Formal total synthesis of hemibrevetoxin B by a convergent strategy

Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1.     

Preferential Uniplanar Orientation of Cellulose Microfibrils Reinvestigated by the FTIR Technique

A simple detection method to observe the uniplanar orientation behavior of native cellulose microfibrils to the cell wall surface by using Fourier transform infrared (FTIR) spectroscopy in the transmission mode is reported. Four bands at 1372, 1355, 1337, and 1317 cm⁻¹ (the latter two have been mentioned previously by Liang and Marchessault (1960, J. Polym. Sci. 43: 85–100)) were found to be sensitive to such orientation: the two middle bands at 1355 and 1337 cm⁻¹ increase remarkably when the 0.60–61 nm lattice planes lie parallel to the cell wall surfaces. The reverse was true when the 0.53–54 nm lattice planes oriented preferentially. Polarization of the two bands at 1372 and 1355 cm⁻¹ was parallel, while that of the other two bands at lower wavenumbers, i.e., at 1337 and 1317 cm⁻¹, was perpendicular to the molecular axis of cellulose. These bands were assigned to OH-related motion, probably to in-plane OH bending, as reported by Maréchal and Chanzy (2000, J. Mol. Spectrosc. 523: 183–196).     

An efficient asymmetric synthesis of Fmoc-l-cyclopentylglycine via diastereoselective alkylation of glycine enolate equivalent

Stereoselective alkylation of the enolate derived from benzyl (2R,3S)-(−)-6-oxo-2,3-diphenyl-4-morpholinecarboxylate (1) with cyclopentyl iodide afforded anti-α-monosubstituted product, benzyl (2R,3S,5S)-(−)-6-oxo-2,3-diphenyl-5-cyclopentyl-4-morpholinecarboxylate (3) in 60% yield. Catalytic hydrogenolysis over PdCl₂ cleaved the auxiliary ring system to give l-cyclopentylglycine (4) in 84% yield. Subsequent protection of the α-amino function with Fmoc-OSu gave Fmoc-l-cyclopentylglycine (5) in high yield.     

Nitroxide spin probe study of probe size,hydrogen bonding and polymer matrix rigidity effects on poly(acrylic acid)/poly(ethylene oxide) complexes

An electron spin resonance (ESR) spin probe study was performed on 1 : 1 by weight poly(acrylic acid) (PAA)/poly(ethylene oxide) (PEO) complex over the 100–450 K temperature range with a series of tetramethylpiperidyloxy‐based spin probes. Measurements of the parameters T_5mT, Ta and Td demonstrated the effects of probe size and the strength of hydrogen bonding. The probes in the series Tempone, Tempo, Tempol and Tamine (respectively 4‐oxo‐, unsubstituted, 4‐hydroxy‐ and 4‐amino‐2,2,6,6,‐tetramethylpiperidine ‐1‐oxyl) displayed noticeable increases in the hydrogen‐bonding effect, as indicated by Ta and Td. These increases correlated with increasing hydrogen bond acceptor strength. On the other hand, as the probe size became larger, T_5mT gradually increased due to the free volume decrease. These effects were analyzed using the established theoretical relationship of T_5mT to probe volume expressed by f. Meanwhile, in order to investigate the effect of polymer matrix rigidity, a similar study was performed with a nitroxide spin probe, 2,2,6,6‐tetramethyl‐1‐piperidine‐1‐oxyl (Tempo), on PAA/PEO complexes of different weight compositions. The quantitative fast motion fraction in the composite ESR spectrum was calculated. The influence of changes in the composition of PAA on the molecular mobility was characterized by changes of the spectral parameters and τ_c. The molecular mobility was shown to diminish with increasing content of PAA in PAA/PEO blends duo to the restriction of the polymer matrix rigidity increase. Copyright © 2003 John Wiley & Sons, Ltd.     

Conformation of Tax-response elements in the human T-cell leukemia virus type I promoter

Background: HTLV I Tax is believed to activate viral gene expression by binding bZIP proteins (such as CRIB) and increasing their affinities for proviral THE target sites. Each 21 by THE target site contains an imperfect copy of the intrinsically bent CRE target site (the TRE core) surrounded by highly conserved flanking sequences. These flanking sequences are essential for maximal increases in DNA affinity and transactivation, but they are not, apparently, contacted by protein. Here we employ non-denaturing gel electrophoresis to evaluate TRE conformation in the presence and absence of bZIP proteins, and to explore the role of DNA conformation in viral transactivation.Results: Our results show that the TRE-1 flanking sequences modulate the structure and modestly increase the affinity of a CREB bZIP peptide for the TRE-1 core recognition sequence. These flanking sequences are also essential for a maximal increase in stability of the CREB-DNA complex in the presence of Tax.Conclusions: The CRE-like TRE core and the TRE flanking sequences are both essential for formation of stable CRIB-TRE-1 and Tax-CREB-TRE-1 complexes. These two DNA segments may have co-evolved into a unique structure capable of recognizing Tax and a bZIP protein.     

