Chitooligosaccharides: Synthesis,characterization and applications

Chitosans with high degree of polymerization and molecular weight exhibit poor aqueous solubility which is an impediment in their applicability. The low molecular weight chitosans (LMWCs) and chitooligosaccharides (COSs) can be used to avoid this hurdle. The development of an efficient process for reducing the molecular weight of chitosan, without altering its chemical structure, is of great interest to produce tailormade chitosans of varying Degree of Acetylation (DAs) and Degree of Polymerization (DPs). The production of well-defined COS-mixtures, or even pure COS, is of great interest since these oligosaccharides are thought to have several interesting bioactivities and applications. For this proper delineation of their characteristics is needed. Hence it is our attempt to provide an overview of difffernt methods and techniques of their production and characterization. Several methods viz. depolymerization under the action of reagents, enzymes, high energy impact and combinations thereof have been employed to get COS by depolymerization of high molecular weight chitosans. Acid hydrolysis (hydrochloric, nitrous, phosphoric acid, hydrogen fluoride) and oxidative reductive depolymerization (mediated by peroxide, ozone, and persulfate) are important routes for synthesis of COSs. These oligomers can be produced from chitin or chitosan as a starting material by enzymatic conversions. For this, numbers of enzymes have been used. Depolymerization under high energy impact and recombinant approaches are also being tried for production of COSs. LMWC and COS, like parent chitosan, can be used for drug delivery and gene delivery. The efficient and productive processes are needed for separation of COSs into its components or mixture of defined characters. The characterization of COS can be carried out by chromatographic and spectroscopic techniques. Importantly COSs display an array of biological activities as antimicrobial, anticancer/antimetastatic, wound healing acceleration, immunostimulation, apoptosis induction or inhibiton, antioxidant, enzyme inhibiton, antihyperlipidemic, antidiabetic, chemoprevention, and many more. A few of the biological actions are reported only sporadically where as some are persistently taken up by the scientific fraternity to substantiate the claims and propose possible mechanisms of action. However there remains the disagreement of results on COS activities. The disagreements can arise due to poor and variable reporting of the properties of COS such as used in the studies as molecular weight, degree of acetylation, molecular weight distribution, and the pattern of N-acetylation etc. With production of COS of well defined characters it might be possible to understand the modes of actions of COS in better ways.     

Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid

We present evidence for a near-resonant mechanism of charge transfer in short peptide nucleic acid (PNA) duplexes obtained through electrochemical, STM break junction (STM-BJ), and computational studies. A seven base pair (7-bp) PNA duplex with the sequence (TA)(3)-(XY)-(TA)(3) was studied, in which XY is a complementary nucleobase pair. The experiments showed that the heterogeneous charge transfer rate constant (k(0)) and the single-molecule conductance (σ) correlate with the oxidation potential of the purine base in the XY base pair. The electrochemical measurements showed that the enhancement of k(0) is independent, within experimental error, of which of the two PNA strands contains the purine base of the XY base pair. 7-bp PNA duplexes with one or two GC base pairs had similar measured k(0) and conductance values. While a simple superexchange model, previously used to rationalize charge transfer in single stranded PNA (Paul et al. J. Am. Chem. Soc. 2009, 131, 6498-6507), describes some of the experimental observations, the model does not explain the absence of an enhancement in the experimental k(0) and σ upon increasing the G content in the duplexes from one to two. Moreover, the superexchange model is not consistent with other studies (Paul et al. J. Phys. Chem. B 2010, 114, 14140), that showed a hopping charge transport mechanism is likely important for PNA duplexes longer than seven base pairs. A quantitative computational analysis shows that a near-resonant charge transfer regime, wherein a mix of superexchange and hopping mechanisms are expected to coexist, can rationalize all of the experimental results.     

