An Interpenetrated Framework Material with Hysteretic CO2 Uptake

A new, twofold interpenetrated metal–organic framework (MOF) material has been synthesized that demonstrates dramatic steps in the adsorption and hysteresis in the desorption of CO₂. Measurement of the structure by powder X‐ray diffraction (PXRD) and pair distribution function (PDF) analysis indicates that structural changes upon CO₂ sorption most likely involve the interpenetrated frameworks moving with respect to each other.     

Elaboration and characterisation of a plasticized cellulose triacetate membrane containing trioctylphosphine oxyde (TOPO): Application to the transport of uranium and molybdenum ions

A cellulose triacetate (CTA) membrane containing trioctylphosphine oxyde (TOPO) as carrier and 2-nitrophenyloctyl ether (NPOE) as a plasticizer was prepared. The membrane CTA + NPOE + TOPO was characterised using chemical techniques as well as Fourier Transform InfraRed (FTIR) spectroscopy, X-ray diffraction and Scanning Electron Microscopy (SEM). The CTA membrane is characterised by well-defined pores; these pores are completely filled with the NPOE and carrier. Surfaces of membranes with TOPO are smooth. The systems constituted by the mixture of CTA + NPOE, CTA + NPOE + TOPO do not give any diffraction. This can be due to the absence of crystallization within the membrane. On the other hand, this result should be attributable to the amorphous state of the structure, which permits us to eliminate the mechanism of transfer of the ions by electron jump. A comparative study of transport across a polymer inclusion membrane (PIM) and a supported liquid membrane (SLM) containing the same carrier in chloroform has shown that uranium or molybdenum transport efficiency was increased using PIM instead of SLM. PIM showed higher stability than SLM, the flux of transport remain constant in the former case after 2 weeks.     

Mass spectrometric analysis of the S-layer proteins from Clostridium difficile demonstrates the absence of glycosylation

Like many other bacterial cell surfaces, the cell wall of Clostridium difficile is also encapsulated by a proteinaceous paracrystalline layer, the surface (S)-layer. In many bacterial species, the S-layer proteins (SLPs) have been shown to be glycosylated, whereas in other species glycosylation is absent. Unusually, the S-layer of C. difficile is composed of two distinct proteins, the high-molecular weight (HMW) and low-molecular-weight (LMW) SLPs. Previous investigations have reported that one or both of these SLPs are glycosylated, though no definitive study has been conducted. We have used a variety of mass spectrometric approaches to analyse SLPs from a number of strains of C. difficile for the presence of associated glycans. Analysis of intact SLPs by matrix assisted laser desorption/ionisation time of flight (MALDI-ToF) mass spectrometry demonstrated that the observed molecular masses matched the predicted masses of the LMW and HMW SLPs. Furthermore, analysis of Cyanogen bromide (CNBr) and tryptic peptides displayed no evidence of post-translational modification. In the first in-depth study of its kind, we unequivocally demonstrate that the S-layer proteins from the C. difficile strains investigated are not glycosylated.     

Shahidine, a novel and highly labile oxazoline from Aegle marmelos: the parent compound of aegeline and related amides

A rare alkaloid, shahidine (1), having an unstable oxazoline core has been isolated as a major constituent from the fresh leaves of Aegle marmelos. It is moisture-sensitive, and found to be the parent compound of aegeline and other amides, however, it is stable in dimethyl sulfoxide. Its structure was established by spectroscopic analysis. Biogenetically, oxazolines may be considered as the precursor of hydroxy amides and oxazoles found in plants. Shahidine (1) showed activity against a few Gram-positive bacteria.     

