Determination of chitin and protein contents during the isolation of chitin from shrimp waste

Accurate determination of chitin and protein contents in crustacean biomass and the intermediate products during the industrial isolation of chitin cannot be made directly from the total nitrogen content, unless the appropriate corrections are applied. This method, however, is affected by the presence of other nitrogen-containing chemical species that are formed endogenously or by the action of microorganisms during the handling of the sample. Therefore, an alternative rapid method to estimate the contents of these components can be very useful both in research and in various fields of application. An original method has been developed to address this problem. The method consists of the development of a set of equations based on the stoichiometric contents of nitrogen of chitin and protein whereby the amounts of each component can be estimated from the value of the total nitrogen content, provided the rest of the proximate composition of the sample is accurately known. In order to validate the procedure, a set of model mixtures of pure chitin and protein concentrate in the solid state, both extracted from shrimp head waste, are used. Excellent agreement between the predicted and real values of chitin and protein are obtained (R2=0.98, slope=0.90). When the proposed method is tested in the analysis of real samples obtained from five different processing protocols of pretreatment of raw shrimp head, it is found that in general the values of protein and chitin contents throughout the various stages of the process vary as expected. [GRAPH: SEE TEXT] Variation of the measured total nitrogen versus calculated stoichiometric total nitrogen of the chitin-protein mixtures.     

Multiple alignment tensors from a denatured protein

The structural content of the denatured state has yet to be fully characterized. In recent years, large residual dipolar couplings (RDCs) from denatured proteins have been observed under alignment conditions produced by bicelles and strained polyacrylamide gels. In this report, we describe efforts to extend our picture of the residual structure in denatured nuclease by measuring RDCs with multiple alignment tensors. Backbone amide 15N-1H RDCs were collected from 4 M urea for a total of eight RDC data sets. The RDCs were analyzed by singular value decomposition (SVD) to determine the number of independent alignment tensors present in the data. On the basis of the resultant singular values and propagated error estimates, it is clear that there are at least three independent alignment tensors. These three independent RDC datasets can be reconstituted as orthogonal linear combinations, (OLC)-RDC datasets, of the eight actually recorded. The first, second, and third OLC-RDC datasets are highly robust to the removal of any single experimental RDC dataset, establishing the presence of three independent alignment tensors, sampled well above the level of experimental uncertainty. The observation that the RDC data span three or more dimensions of the five-dimensional parameter space demonstrates that the ensemble average structure of denatured nuclease must be asymmetric with respect to these three orthogonal principal axes, which is not inconsistent with earlier work demonstrating that it has a nativelike topology.     

Application of external micro-spectrophotometric detection to improve sensitivity on microchips

The goal of this work was to increase the sensitivity of a UV–Vis spectrophotometer by decreasing the background noise and lengthening the optical path. A microphotometer has been modified to precisely select very small parts of a microfluidic channel pattern of a chip and to measure light absorbance on a magnified area of the selected part of the channel. The viability of combining a projection microscope and a spectrophotometer for external absorbance measurements on disposable PDMS chips was studied. Besides the external direct detection above a microfluidic channel, the optical pathlength was lengthened by detecting in the region of the perpendicular exit port. Increasing the cross-sectional area of the zone of irradiation improved the signal-to-noise ratio and the limits of detection (LOD).     

Structure and stereochemistry of novel ecdysteroids from the roots of Serratula wolffii

Three new natural ecdysteroids viz. 22‐dehydro‐20‐deoxy‐ajugasterone C (1), 1‐hydroxy‐22‐deoxy‐20,21‐didehydro‐ecdysone (2) and 22‐deoxy‐20,21‐didehydro‐ecdysone (3) were isolated from the methanol extract of the roots of Serratula wolffii. The structures of compounds 1–3 were established by various spectroscopic techniques, including one‐ and two‐dimensional NMR, circular dichroism and mass spectroscopic methods. Copyright © 2010 John Wiley & Sons, Ltd.     

Charge-Separated and Lewis Paired Metal–Organic Framework for Anion Exchange and CO2 Chemical Fixation

Charge-separated metal–organic frameworks (MOFs) are a unique class of MOFs that can possess added properties originating from the exposed ionic species. A new charge-separated MOF, namely, UNM-6 synthesized from a tetrahedral borate ligand and Co²⁺ cation is reported herein. UNM-6 crystalizes into the highly symmetric P43n space group with fourfold interpenetration, despite the stoichiometric imbalance between the B and Co atoms, which also leads to loosely bound NO₃⁻ anions within the crystal structure. These NO₃⁻ ions can be quantitatively exchanged with various other anions, leading to Lewis acid (Co²⁺) and Lewis base (anions) pairs within the pores and potentially cooperative catalytic activities. For example, UNM-6-Br, the MOF after anion exchange with Br⁻ anions, displays high catalytic activity and stability in reactions of CO₂ chemical fixation into cyclic carbonates.     

