Direct observations of freeze-etching processes of ice-embedded biomembranes by atomic force microscopy

We have fabricated a cryogenic atomic force microscope that is designed for structural investigation of freeze-fractured biological specimens. The apparatus is operated in liquid nitrogen gas at atmospheric pressure. Freeze-fracturing, freeze-etching and subsequent imaging are carried out in the same chamber, so that the surface topography of a fractured plane is easily visualized without ice contamination. A controlled superficial sublimation of volatile molecules allows us to obtain three-dimensional views of ultrastructures of biological membranes.     

Spectroscopic properties and amplified spontaneous emission of a new derivative of fluorescein

The new laser dye, 2-(6-acryloyloxy-3-oxo-3H-xanthen-9-yl)-benzoic acid ethyl ester [AOXBE] has been synthesized. Its chemical structure was confirmed by ¹HNMR, IR, MS and elemental analysis. This new dye was covalently bonded with methyl methacrylate (MMA) and 2-hydroxy ethyl-methacrylate (HEMA) copolymer backbone. Its optical properties were experimentally investigated. Amplified spontaneous emission (ASE) and photostability were studied by pumping the dye polymeric sample with a 355 nm (8 ns) pulsed Nd:YAG laser. PACS 42.55.Mv; 42.70.Hj; 42.70.Jk; 42.55.Px     

Monitoring the brain metabolites of children with acute encephalopathy caused by the H1N1 virus responsible for the 2009 influenza pandemic: a quantitative in vivo H MR spectroscopy study

Background and Purpose

Influenza viral infection, which results in central nervous system dysfunction, is a major cause of acute encephalopathy (AE). The purpose of this study was to investigate the changes in the concentrations of brain metabolites in children with AE using single-voxel magnetic resonance spectroscopy (MRS) and to provide diagnostic information about the relationship between the symptoms of AE and metabolite concentrations.

Materials and Methods

The subjects were 10 children (mean age: 6.2 years; range: 1–13) with AE caused by the novel influenza A virus responsible for the 2009 influenza pandemic. The serial MRS data (TE/TR=30/5000 ms, 3 T) acquired from the basal ganglia (BG) and centrum semiovale (CS) of each patient were categorized into three periods: (1) initial neurological symptom presentation and the start of treatment (n= 10), (2) short-term follow-up (n= 9) and (3) long-term follow-up (n= 3). As controls, the magnetic resonance (MR) spectra of eight age-matched children were also investigated.

Results

In both regions, the concentrations of the major metabolites (N-acetylaspartate, creatine, choline, myo-inositol, glutamate/glutamine complex and glutamate) only showed minor fluctuations between the three periods. On the other hand, higher levels of taurine (Tau) were observed in the BG during the second period (P=.005), and increased levels of glucose were observed in the CS during the first (P=.005) and second (P=.036) periods.

Conclusions

Serial monitoring of brain metabolite changes was carried out with a clinical MR system. The concentrations of major metabolites only displayed very minor fluctuations in response to mild H1N1-related AE. However, a higher Tau concentration was found to be associated with neurological symptoms. Further studies are required to improve our understanding of the detailed activity of Tau in AE.     

Synthesis of ternary and quaternary graphite intercalation compounds containing alkali metal cations and diamines

A series of ternary graphite intercalation compounds (GICs) of alkali metal cations (M = Li, Na, K) and diamines [EN (ethylenediamine), 12DAP (1,2-diaminopropane), and DMEDA (N,N-dimethylethylenediamine)] are reported. These include stage 1 and 2 M-EN-GIC (M = Li, d(i) = 0.68-0.84 nm; M = Na, d(i) = 0.68 nm), stage 2 Li-12DAP-GIC (d(i) = 0.83 nm), and stage 1 and 2 Li-DMEDA-GIC (d(i) = 0.91 nm), where d(i) is the gallery height. For M = Li, a perpendicular-to-parallel transition of EN is observed upon evacuation, whereas for M = Na, the EN remains in parallel orientation. Li-12DAP-GIC and Li-DMEDA-GIC contain chelated Li(+) and do not show the perpendicular-to-parallel transition. We also report the quaternary compounds of mixed cations (Li,Na)-12DAP-GIC and mixed amines Na-(EN,12DAP)-GIC, with d(i) values in both cases between those of the ternary end members. (Li,Na)-12DAP-GIC is a solid solution with lattice dimensions dependent on composition, whereas for Na-(EN,12DAP)-GIC, the lattice dimension does not vary with amine content.     