Specific detection of Campylobacter jejuni using the bacteriophage NCTC 12673 receptor binding protein as a probe

Campylobacter jejuni is found in the intestines of poultry, cattle, swine, wild birds and pet animals and is the major cause of foodborne gastroenteritis in developed countries. We report the use of the receptor binding protein (RBP) of Campylobacter bacteriophage NCTC 12673 for the specific capture of Campylobacter jejuni bacteria using RBP-derivatized capturing surfaces. The Gp48 RBP was expressed as a glutathione S-transferase-Gp48 (GST-Gp48) fusion protein and immobilized onto surface plasmon resonance (SPR) surfaces using glutathione self-assembled monolayers (GSH SAM). Bovine serum albumin (BSA) was used to block any non-specific binding. Glutathione SAM leads to an oriented attachment of the protein, resulting in a two- to three-fold improvement of bacterial capture when compared to dithiobis(succinimidyl propionate) (DTSP) SAM-based unoriented attachment. The specificity of recognition was confirmed using Salmonella enterica subsp. enterica serovar Typhimurium as a negative control, which indeed showed negligible binding. The detection limit of the RBP-derivatized SPR surfaces was found to be 10(2) cfu/ml. Finally, GST-Gp48 was also immobilized onto magnetic beads that were successfully used to capture and pre-concentrate the host pathogen from suspension.     

Unsymmetrical diimine complexes of iron(II) and manganese(II): synthesis, structure and photoluminescence of an isomer

Two bis(unsymmetrical diimine) complexes of (L(NO(2))(?1))(L(NO(2))(?2))M(II)Cl(2) family with M = Fe and Mn, are reported (L(NO(2))(?) = (E)-3-nitro-N-(pyridine-2-ylmethylene)aniline; ? = dihedral angle between the diimine unit including pyridine ring and the phenyl ring planes). Pure tcc-(L(NO2)(33.6))(L(NO2)(79.3))Fe(II)Cl(2)·0.5H(2)O (1) and tcc-(L(NO2)(32.0))(L(NO2)(79.4))Mn(II)Cl(2)·0.5H(2)O (2) isomers have been successfully isolated in high yields and characterized by elemental analyses, variable temperature magnetic susceptibility measurements, IR, mass, UV-vis and M?ssbauer spectra including the single-crystal X-ray structure determinations that identified strong intermolecular non-bonding interactions in lattice (tcc refers to trans-cis-cis positions with respect to pyridine N-imine N-Cl donors). Geometries optimizations of all possible tcc, ttt, ctc, ccc and cct isomers of iron at the B3LYP/DFT level in gas-phase have shown that the tcc-isomer incorporating two non-equivalent ligands as in (L(NO(2))(42))(L(NO(2))(61))Fe(II)Cl(2), 1 (g), is stabilized by 6-20 kJ mol(-1) compared to other isomers where two ligands are equivalent. The frozen methanol glasses of 1 and 2 are luminescent at 77 K (1: λ(ext) = 370, λ(em) = 521 nm, χ(2) = 1.3, τ(avg) = 0.57 ns; 2: λ(ext) = 368, λ(em) = 524 nm, χ(2) = 1.1, τ(avg) = 0.90 ns). The DFT calculations have identified four closely spaced localized π(*) orbitals comprising of two non-equivalent ligands as UPMOs. The features contrast the tcc-isomer of (L(?))(2)Fe(II)Cl(2) (3), congener of 1 without -NO(2) substitution and non-emissive (bpy)(2)Fe(II)Cl(2) (4) where two ligands are equivalent. TD-DFT calculations have assigned intra-ligand (IL) and ligand to ligand charge transfer (LLCT) dominated excited states as the origin of luminescence of 1 and 2.     

Application of ethyl chloroformate derivatization for solid-phase microextraction–gas chromatography–mass spectrometric determination of bisphenol-A in water and milk samples

A simple and rapid analytical method based on in-matrix ethyl chloroformate (ECF) derivatization has been developed for the quantitative determination of bisphenol-A (BPA) in milk and water samples. The samples containing BPA were derivatised with ECF in the presence of pyridine for 20 s at room temperature, and the non-polar derivative thus formed was extracted using polydimethylsiloxane solid-phase microextraction (SPME) fibres with thicknesses of 100 μm followed by analysis using gas chromatography–mass spectrometry. Three alkyl chloroformates (methyl, ethyl and isobutyl chloroformate) were tested for optimum derivatisation yields, and ECF has been found to be optimum for the derivatisation of BPA. Several parameters such as amount of ECF, pyridine and reaction time as well as SPME parameters were studied and optimised in the present work. The limit of detection for BPA in milk and water samples was found to be 0.1 and 0.01 μg L⁻¹, respectively, with a signal-to-noise ratio of 3:1. The limit of quantitation for BPA in milk and water was found to be 0.38 and 0.052 μg L⁻¹, respectively, with a signal-to-noise ratio of 10:1. In conclusion, the method developed was found to be rapid, reliable and cost-effective in comparison to silylation and highly suitable for the routine analysis of BPA by various food and environmental laboratories.     

