Comparison of CE-MS and LC-MS Analyses of Avian Eggshell Matrix Proteins

CE-MS and HPLC-MS methods were developed and compared for the analysis of insoluble proteins in an avian eggshell matrix. The eggshell was gradually decalcified to obtain four distinct layers (cuticle, two palisade and a mammillary layer). The insoluble proteinaceous films from these layers were chemically and/or enzymatically splitted with CNBr/trypsin and proteinase K. The generated peptides were separated by CE and HPLC on-line coupled to MS detection. Capillary electrophoresis (CE) was coupled to an ion-trap electrospray ionization mass spectrometer (Agilent LC-MSD Trap XCT-Ultra) using a grounded needle carrying a flow of sheath liquid (5 mM ammonium acetate/2-propanol, 1:1, at flow-rate 3 μL min^?1). Five main proteins were identified: ovocleidin-116, ovocalyxin-32, ovocalyxin-36, ovocleidin-17 and ovalbumin. The distribution of these proteins in the eggshell was found to be dependent on the location/layer. In the outermost layer (the cuticle layer) the dominant protein is ovocalyxin-32; ovocleidin-116 is distributed throughout all layers while ovalbumin is present only in the internal mammillary layer. The CE-MS peptide maps of eggshell proteins were compared to the HPLC-MS ones, and a different mechanism of separation (migration/elution order) was demonstrated for both methods.     

Modification of flow properties of concentrated lignite dispersions

Concentrated water-based lignite suspensions (pastes) possess unpleasant flow behaviour. Under extrusion-like conditions suspension is rapidly compacted, viscosity rises considerably and flow effectively ceases. Using diluted aqueous solution of carboxymethylcellulose sodium salt as a dispersion medium eliminates this adverse phenomenon and keeps liquid-like flowing of suspension. Moreover, effective dilatant suspension behaviour is transformed to pseudoplastic.     

An abstract analogon of the de Branges-Rovnyak functional model

Given a Hilbert spaceK generated by two of its subspaces,K=K ₁K ₂, we investigate the representation ofK inK ₁K ₂ which assigns to eachk K the pairPk=P(K ₁)k P(K ₂)k consisting of its orthogonal projections ontoK ₁ andK ₂.A part of this work was done during the visit of the second author at the University of Sevilla, Spain in September-October 1989. The support of Junta Andalusia is gratefully aknowledged.     

Design,synthesis and anti-mycobacterial evaluation of some new <Emphasis Type="Italic">N</Emphasis>-phenylpyrazine-2-carboxamides

N-Phenylpyrazine-2-carboxamides (anilides of pyrazinoic acids with simple substituents in various positions) were previously shown to possess significant biological activities in vitro, markedly anti-mycobacterial and photosynthesis-inhibiting activity. Based on structure-activity relationships (SAR) extracted from previously published series, 25 new anilides of non-substituted pyrazinoic acid (POA), 5-CH₃-POA, 6-Cl-POA, 5-tert-butyl-POA and 5-tert-butyl-6-Cl-POA were designed and synthesised. The phenyl part was substituted with simple hydrophobic substituents chosen from methyl and halogens. 5-tert-Butyl-N-(5-fluoro-2-methylphenyl)pyrazine-2-carboxamide (9), N-(3-chloro-4-methylphenyl)-5-methylpyrazine-2-carboxamide (12), 6-chloro-N-(3-chloro-4-methylphenyl)pyrazine-2-carboxamide (13) and 6-chloro-N-(5-iodo-2-methylphenyl)pyrazine-2-carboxamide (18) possessed whole cell anti-mycobacterial activity in vitro against Mycobacterium tuberculosis H37Rv with minimum inhibitory concentration (MIC) of around 10 μM. Importantly, no cytotoxicity in the HepG2 model was detected in vitro at the concentrations tested and the estimated IC50 values were in hundreds of μM, indicating promising selectivity. N-(3-Chloro-4-methylphenyl)pyrazine-2-carboxamide (11) and N-(4-chloro-2-iodophenyl)pyrazine-2-carboxamide (21) exerted significant activity against Mycobacterium kansasii with MIC 12.6 μM and 8.7 μM, respectively. No activity was detected against Mycobacterium avium. SAR were in accordance with those observed for the derivatives previously published.     