Structural and optical properties of nano-structured tungsten-doped ZnO thin films grown by pulsed laser deposition

Novel highly c-oriented tungsten-doped zinc oxide (WZO) thin films with 1 wt% were grown by pulsed laser deposition (PLD) technique on corning 1737F glass substrate. The effects of laser energy on the structural, morphological as well as optical transmission properties of the films were studied. The films were highly transparent with average transmittance exceeding 87% in the wavelength region lying between 400 and 2500 nm. X-ray diffraction analysis (XRD) results indicated that the WZO films had c-axis preferred orientation with wurtzite structure. Film thickness and the full width at half maximum (FWHM) of the (0 0 2) peaks of the films were found to be dependent on laser fluence. The composition determined through Rutherford backscattering spectroscopy (RBS) appeared to be independent of the laser fluence. By assuming a direct band gap transition, the band gap values of 3.36, 3.34 and 3.31 eV were obtained for corresponding laser fluence of 1, 1.7 and 2.7 J cm⁻², respectively. Compared with the reported undoped ZnO band gap value of 3.37 eV, it is conjectured that the observed low band gap values obtained in this study may be attributable to tungsten incorporation in the films as well as the increase in laser fluence. The high transparency makes the films useful as optical windows while the high band gap values support the idea that the films could be good candidates for optoelectronic applications.     

Sequence Analysis for Alternating Copolymers by MALDI‐TOF‐MS: Importance of Initiator Selectivity for Comonomer Pair

A special initiator for metal‐catalyzed living radical polymerization facilitates sequence analyses by matrix‐assisted laser desorption/ionization time of flight mass spectrometry (MALDI‐TOF‐MS) of alternating copolymers from styrene and maleimide derivatives. The initiator is a malonate‐based alkyl halide (DEMM‐Br), in which two ester groups are attached on the carbon neighboring to bromide, and poor electron density of the radical species allows determination of next unit to the initiator in resultant alternating copolymers due to the selective initiation to styrene derivative. Thanks to the well‐defined α‐end group, sequence of the oligomeric products via radical copolymerization of PMS and EMI with DEMM‐Br can be more simply analyzed by MALDI‐TOF‐MS, and indeed the following are clarified: the crossover propagation is almost perfectly controlled regardless of the injection ratio; a minor error event of the disordered alternating sequence containing St–St sequential unit could take place; the minor error can be suppressed with an excess amount of maleimide.

     

Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.

This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures.     

Radical polymerisation of styrene in porous coordination polymers

The first radical polymerisation of styrene in porous coordination polymers has been carried out, providing stable propagating radicals (living radicals), and a specific space effect of the host frameworks on the monomer reactivity is demonstrated.     

Effects of Temperature and Mobile Phase Condition on Chiral Recognition of Poly(l-phenylalanine) Chiral Stationary Phase

Characteristics of the chiral stationary phase with poly(l-phenylalanine) peptide selector, which was in ??-helical state, was reported. Since environmental factors affect peptide conformation, the changes in enantioselectivity were examined depending on column temperature and mobile phase conditions (ionic strength, pH, mobile phase composition). Column temperature and pH drastically affected the enantioselectivity. Based on these changes, the relation between chiral recognition and secondary structure of the peptide selector was discussed. The column stability during sequential analysis under different separation conditions was also evaluated.     

Synthesis and Magnetic Property of Polyacetylene Bearing πConjugated Bis(Diphenylene)Phenylallyl Radical

Abstract

m- and p Bis(diphenylene)propenylphenylacetylene (m-, p-8) were synthesized and polymerized with WCI₆, MoCl₅, and Rh catalyst, yielding solvent-soluble poly(phenylacetylene)s bearing a π-conjugated bis(di-phenylene)propenyl groups (m-, p-7a). The polymers gave their polyanion derivatives, which were electrolytically and chemically oxidized to yield the corresponding polyradicals (m-, p-7b). The polyradicals were chemically very stable due to the resonance stabilization of an unpaired electron whose spin concentration could be increased up to ca. 2 × 10²³ spins per molar monomer unit. ESR spectroscopy suggested an antiferro-magnetic interaction between unpaired electrons.