrene coupling to azoarenes from arylazides

Unusual N-N coupling of aryl azides to yield azoarenes is demonstrated by the Ru(I) metalloradical, [SiP(iPr)(3)]Ru(N(2)) (4) ([SiP(iPr)(3)] = (2-iPr(2)PC(6)H(4))(3)Si(-)). The yield of the azoarene is dependent on the substituent on the aryl azide, and the reaction is catalytic for p-methoxy and p-ethoxy phenyl azides, while no azoarene is observed for p-trifluoromethylphenyl azide. Studies aimed at probing the viability of a bimolecular coupling mechanism of metal imide species, as shown in the related [SiP(iPr)(3)]Fe system, have led to the isolation of several structurally unusual complexes including the ruthenium(IV) imide, 7-OMe, as well as the Ru(II) azide adduct 8-OMe. One electron reduction of 7-OMe complex led to the isolation of the formally Ru(III) imide complex, [SiP(iPr)(3)]Ru(NAr) (Ar = p-MeOC(6)H(4), 5-OMe). EPR spectroscopy on 5-OMe suggests that the complex is electronically similar to the previously reported imide complex, [SiP(iPr)(3)]Ru(NAr) (Ar = p-CF(3)C(6)H(4,)5-CF(3)), and features radical character on the NAr moiety, but to a greater degree. The stability of 5-OMe establishes that bimolecular coupling of 5-OMe is kinetically inconsistent with the reaction. Further studies rule out mechanisms in which 5-OMe reacts directly with free aryl azide or a transient Ru(I) azide adduct. Together, these studies show that 5-OMe is likely uninvolved in the catalytic cycle and demonstrates the influence of the metal center on the mechanism of reaction. Instead, we favor a mechanism in which free aryl nitrene is released during the catalytic cycle and combines with itself or with free aryl azide to yield the azoarene.     

Intermolecular Radical Reaction of O,Se-Acetals Generated via Seleno-Pummerer Rearrangement

A new general protocol for the synthesis of O,Se-acetals using the seleno-Pummerer reaction has been developed, and their radical-based two- and three-component coupling reactions were studied. The three-component coupling employed the O,Se-acetal, cyclopentenone, and an allylstannane derivative, and enabled stereoselective installations of α-acyloxy alkyl and functionalized allyl groups to generate the 2,3-trans-disubstituted cyclopentanone in a single operation. The obtained highly functionalized structure was used as an intermediate for facile assembly of the zedoarondiol carboskeleton.     

Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III)

A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]?4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M???M distance being relatively large at 9?? due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3?K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.