Swelling of poly(N-isopropylacrylamide) gels in water-aprotic solvent mixtures

The swelling volume of poly(N-isopropylacrylamide) (PIPAAm) gel in aprotic solvents (acetonitrile (AcN)-, tetrahydrofuran (THF)-, 1,4-dioxane (DO)- and dimethylsulfoxide (DMSO))-water mixtures was measured at 25°C. The gel swollen in water shrank first and then reswelled with addition of the aprotic solvents. At an intermediate mole fraction (XDMSO) range of DMSO-water mixtures, the gel demonstrated a reentrant swelling phenomenon the hydrated gel shrank first on addition of a small amount of solvent, showed a typical wide reentrant transition, and gradually reswelled in the range near pure solvent. On the other hand, the gels in AcN-, THF-, and DO-water mixtures demonstrated a reentrant-convex swelling phenomenon: the gels reswelled after a reentrant phase transition in low Xorg (XAcN, XTHF and XDO), showed a maximum swelling in the intermediate Xorg region, and shrank again gradually in the high Xorg region. Such a swelling behavior of the gel was interpreted by correlating with solution properties of the aqueous aprotic solvent mixtures.The strength of hydrogen bonding around amide groups of the homopolymer was examined in pure solvents (water, THF, and DMSO) and in all proportion of aqueous THF to observe the relation with swelling behavior of gel by spectrum analysis of the amide I and II bands of Fourier Transform Infrared Spectroscopy (FT-IR). The swelling properties of gels in solvents and the aqueous mixtures were well correlated with the peak shifts of amide groups of the homopolymer.     

Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

Comprehensive Metabolite Profiling in Genetic Resources of Garlic (Allium sativum L.) Collected from Different Geographical Regions

Garlic (Allium sativum) is the second most important Allium crop that has been used as a vegetable and condiment from ancient times due to its characteristic flavor and taste. Although garlic is a sterile plant that reproduces vegetatively through cloves, garlic shows high biodiversity, as well as phenotypic plasticity and environmental adaptation capacity. To determine the possible mechanism underlying this phenomenon and to provide new genetic materials for the development of a novel garlic cultivar with useful agronomic traits, the metabolic profiles in the leaf tissue of 30 garlic accessions collected from different geographical regions, with a special focus on the Asian region, were investigated using LC/MS. In addition, the total saponin and fructan contents in the roots and cloves of the investigated garlic accessions were also evaluated. Total saponin and fructan contents did not separate the garlic accessions based on their geographical origin, implying that saponin and fructan contents were clone-specific and agroclimatic changes have affected the quantitative and qualitative levels of saponins in garlic over a long history of cultivation. Principal component analysis (PCA) and dendrogram clustering of the LC/MS-based metabolite profiling showed two major clusters. Specifically, many Japanese and Central Asia accessions were grouped in cluster I and showed high accumulations of flavonol glucosides, alliin, and methiin. On the other hand, garlic accessions grouped in cluster II exhibited a high accumulation of anthocyanin glucosides and amino acids. Although most of the accessions were not separated based on country of origin, the Central Asia accessions were clustered in one group, implying that these accessions exhibited distinct metabolic profiles. The present study provides useful information that can be used for germplasm selection and the development of new garlic varieties with beneficial biotic and abiotic stress-adaptive traits.     

Photochemical ligation of DNA conjugates through anthracene cyclodimer formation and its fidelity to the template sequences

Anthracene readily forms photoadducts, anthracene dimers, and this photodimerization reaction has been well characterized. In general, however, the reaction requires close proximity and certain spatial alignment of both reaction partners. DNA could provide an ideal scaffold for accelerating the photocyclic addition. We synthesized a number of anthracene-DNA conjugates. The sequences of the conjugates, 5'AntODNn and 3'AntODNn (the length of methylene linkers: n = 3 or 6), were designed to bind adjacent sequences of the template with the anthracene units directed such that they stacked with each other. The conjugates were only dimerized in the presence of the template by light irradiation. The efficiency was affected by one-base displacement in the template sequence.     

The effect of local structural disruption on the yield of photochemical ligation between anthracene-oligonucleotide conjugates.

The techniques of chemical ligation have attracted great attention as an alternative to enzymatic joining of DNA ends. Here we introduce the photoligation of anthracene-modified ODN conjugates through anthracene cyclodimer formation. The effect of the positions and the kinds of single base mismatch on the template was evaluated using eight templates with one-base displacements. We found out that the yield of the ligation was affected by mispairing in a position-dependent manner. Such results would be attributed to the disruption of the local structure at the ligation site.     

