Collagen stabilization and modification using a polyepoxide, triglycidyl isocyanurate

This paper reports a study on the crosslinking behaviour of dermal collagen with the polyepoxide triglycidyl isocyanurate (TEPIC), which is thought to introduce a specific stabilization effect into a collagen matrix. TEPIC shows a higher reactivity towards collagen compared to glycerol triglycidyl ether, a water-soluble epoxide with the same tri-functionality but having an aliphatic backbone in its molecular structure, and one of the most commonly used epoxide monomers reported in the literature. Significant stabilization of the collagen matrix treated with TEPIC has been shown in our work, based on the examination of hydrothermal properties, thermal degradation and enzyme degradation properties, amino acid analysis and measurement of mechanical properties. Collagen's dimensional stability was also found to be improved, from tensile testing and fibre morphology observations (here by scanning electron microscopy). The overall stabilization effect of TEPIC is comparable or better than the conventionally used crosslinker, glutaraldehyde, and so implies that a stable three-dimensional, covalent network is formed by the TEPIC within the collagen supermolecule, instead of the two-dimensional crosslinked bridging systems in the case of glutaraldehyde. These results also suggest that the additional stabilization by TEPIC may relate to its triazine nucleus, which introduces a more rigid conformation into the collagen polypeptide chains. In addition, the treated collagen matrix has been found to have increased adsorption ability for anionic dyes. This study has shown that TEPIC can be considered as one of the more effective aldehyde alternatives, which could have a potential significance in leather and textile industrial applications.     

Solid-phase combinatorial synthesis of benzothiazoles, benzimidazoles, and benzoxazoles using a traceless linker

New methodology for the solid-phase synthesis of benzothiazoles, benzimidazoles, and benzoxazoles has been developed by using a traceless 4-alkoxy-aniline linker. The desired products were released from the polymer support by imine-exchange process coupled with air oxidation. Combinatorial library consisting of 36 members has been synthesized using this linker. The yields are low to good, which highly depend on the building blocks. Recycling of the polymer support was also investigated.     

Iron-catalyzed olefin cis-dihydroxylation using a bio-inspired N,N,O-ligand

Nature has evolved enzymes that carry out the cis-dihydroxylation of C=C bonds in the biodegradation of arenes in the environment. These enzymes, called Rieske dioxygenases, have mononuclear iron centers coordinated to a 2-His-1-carboxylate facial triad motif that has emerged as a common structural element among many nonheme iron enzymes. In contrast, olefin cis-dihydroxylation is conveniently carried out by OsO4 and related species in synthetic procedures. To develop more environmentally benign strategies for carrying out these transformations, we have designed Ph-DPAH [(di-(2-pyridyl)methyl)benzamide], a tridentate ligand that mimics the facial N,N,O site of the mononuclear iron center in the Rieske dioxygenases. Its iron(II) complex has been found to catalyze olefin cis-dihydroxylation almost exclusively and with high H2O2 conversion efficiency on a wide range of substrates. and 18O labeling experiments suggest the participation of an FeV oxidant.     

Synthesis of a polypseudorotaxane, polyrotaxane, and polycatenane using ‘click’ chemistry

The synthesis of a polypseudorotaxane, polyrotaxane, and polycatenane containing the electron-deficient cyclophane cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) subunit in the side chain is described. These interlocked supramolecular polymers have been prepared from an azide-functionalized polystyrene derivative and an acetylene-functionalized [2]rotaxane, [2]catenane and their parent tetracationic cyclophane via Cu(I)-catalyzed 1,3 dipolar cycloadditions (‘click chemistry’). The synthesis and characterization of the polymers and intermediates has been described using IR, ¹H NMR, UV spectroscopies, and voltammetry. We have shown that the CBPQT⁴⁺ unit of the side chain polystyrene derivative has the ability to reversibly undergo complexation with a complementary dialkoxynaphthalene derivative.     

Production of pyrans, pyridazines, pyrimidines, pyrazines and triazine compounds using benzoylacetonitriles as a precursor

Benzoylacetonitriles are easily available and have high chemical reactivity due to the presence of three active moieties; nitrile, carbonyl, and active methylene functions. This review article represents a survey covering the synthetic strategies leading to five six-membered heterocycles; pyrans, pyridazines, pyrimidines, pyrazines, and triazine compounds; utilizing benzoylacetonitriles as starting precursor since 1985. The reactions are subdivided into groups that cover the synthetic methods of these heterocycles.     

Determination of free,esterified, and total serum cholesterol using a sensitive color reaction

A method is described for the enzymatic determination of free and total cholesterol sequentially in either whole serum or the HDL fraction. Measurement of low levels of free cholesterol is facilitated by the substitution of sodium 2-hydroxy-3,5-dichlorobenzene-sulfonate for phenol in the peroxidase-catalyzed indicator reaction. Both free and total cholesterol may be measured in the same tube or separately. These alternatives may appeal to investigators who for various reasons may prefer to perform these determinations either sequentially or separately. The sequential approach is a means of conserving the relatively expensive enzymatic reagents.     