Iridium(III) Complexes with Sulfonyl and Fluorine Substituents: Synthesis,Stereochemistry and Effect of Functionalisation on their Photophysical Properties

The synthesis and photophysical and electrochemical characterisation of new heteroleptic iridium complexes with electron‐withdrawing sulfonyl groups and fluorine atoms bound to phenylpyridine ligands are reported. The emission energy of these materials strongly depends on the position of the sulfonyl groups and on the number of fluorine substituents. A 90 nm wide tuning range of photoluminescence from the blue‐green (λ_em=468 nm) of iridium(III)bis[2‐(4′‐benzylsulfonyl)phenylpyridinato‐N,C2′][3‐(pentafluorophenyl)‐pyridin‐2‐yl‐1,2,4‐triazolate] to the orange (λ_em=558 nm) of iridium(III)bis[2‐(3′‐benzylsulfonyl)phenylpyridinato‐N,C2′](2,4‐decanedionate) has been achieved. Emission quantum yields ranging from 47 to 71 % have also been found for degassed solutions of the complexes, and a surprisingly high value of 16 % was recorded for iridium(III)bis[2‐(5′‐benzylsulfonyl‐3′,6′‐difluoro)phenylpyridinato‐N,C2′](2,4‐decanedionate) in air‐equilibrated dichloromethane. A unusual stereochemistry of the benzylsulfonyl‐substituted dimer and heteroleptic complexes has been detected by ¹H NMR spectroscopy, and is characterised by the mutual cis disposition of the pyridyl nitrogen atoms of the phenylpyridine ligands, which differs from the most common trans arrangement reported in the literature.     

Selective Separation of Oxy-PAH from n-Alkanes and PAH in Complex Organic Mixtures Extracted from Airborne PM2.5

A fast and simple fractionation method was optimized to selectively separate oxy-PAH from polycyclic aromatic hydrocarbons (PAH) and n-alkanes contained in solvent extracted organic matter (SEOM) from atmospheric particles with an aerodynamic diameter ≤2.5 μm (PM_2.5). Samples were collected in Mexico City. Multivariate parameters were adjusted on a standard mixture, and on SEOM spiked with pure standard mixture solutions: type and amount of phase; packing densities; type, proportion and amount of solvents, and elution flow rates were tested under several elution schemes. Cyanopropylsilyl-bonded phase material was the selected stationary phase. The separation method was applied to real samples of SEOM (2.6, 5.6 and 8.5 mg) spiked with n-alkanes, PAH and oxy-PAH. n-Alkanes overlapped with PAH due to an excess of n-alkanes in real samples overloading the capacity of the stationary phase. Oxy-PAH was separated totally from n-alkanes and PAH. Mean recoveries ± confidence intervals (95%) for n-alkanes ranged from 53 ± 17% (n-tetracontane) to 101 ± 11% (n-hexacosane); for PAH from 58 ± 5% (phenanthrene) to 85 ± 9% (benzo[k]fluoranthene); and for oxy-PAH from 68 ± 12% (9,10-dihydrobenzo[a]pyren-7(8H)one) to 108 ± 9% (1,2-benzopyrone). This method is an efficient fractionation procedure to be applied to oxy-PAH, PAH and n-alkanes in complex organic mixtures extracted from PM_2.5.     

A theoretical study on three conformational structures of 2,6‐distyrylpyridine

Ab initio methods at the levels HF/cc‐pVDZ, HF/6‐31G(d,p), MP2/cc‐pVDZ, and MP2/6‐31G(d,p), as well as methods based on density functional theory (DFT) employing the hybrid functional B3LYP with the basis sets cc‐pVDZ and 6‐31G(d,p), have been applied to study the conformers of 2,6‐distyrylpyridine. Bond distances, bond angles, and dihedral angles have been calculated at the B3LYP level. The calculated values were in good agreement with those measured by X‐ray diffraction analysis of 2,6‐distyrylpyridine. The values calculated using the Hartree‐Fock method and second‐order perturbation theory (MP2) were inconsistent. The optimized lowest‐energy geometries were calculated from the reported X‐ray structural data by the B3LYP/cc‐pVDZ method. Three conformations, A, B, and C, were proposed for 2,6‐distyrylpyridine. Calculations at the three levels of theory indicated that conformation A was the most stable structure, with conformations C and B being higher in energy by 1.10 and 2.57 kcal/mol, respectively, using the same method and basis function. The same trend in the relative energies of the three possible conformations was observed at the two levels of theory and with the different basis sets employed. The reported X‐ray data were utilized to optimize total molecular energy of conformation A at the different calculation levels. The bond lengths, bond angles, and dihedral angles were then obtained from the optimized geometries by ab initio methods and by applying DFT using the two basis functions cc‐pVDZ and 6‐31G(d,p). The values were analyzed and compared. The calculated total energies, the relative energies of the molecular orbitals, the gap between them, and the dipole moment for each conformational structure proposed for 2,6‐distyrylpyridine are also reported. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