Theoretical study of the vibrational frequencies of carbon disulfide

A benchmark comparison for different computational methods and basis sets has been presented. In this study, five computational methods (Hartree–Fock (HF), MP2, B3LYP, MPW1MP91, and PBE1PBE) along with 18 basis sets have been applied to optimize the geometry of carbon disulfide (CS₂), and further calculate the vibrational frequencies of the optimized geometries. The differences between the calculated frequencies and corresponding experimental data are used to evaluate the efficiency of each combination of computational method and basis set. The comparison of frequency difference indicates that B3LYP generally gives the best prediction of frequencies for CS₂, whereas the other two density functional theory (DFT) methods, i.e., MPW1PW91 and PBE1PBE, often give parallel results. Although MP2 predicts the frequencies with accuracy almost as good as those from DFT methods, in a particular case, HF calculation outperforms MP2 as well as MPW1PW91 and PBE1PBE for prediction of the frequency of asymmetrical stretching for CS₂. © 2013 Wiley Periodicals, Inc.     

A quotient curve of the Fermat curve of degree twenty-three attaining the Serre bound

The curve in the title is a non-maximal curve of genus 11, which has a defining equation analogous to the Klein quartic's. We study its properties and show how to apply it to coding theory.     

The isolation and structure elucidation of new cassane diterpene-acids from Caesalpinia crista L. (Fabaceae), and review on the nomenclature of some Caesalpinia species

New cassane diterpene-acids, neocaesalpins H and I, were isolated from the leaves of Caesalpinia crista (Fabaceae), and their structures were deduced on the basis of the spectroscopic and chemical basis. These compounds were characterized as having an alpha,beta-butenolide hemiacetal ring that is rare in nature. The lacking of 5-hydroxy group also distinguished neocaesalpins H and I from cassane diterpenes (caesalpins) occurring in other Caesalpinia species from the phytochemical viewpoint. The nomenclature of three Caesalpinia species was also reviewed, and it was found that some species belonging to the genus Caesalpinia are improperly named and should be changed to valid names.     

Effects of pressure and temperature on the solubility of monosodium L-glutamate monohydrate in water

Abstract

The solubility of monosodium L-glutamate monohydrate (MSG.H₂O) in water was measured at pressures in the range of 0.10-300MPa and 298.15K. The density of MSG solution at high concentrations and heat of solution at saturated concentration were also measured at atmospheric pressure. The solubility, m_s, increased with increasing pressure and the pressure coefficient, Θ_p, [?(? In m_s,? p)_T] at 0.10 MPa was (2.0 ± 0.1) × 10-¹⁰Pa-1. It agrees well with (2.1 ±0.2)× 10-¹⁰ Pa-¹ thermodynamically estimated using the partial molar volume, the activity coefficient of the solute in solution, and the molar volume of the crystal. The excellent agreement at 0.10MPa gives us confidence in the solubility data at higher pressures. The heat of solution data and other pertinent values were used to calculate the temperature coefficient of solubility, Θ_T [? (? In m_s/?(1/T))_p], by a thermodynamic equality. The resulting Θ_T compares well with the data directly measured by Ogawa.     

Diffusion and reactions of interstitial oxygen species in amorphous SiO2: A review

This article briefly summarizes the diffusion and reactions of interstitial oxygen species in amorphous SiO₂ (a-SiO₂). The most common form of interstitial oxygen species is oxygen molecule (O₂), which is sensitively detectable via its characteristic infrared photoluminescence (PL) at 1272 nm. The PL observation of interstitial O₂ provides key data to verify various processes related to interstitial oxygen species: the dominant role of interstitial O₂ in long-range oxygen transport in a-SiO₂; formation of the Frenkel defect pair (Si–Si bond and interstitial oxygen atom, O⁰) by dense electronic excitation; efficient photolysis of interstitial O₂ into O⁰ with F₂ laser light (λ = 157 nm, hν = 7.9 eV); and creation of interstitial ozone molecule via reaction of interstitial O₂ with photogenerated O⁰. The efficient formation of interstitial O⁰ by F₂ laser photolysis makes it possible to investigate the mobility, optical absorption, and chemical reactions of interstitial O⁰. The observed properties of O⁰ are consistent with the model that O⁰ takes the configuration of Si–O–O–Si bond. Interstitial O₂ and O⁰ react with dangling bonds, oxygen vacancies, and chloride groups in a-SiO₂. Reactions of interstitial O₂ and O⁰ with mobile interstitial hydrogen species produce interstitial water molecules and hydroperoxy radicals. Interstitial hydroxyl radicals are formed by F₂ laser photolysis of interstitial water molecules.