Convenient preparation of cyclic acetals,using diols,TMS-source,and a catalytic amount of TMSOTf

With use of diol, alkoxysilane, and a catalytic amount of trimethylsilyl trifluoromethanesulfonate (TMSOTf), carbonyl compounds are converted to acetals in good yields under mild conditions. This procedure, which was carried out without synthesizing the silylated diols, is a more convenient adaptation of Noyori's method. This acetalization applies to not only simple but also conjugated carbonyl compounds. Moreover, various TMS compounds, including solid supported compounds, are effective for this method instead of alkoxylsilane.     

Maple syrup analysis for137Cs,K, and B,using a low-background counting system and PGAA

Fifteen maple syrups were analyzed for¹³⁷Cs and K (via⁴⁰K) by using a low-background -ray counting system, and for B and K by using neutron capture prompt -ray activation analysis (PGAA). For low-background -ray counting, 3 limits of detection (24-hour counts) were 0.03 Bq¹³⁷Cs/kg and 10 mg K/kg for 3.5-L portions and 0.08 Bq¹³⁷Cs/kg and 20 mg K/kg for 1.0-L portions. K concentrations determined by the two methods (using 2-g portions for PGAA) were in excellent agreement. The products were obtained in 1991, with one produced in Maryland, three in New York, four in Pennsylvania, two in New Hampshire, and five in Canada. The average activity concentration for Canadian syrups (2.8 Bq¹³⁷Cs/kg) was nearly a factor of 20 greater than the average (0.15 Bq¹³⁷Cs/kg) for the other syrups, but all¹³⁷Cs activity concentrations were at least 100 times lower than those for which controls would be recommended according to Federal Radiation Council guidance. The data exhibited distinct groupings related to the sources of the products when the ratios of¹³⁷Cs activity to K content (Bq_Cs/mg_K) were plotted vs. B concentrations.     

A radioxenon detection system using CdZnTe,an array of SiPMs,and a plastic scintillator

This paper presents the design and characterization of a prototype compact beta–gamma radioxenon detection system that utilizes a coplanar CdZnTe crystal, an array of SiPMs, and a plastic scintillator. The detector is directly mounted on a custom PCB. The system provides the advantage of room-temperature operation, while being compact, low noise, and with simple readout electronics. Preliminary measurements using ¹³⁷Cs, ¹³⁵Xe, and ^133/133mXe were conducted to optimize various system parameters to achieve optimal resolution of key photopeaks. The purpose of this research was to explore the potential of these radiation detection elements for use in beta–gamma coincidence applications.     

Self-assembly of metallamacrocycles using a dinuclear organometallic acceptor: synthesis, characterization, and sensing study

A dinuclear organometallic acceptor 4,4'-bis[trans-Pt(PEt(3))(2)(O(3)SCF(3))(ethynyl)]biphenyl (1) containing Pt-ethynyl functionality is synthesized. Multinuclear NMR ((1)H, (31)P, and (13)C), infrared (IR), and electrospray ionization mass spectrometry (ESI-MS) including single-crystal X-ray diffraction analysis established the formation of 1. Equimolar treatment of acceptor 1 separately with three different "clip" type ditopic donors (L(a)-L(c)) yielded [2 + 2] self-assembled three metallamacrocycles 2a-2c, respectively. These macrocycles were characterized by various spectroscopic techniques, and their sizes/shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) simulations. Attachment of unsaturated ethynyl functionality to biphenyl building unit helped to make the macrocycles (2a-2c) π-electron rich and thereby fluorescent in nature. Furthermore, 2c in solution has been examined to be suitable for sensing electron-deficient nitroaromatic like picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 2c showed a marked quenching of initial emission intensity upon titrating with picric acid (PA), and it exhibited the largest fluorescence quenching response with high selectivity among various other electron deficient aromatic compounds tested.     

Adsorption and desorption studies of a water soluble dye, Quinoline Yellow, using waste materials

Bottom ash, a power plant waste, and de-oiled soya, an agricultural waste material, were employed for the removal and recovery of Quinoline Yellow, a water-soluble dye. Characterization of adsorbent materials was made by their infrared and differential thermal analysis curves. Along with batch adsorption studies, which involve effect of pH, adsorbate concentration, sieve size, adsorbent dosage, contact time, temperature, etc., kinetic studies and column operations were also made to remove the dye from wastewater. On the basis of kinetic studies, specific rate constants involved in the processes were calculated and first-order adsorption kinetics was observed in both the cases. The paper also incorporates Langmuir and Freundlich adsorption isotherm models, which are used to calculate thermodynamic parameters and also to suggest a plausible mechanism of the ongoing adsorption processes. Fixed bed columns were prepared for both the adsorbents and bulk removal of the dye was achieved by eluting aqueous solution of the dye and saturation factor for both columns were evaluated. Dilute NaOH solution was then percolated through the exhausted columns to recover the adsorbed dye.     