Performance and selectivity of polymeric pseudostationary phases for the electrokinetic separation of amino acid derivatives and peptides

Two polymeric pseudostationary phases, one an acrylamide polymer and the second a siloxane polymer, have been investigated for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized amino acids and small peptides. The dervatized amino acids were detected by UV absorbance and laser-induced fluorescence (LIF) detection. The polymers provided very high efficiency and good selectivity for the separation of the amino acids. The separation selectivity using the polymers was significantly different from that of SDS micelles, and there were subtle differences in selectivities between the polymers. Although very good detection limits were obtained with LIF detection, a significant background signal was observed when the polymers were not washed to remove fluorescent impurities. The polymers did not separate the peptides very well. It is postulated that the fixed covalent structure of the polymers prevents them from interacting strongly or efficiently with the peptides, which are large in relation to the analytes typically separated by electrokinetic chromatography using polymers.     

A two-state model for selective solubilization of benzene-limonene mixtures in sodium dihexyl sulfosuccinate microemulsions

When surfactants are used to solubilize oil, the oil to be solubilized is often a mixture of components with differing properties, for example, solubilization of drug molecules in microemulsion formulations, remediation of organic polluted aquifers using surfactants, and so forth. Previous research has demonstrated that selective solubilization of one organic component over the other may occur if the organic components are dissimilar. In this research, we investigated selective solubilization from benzene-limonene mixtures in Winsor type I and III microemulsion systems containing water, sodium di-n-hexyl sulfosuccinate, and NaCl. The effect of the oil phase composition and the electrolyte concentration on the selectivity was studied. It was found that the selectivity toward benzene was highest at low electrolyte and benzene concentrations, decreasing as the electrolyte or benzene concentration increased. The results are discussed on the basis of the two-state solubilization theory and by correlating the curvature of the surfactant film in the microemulsion with changes of the electrolyte concentration and the oil phase composition. A simple mathematical model is developed for the selectivity, which combines the two-state solubilization theory and the net-average curvature model of microemulsion solubilization to yield close agreement with the experimental data.     

Sn-containing liquid crystalline side group homopolymers with two glass transitions

Three homologous tin-containing homopolymers with a terminal CN-dipole in the side group have been synthesized and characterized by dynamical calorimetry, polarization microscopy, X-ray and dielectric methods. AFM was used to evaluate the texture at room temperature. Four different phase transitions were detected by DSC. The high temperature phases were identified by polarization microscopy as SmA and SmC. AFM-measurements show focal-conic domains at room temperature and confirm so the smectic nature of all phases. X-ray measurements on nonoriented samples give hints to a phase segregation on nanometer scale. Dielectric investigation and temperature-modulated DSC (TMDSC) confirm clearly phase separation by appearance of two glass transitions related to the liquid order of the main chains and the liquid crystalline of the side groups.     

Comparative Study on Decomposition of CFCl<Subscript>3</Subscript> in Thermal and Cold Plasma

Decomposition of CFCl₃ was investigated in an RF inductively coupled thermal reactor in neutral, oxidative and reductive conditions, and in a silent electric discharge (cold plasma) in neutral and oxidative conditions, respectively. In RF thermal plasma reactor, in neutral conditions, mainly gaseous products and minor amount of solid soot was formed. About 50% the soot could be extracted by toluene. Both the gas phase and the extract contained a wide range of aliphatic and aromatic compounds including chlorine and fluorine containing polyaromatic hydrocarbons (PAHs). In oxidative conditions much less soot was formed as compared to the neutral case. The solid product contained about 45% extractable fraction even in oxidative conditions. However, the extract contained less PAHs than in neutral conditions. In reducing atmosphere the soot yield was similar to the neutral case, but the soot contained 29% extractable fraction only. The extract consisted of polyhalogenated aromatic and polyaromatic hydrocarbons as main components. In neutral conditions different chlorofluorocarbons (CFCs) and chlorine were detected as gaseous products in cold plasma. In oxidative conditions, as final products of decomposition CO₂, CFCs and Cl₃ were formed.     

Self-assembly of a hexagonal phase of wormlike micelles containing metal nanoclusters

Stable nanoclusters (approximately 2 nm in diameter) of copper, silver, gold, palladium, and ruthenium coated with hydrophobic coronas are easily trapped in self-assembled "soft crystal" hexagonal phase gels made of water and surfactants. The system's crystal structure and phase behavior are studied in detail. A partial phase diagram showing the hexagonal phase region for the water/SDS/toluene region is presented. High-energy X-ray scattering and cross-polarized optical microscopy experiments show that the clusters are tightly confined within the tubes. The thermal gel-fluid transitions of the hexagonal phase are investigated, and it is shown that the hexagonal phase can melt and recrystallize repeatedly. The melt/gel cycles enable easy trapping of various metal clusters in pre-prepared hexagonal phases. In contrast to spherical micelles, the hexagonal phase doped with metal clusters can grow without limit, basically up to the container walls (Ru-doped soft crystals grew to 0.5 mm over 2 months, forming wormlike tubes that are more than 50 microm long but only 7-10 nm in diameter).