Tuning the mesogenic properties of 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals: the effect of a phenoxy end-group in two sterically equivalent series

Two sterically equivalent series of phenoxy-terminated 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals were synthesised, and their mesogenic properties were characterised by polarised optical microscopy and differential scanning calorimetry (DSC). The phenoxy end-group causes a significant increase in melting point and inhibits – at least partially – the mesomorphism of these materials relative to the parent isomers; in most cases, the broad enantiotropic SmC phase formed by the parent isomers is suppressed by the addition of the phenoxy end-group. However, detailed analyses by small-angle X-ray scattering and monodomain 2D X-ray scattering suggest that these compounds form a SmA phase with a partially intercalated bilayer structure in which the phenoxy end-groups are nanosegregated. Such an intercalated bilayer structure might enable the tuning of smectogenic properties by appropriate substitution of the phenoxy end-groups.     

Kinetics of carbon steel dissolution in ammonium chloride solution containing sodium thiosulfate

The dissolution behavior of carbon steel in ammonium chloride (NH₄Cl) solution containing sodium thiosulfate (Na₂S₂O₃) of various concentrations (0.01 and 0.1 M) was investigated using electrochemical impedance spectroscopy (EIS) and other nonelectrochemical techniques. The weight loss and polarization measurements indicate a significant increase in the NH₄Cl corrosion rate of carbon steel on addition of Na₂S₂O_3. The EIS measurements exhibited two capacitive loops at multiple direct current (dc) potentials for both the concentrations. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to analyze the impedance data. A four-step mechanism with two intermediate adsorbate species of same charge was proposed to explain the dissolution behavior of carbon steel in the given system. The surface coverage values enumerated that the surface was entirely covered with adsorbed species unlike in the pure NH₄Cl system. Charge transfer resistance and polarization resistance values estimated from RMA parameters indicate the increase in a dissolution rate with dc potential. The surface morphology was inspected via field emission scanning electron microscopy, and the corrosion products including surface state of carbon steel electrode were analyzed using energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

Generalizing Rosenbluth's Algorithm to Include Along‐the‐Chain Intramolecular Energies

We incorporate the Boltzmann factors for inter‐monomer bending energy into the monomer growth direction choice in Rosenbluth's algorithm to model chains of arbitrary nearest‐neighbor rigidity. This allows for the consideration of compact (bent state lower in energy), free (straight and bent state equal in energy), or extended chains (bent state higher). We validate against, and compare to, various other results, showing very good agreement with known results for short chains and demonstrate the ability to model chains up to 500 segments long, far beyond the length at which the normal Rosenbluth method becomes unstable for reasonable nonzero bending energies. This approach is easily generalizable both to other energies determinable during chain growth, for example, polymers composed of more than one type of monomer with differing monomer interaction energies, as well as to other chain production algorithms. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1684–1691     

Electrical Impedance Spectroscopic Study of CNT/Ethylene-alt-CO/Propylene-alt-CO Polyketones Nanocomposite

Impedance spectroscopy was utilized to investigate the dielectric properties, ac conductivity and charge transport mechanisms in propylene-alt-CO/ethylene-alt-CO (EPEC) random terpolymer filled with multi-walled carbon nanotubes (MWCNT) as a function of nanofiller content, frequency, and temperature. Equivalent resistor-capacitor (RC) circuit models were proposed to describe the impedance characteristics of the unfilled terpolymer and the nanocomposite at different temperatures. For the nanocomposites, the ac conductivity tended to be frequency independent at low frequencies. At high frequencies, the ac conductivity increased with frequency. The dc conductivity (i.e., plateau of the ac conductivity at low frequencies) at room temperature increased from 10^?9 (Ω·m)^?1 for the unfilled polymer to l0^?3 (Ω·m)^?1 for the 6 wt% MWCNT/EPEC nanocomposite. At low temperatures, the equivalent RC model for EPEC-0 and EPEC-2 was found to consist of a parallel RC circuit. However, for 6 wt% MWCNT/EPEC nanocomposite, an RC model consisting of an R/constant phase element (CPE) circuit and a resistor in series was required to describe the impedance behavior of the nanocomposite.     

Modeling and character analyzing of multiple fractional-order memcapacitors in parallel connection

Recently,the memory elements-based circuits have been addressed frequently in the nonlinear circuit theory due to their unique behaviors.Thus,the modeling and characterizing of the mem-elements become essential.In this paper,the analysis of the multiple fractional-order voltage-controlled memcapacitors model in parallel connection is studied.Firstly,two fractional-order memcapacitors are connected in parallel,the equivalent model is derived,and the characteristic of the equivalent memcapacitor is analyzed in positive or negative connection.Then a new understanding manner according to different rate factor K and fractional orderαis derived to explain the equivalent modeling structure conveniently.Additionally,the negative order appears,which is a consequence of the combination of memcapacitors in different directions.Meanwhile,the equivalent parallel memcapacitance has been drawn to determine that multiple fractional-order memcapacitors could be calculated as one composite memcapacitor.Thus,an arbitrary fractional-order equivalent memcapacitor could be constructed by multiple fractional-order memcapacitors.