Human genomic DNA analysis using a semi-automated sample preparation, amplification, and electrophoresis separation platform

The growing importance of analyzing the human genome to detect hereditary and infectious diseases associated with specific DNA sequences has motivated us to develop automated devices to integrate sample preparation, real-time PCR, and microchannel electrophoresis (MCE). In this report, we present results from an optimized compact system capable of processing a raw sample of blood, extracting the DNA, and performing a multiplexed PCR reaction. Finally, an innovative electrophoretic separation was performed on the post-PCR products using a unique MCE system. The sample preparation system extracted and lysed white blood cells (WBC) from whole blood, producing DNA of sufficient quantity and quality for a polymerase chain reaction (PCR). Separation of multiple amplicons was achieved in a microfabricated channel 30 microm x 100 microm in cross section and 85 mm in length filled with a replaceable methyl cellulose matrix operated under denaturing conditions at 50 degrees C. By incorporating fluorescent-labeled primers in the PCR, the amplicons were identified by a two-color (multiplexed) fluorescence detection system. Two base-pair resolution of single-stranded DNA (PCR products) was achieved. We believe that this integrated system provides a unique solution for DNA analysis.     

Predicting the reactivity of ambidentate nucleophiles and electrophiles using a single, general-purpose, reactivity indicator

We recently proposed a new reactivity indicator, termed the "general-purpose reactivity indicator", Xi, which describes not only the classical reactivity paradigms, but also describes reactions that are neither frontier-orbital nor electrostatically controlled. This indicator was proposed to be especially useful for reactants with multiple reactive sites, especially if the nature of the reactivity at those sites was different. This suggests that this reactivity indicator is especially appropriate for ambidentate molecules; this paper confirms this hypothesis. The general-purpose reactivity indicator not only identifies the most reactive sites, it also identifies which substrates prefer which reactive sites. In particular, the reactivity indicator allows one to clearly distinguish which sites of an ambidentate molecule are most reactive when electron transfer from the attacking reagent is large (a soft reagent) and which sites are most reactive when the attacking reagent is hard and highly charged (so that electron transfer is relatively insignificant). To illustrate the efficacy of the indicator for nucleophiles we consider SCN(-), SeCN(-), NO(2)(-), SO(3)(2-). For electrophiles we consider dimethyl carbonate, N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS), and 1-chloro-2,4,6-trinitrobenzene (CNB).     

Synthesis of a tetraoxy-bis-nortaxadiene, en route to taxol, using a cascade radical cyclisation sequence

Concise syntheses of the substituted enynediones 28a, 33b and 36 starting from the cyclohexenealdehyde 18, corresponding to ring A in the taxanes, and the vinylstannane 24, are described. Treatment of 36 with Bu₃SnH-AIBN did not lead to the oxy-substituted taxadiene 37 expected from a tandem radical macrocyclisation-radical transannulation sequence; instead, a mixture of unidentified products resulted. When the PMB ether 33b corresponding to the alcohol 36 was treated with Bu₃SnH-AIBN under similar conditions, p-anisaldehyde was isolated, as a major by-product, but no evidence for the formation of a taxadiene could be observed. In contrast, the iododienynedione 41, i.e., deoxy 36, underwent a tandem radical macrocyclisation-transannulation sequence, when treated with Bu₃SnH-AIBN, leading to the tetraoxy-bis-nortaxadiene 42 in 44% yield. Attempts to synthesise the alcohol 28b from the silyl ether 28a en route to the iodide 28c instead gave the substituted tetrahydrofuran 29 via an intramolecular oxy-Michael reaction.     

Sorption-spectrophotometric determination of lanthanum,gadolinium, and ytterbium using chlorophosphonazo III on a PANF-Chel adsorbent

The possibilities of the sorption-spectroscopic determination of the sum of rare-earth elements have been studied on an example of La, Gd, and Yb as representatives of the light, middle, and heavy rare earth elements. The determination is carried out after the sorption from solutions with pH 3 onto the surface polyacrylonitrile fiber loaded with a Chel-100 ion exchanger followed by complexation with Chlorophosphonazo III. A dynamic version of the sorption-spectroscopic determination of the sum of La, Gd, and Yb has been developed for the concentration range 5–30 ng/mL with a detection limit of 3 ng/mL. The method was tested in the analysis of model solutions of CaCl₂, FeCl₃, and TiCl₄; RSD < 20%.     