Vanadium complexes immobilized on solid supports and their use as catalysts for oxidation and functionalization of alkanes and alkenes

This review mainly discusses the immobilization strategies that have been used for vanadium complexes, typically mesoporous material, zeolites and polymers, the characterization procedures for the obtained materials, and their catalytic applications. The retention of the active metal compound within the catalyst may be based on (i) adsorption, (ii) the formation of covalent bonds between metal ligand and support, (iii) ion exchange, (iv) encapsulation, or (v) entrapment. The heterogenized complexes are used as catalysts for oxidations and functionalization of alkanes, alkenes and other substrates, and an account of the various applications reported is given.     

Effect of ionic liquid on dielectric, mechanical and dynamic mechanical properties of multi-walled carbon nanotubes/polychloroprene rubber composites

This paper focuses on the influence of ionic liquid on carbon nanotube based elastomeric composites. Multi-walled carbon nanotubes (MWCNTs) are modified using an ionic liquid at room temperature, 1-butyl 3-methyl imidazolium bis (trifluoromethylsulphonyl) imide (BMI) and modified MWCNTs exhibit physical (cation–π/π–π) interaction with BMI. The polychloroprene rubber (CR) composites are prepared using unmodified and BMI modified MWCNTs. The presence of BMI not only increases the alternating current (AC) electrical conductivity and polarisability of the composites but also improves the state of dispersion of the tubes as observed from dielectric spectroscopy and transmission electron microscopy respectively. In addition to the hydrodynamic reinforcement, the formation of improved filler–filler networks is reflected in the dynamic storage modulus (E′) for modified MWCNTs/CR composites in amplitude sweep measurement upon increasing the proportion of BMI. Hardness and mechanical properties are also studied for the composites as a function of BMI.     

Heavy metals adsorption by novel EDTA-modified chitosan-silica hybrid materials

Ionic liquid based microemulsions were characterized by absorption solvatochromic shifts, (1)H NMR and kinetic measurements in order to investigate the properties of the ionic liquid within the restricted geometry provided by microemulsions and the interactions of the ionic liquid with the interface. Experimental results show a significant difference between the interfaces of normal water and the new ionic liquid microemulsions. Absorption solvatochromic shift experiments and kinetic studies on the aminolysis of 4-nitrophenyl laurate by n-decylamine show that the polarity at the interface of the ionic liquid in oil microemulsions (IL/O) is higher than at the interface of water in oil microemulsions (W/O) despite the fact that the polarity of [bmim][BF(4)(-)] is lower than the polarity of water. (1)H NMR experiments showed that an increase in the ionic liquid content of the microemulsion led to an increase in the interaction between [bmim][BF(4)(-)] and TX-100. The reason for the higher polarity of the microemulsions with the ionic liquid can be explained in terms of the incorporation of higher levels of the ionic liquid at the interface of the microemulsions, as compared to water in the traditional systems.     

Hierarchical organization of a robust porphyrin cage self-assembled by hydrogen bonds

Porphyrins appended with four rigid hydrogen bonding motifs on the meso positions were synthesized and self-assembled into a cofacial cage with four complementary bis(decyl)melamine units in dry solvents. The hydrocarbon chains on the melamine mediate the formation of nanofilms on surfaces as the solvent slowly evaporates.     

Automatic locking of a parametrically resonating,base-excited,nonlinear beam

Nonlinear Dynamics - Described is a closed-loop control scheme capable of stabilizing a parametrically excited nonlinear structure in several vibration modes. By setting the relative phase between...