The effect of gamma irradiation on glass transition temperature and thermal stability of Se96Sn4 chalcogenide glass

Se₉₆Sn₄ chalcogenide glass was prepared by melt quenching technique and exposed, at room temperature, to different doses of 4, 8, 12, 24 and 33 kGy of high-energy ⁶⁰Co gamma irradiation. Differential scanning calorimeter (DSC) was used under non-isothermal condition to determine the glass transition temperature T_g, onset T_c and peak T_p temperatures of crystallization, of un-irradiated and γ-irradiated samples, at four different heating rates. The variation of T_g with heating rates was utilized to calculate the glass transition activation energy E_t for un-irradiated and γ-irradiated glass, using the methods suggested by Kissinger and Moynihan. Based on the obtained values of the characteristic temperatures T_g, T_c and T_p, thermal stability was monitored through the calculation of the S parameter and the crystallization rate factor 〈K_p〉 for irradiated and un-irradiated glass. Results reveal that, as γ-dose increases T_g increases up to 12 kGy then decreases at higher doses but remains more than that of un-irradiated glass. Meanwhile, both E_t and 〈K_p〉 attain their minimum values at the same dose of 12 kGy and the glass is thermally stable at this particular dose.     

Use of ionic liquid for the enzyme‐catalyzed polymerization of phenols

Ionic liquid and buffer mixture media are first reported in the peroxidase‐catalyzed polymerization of phenol. Yield of 100% with molecular weights of 7000 KDa, as assessed by size‐exclusion chromatography (SEC), were attained using 1‐butyl‐3‐methylimidazolium tetrafluoroborate–buffer mixtures with added hydrogen peroxide. The simplicity of the process and the low vapor pressure of the solvent media allow an eco‐friendly alternative to the general synthesis of polyphenolic‐type biopolymers. Evidence for the consequent polyphenol (PPO) was obtained from solid‐state ¹³C cross‐polarization magic angle spinning (CP‐MAS) NMR spectroscopy and FT‐IR. Copyright © 2009 John Wiley & Sons, Ltd.     

Specific Deuteration in Patuletin and Related Flavonoids via Keto–Enol Tautomerism: Solvent‐ and Temperature‐Dependent 1H‐NMR Studies

An H/D exchange process in patuletin ( 1 ) and its derivatives in D‐donor solvents (e.g., CF₃COOD), which occurs regioselectively at C(8) was observed for the first time during NMR studies. The effect of substituents and temperature on the deuteration of various flavonoids (see Fig. 1) which include apigenin, chrysin, galangin, kaempferol, luteolin, morin, myricetin, patuletin, patulitrin, and quercetin, as well as derivatives of patuletin was examined extensively under NMR conditions. The rate constant of deuteration at C(8) of patuletin ( 1 ) and two flavones, luteolin ( 3 ) and apigenin ( 12 ), was also determined in CF₃COOD. The D‐atom was introduced into the flavonoids via a keto–enol tautomerism (Scheme 1). During these studies, monodeuterated patuletin was also obtained as a new compound. The examined flavonoids have been reported to possess significant pharmacological activities, and their deuterated derivatives would be of importance for the identification and quantification of these compounds in biological matrices.