Functionalization of cotton with poly-NiPAAm/chitosan microgel. Part I. Stimuli-responsive moisture management properties

Stimuli-responsive microgel, based on synthetic polymer (poly-NiPAAm) and biopolymer (chitosan), was incorporated onto cotton fabric surface by pad-dry-cure method using 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinker. In order to assess the moisture management properties of cotton functionalized with responsive microgel, the effects of temperature, relative humidity and concentration of microgel on water vapour transmission rate (WVTR) and moisture content (MC) were quantified. Since the use of experimental design is considered as a highly attractive feature in dealing with experiments and variables of this nature, the effects were quantified by using a central composite design. The regression equations obtained from the statistical analysis allowed the prediction of WVTR and MC at different ambient conditions. Material properties such as crease recovery and whiteness were also measured. The results indicate that both relative humidity and temperature significantly influence studied responses (WVTR and MC), showing that good perspiration can be achieved at lower humidity levels and at higher temperatures. The observed phenomena are attributed to controlled expansion (or contraction) of the surface incorporated microgel, which acts as a sensor of temperature and as a valve to regulate the water vapour permeability of functionalized cotton.     

Structural characterization and thermal behaviour of biological hydroxyapatite

Thermal study and structural characterization of biological hydroxyapatite (HA) samples were done as well as their comparison with commercial and synthetic samples in this study. The X-ray micro analyser shows that all three samples of human teeth (HT1–HT3) contain two types of HA structures with different crystallite sizes, unlike sample of bovine thigh-bone (BTB). The bone sample was composed only of one HA phase with varied porosity. The molar Ca/P ratio in biological samples was lower compared to theoretical ratio for pure HA; moreover, in the case of teeth, Ca/P ratio varyies between the centre and the periphery of the cross-sectional samples. Thermogravimetry of the biological samples showed mass decreases—three regions for the bone and four regions for the teeth. In comparison, commercial HA has only two-step weight loss and synthetic HA three-step weight loss. After the calcination up to 1280 °C all the samples of teeth transformed into whitlockite, β-(Ca,Mg)₃(PO₄)₂ (98 wt%) and 2 wt% HA. Besides, HT3 contained further trace amount of hilgenstockite (HIL, Ca₄P₂O₉). The sample BTB partly transited from natural HA into HIL (6 wt%) and lime, CaO (14 wt%). X-ray powder diffraction (XRD) proved occurrence of HIL (9 wt%) beside stability part HA (91 wt%) in the commercial HA after thermal treatment but the synthetic HA composed from Ca₃(PO₄)₂ (74 wt%) and HA (26 wt%).     

Enthalpic structural relaxation in Te-Se glassy system

Differential scanning calorimetry (DSC) measurements were used to study enthalpic structural relaxation in the Te_ySe_(1−y) glassy system. The examined compositions were y = 0.1, 0.2 and 0.3. Single set of Tool-Narayanaswamy-Moynihan parameters was obtained from the curve-fitting procedure for each studied glass. A comparison with our previous measurements on a-Se was made and the development of particular TNM parameters with increasing Te content was discussed in terms of changes in molecular structure of the material. The curve-fitting results were further verified by several independent non-fitting methods.     

Antitumor Efficacy of Colon‐Specific HPMA Copolymer/9‐Aminocamptothecin Conjugates in Mice Bearing Human‐Colon Carcinoma Xenografts

The antitumor activity of a colon‐specific N‐(2‐hydroxypropyl)methacrylamide (HPMA) copolymer – 9‐aminocamptothecin (9‐AC) conjugate (P‐9‐AC) was assessed in orthotopic and subcutaneous animal (HT29 xenograft) tumor models. P‐9‐AC treatment of mice bearing orthotopic colon tumors, with a dose of 3 mg/kg of 9‐AC equivalent every other day for 6 weeks, resulted in regression of tumors in 9 of 10 mice. A lower dose of P‐9‐AC (1.25 mg/kg of 9‐AC equivalent) every other day for 8 weeks inhibited subcutaneous tumor growth in all mice. No liver metastases were observed. Colon‐specific release of 9‐AC from polymer conjugates enhanced antitumor activity and minimized the systemic toxicity.

     

Photodissociation dynamics of ionic argon pentamer

Photodissociation of the ionized argon pentamer, Ar(5)(+), is studied using an extended diatomics-in-molecules interaction model with the inclusion of the spin-orbit coupling and various dynamical approaches. A thorough comparison with the experimental data available in the literature is presented, including photofragment abundances and their kinetic and internal energy distributions. New predictions are reported for ultraviolet photoexcitation energies, a range that has not been studied before either experimentally or theoretically.     

Enzymatic glycosylation of small molecules: challenging substrates require tailored catalysts

Glycosylation can significantly improve the physicochemical and biological properties of small molecules like vitamins, antibiotics, flavors, and fragrances. The chemical synthesis of glycosides is, however, far from trivial and involves multistep routes that generate lots of waste. In this review, biocatalytic alternatives are presented that offer both stricter specificities and higher yields. The advantages and disadvantages of different enzyme classes are discussed and illustrated with a number of recent examples. Progress in the field of enzyme engineering and screening are expected to result in new applications of biocatalytic glycosylation reactions in various industrial sectors.