Computing resonance energies, widths, and wave functions using a Lanczos method in real arithmetic

We introduce new ideas for calculating resonance energies and widths. It is shown that a non-Hermitian-Lanczos approach can be used to compute eigenvalues of H+W, where H is the Hamiltonian and W is a complex absorbing potential (CAP), without evaluating complex matrix-vector products. This is done by exploiting the link between a CAP-modified Hamiltonian matrix and a real but nonsymmetric matrix U suggested by Mandelshtam and Neumaier [J. Theor. Comput. Chem. 1, 1 (2002)] and using a coupled-two-term Lanczos procedure. We use approximate resonance eigenvectors obtained from the non-Hermitian-Lanczos algorithm and a very good CAP to obtain very accurate energies and widths without solving eigenvalue problems for many values of the CAP strength parameter and searching for cusps. The method is applied to the resonances of HCO. We compare properties of the method with those of established approaches.     

Potential of using a single fermenter for biomass build-up,starch hydrolysis,and ethanol production

Data on conversion of starch on biomass and ethanol bySchwanniomyces castellii in an aerobic-anaerobic solid state fermentation is reported.Schwanniomyces castellii grew exponentially in the aerobic phase (12 h) and simultaneously hydrolyzed nearly half (55%) of the starch initially present. The accumulation of glucose increased up to 12 h, whereas maltose was nearly absent beyond 7 h. Shift of metabolism from oxidative to fermentative pattern was observed about 10 h as a result of the build-up of CO₂ level and faster utilization of O₂. The ethanol production in the anaerobic phase reached the level of 89.3 mg ethanol/g initial dry matter by the end of 30 h. A total of 92.9% of the starch is utilized during the fermentation. The overall ethanol conversion yields are 57.8% of the theoretical value, whereas in the anaerobic phase it was found to be 94.4%. The cell shape, its morphology, and the type of attachment to the solid support were found to be similar in aerobic and anaerobic phases of fermentation. Data given in this work indicate the feasibility of using one single fermenter for aerobic growth to generate inoculum as well as to simultaneously hydrolyze the starch and subsequent anaerobic fermentation to produce ethanol.     

Decontamination of VX, GD, and HD on a surface using modified vaporized hydrogen peroxide

Vaporized hydrogen peroxide (VHP) has proven efficacy for biological decontamination and is a common gaseous sterilant widely used by industry. Regarding chemical warfare agent decontamination, VHP is also effective against HD and VX, but not GD. Simple addition of ammonia gas to VHP affords reactivity toward GD, while maintaining efficacy for HD (and bioagents) and further enhancing efficacy for VX. Thus, modified VHP is a broad-spectrum CB decontaminant suitable for fumigant-type decontamination scenarios, i.e., building, aircraft, and vehicle interiors and sensitive equipment. Finally, as an interesting aside to the current study, commercial ammonia-containing cleaners are also shown to be effective surface decontaminants for GD, but not for VX or HD.     

Determination of carbendazim, thiabendazole and fuberidazole using a net analyte signal-based method

The net analyte signal (NAS)-based method HLA/GO, modification of the original hybrid linear analysis (HLA) method, has been used to determine carbendazim, fuberidazole and thiabendazole in water samples. This approach was used after a solid-phase extraction (SPE) step, using the native fluorescence emission spectra of real samples, previously standardized by piecewise direct standardization (PDS). The results obtained show that the modification of HLA performs in a similar way that partial least-squares method (PLS-1). The NAS concept was also used to calculate multivariate analytical figures of merit such as limit of detection, selectivity, sensitivity and analytical sensitivity (γ⁻¹). With this purpose, blanks of methanol and ternary mixtures, with the target analyte at low concentration and the other two ranging according to the calibration matrix, were used, with different results. Detection limits calculated in the last way are more realistic and show the influence of the other components in the sample. Selectivity for carbendazim is higher than the corresponding values for fuberidazole and thiabendazole, whereas sensitivity, as well as the values obtained for their detection limits, are lower for carbendazim, followed by thiabendazole and fuberidazole. Results obtained by modification of HLA vary in the same way that the ones obtained by PLS-1.     

Ion chromatography of aluminium, gallium and indium using a complexing mobile phase

Summary The elements Al, Ga and In were analyzed by ion chromatography using a complexing mobile phase and a refractive index monitor as detector. Linearities between detector response and concentration were found up to 100 /g or more (with respect to the metal ion), detection limits being below 1 g/g. Additionally, the simultaneous codetermination of simple anions like chloride, nitrate, sulphate and others were investigated along with interferences from other common cations.Dedicated to Prof. Dr. R. Pietsch on the occasion of his 65th birthday on November 9, 1990.