DNA as a bioligand supported on magnetite for grafting palladium nanoparticles for cross-coupling reaction

The utilization of deoxyribonucleic acid (DNA) in nanotechnology is a promising area of research wherein the distinct properties of DNA are exploited for the design and development of new materials and applications. The biodegradability and natural profusion of DNA makes it highly suitable for use in various fields. In this report, we have treated DNA as a bioligand, supported on functionalized magnetite for the grafting of palladium (Pd) nanoparticles to make Pd-DNA bio-nanocatalyst. The Pd-DNA was subjected to Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Brunauer–Emmett–Teller, energy dispersive X-ray spectroscopy, vibrating sample magnetometry, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectrometry analysis. The prepared Pd-DNA was found to be highly efficient in catalyzing Suzuki–Miyaura cross-coupling reaction with excellent yields when compared with commercially available palladium-based catalysts. Also, the Pd-DNA could be easily recovered from the reaction mass using an external magnet and recycled up to six times without substantial loss of activity. Furthermore, Felbinac, a non-inflammatory drug, was synthesized in quantitative yields using the Pd-DNA bio-nanocatalyst.     

New class of aggregates in aqueous solution: an NMR, thermodynamic, and dynamic light scattering study

We investigated the aggregation properties of two classes of aromatic and hydrophobic compounds, namely chloroacetamides and ethyl 3-phenyl-2-nitropropionates, in moderately concentrated aqueous solution (millimolar range). The identification of all species present in solution under specific experimental conditions was performed by 1D and 2D NMR, pulsed gradient spin-echo NMR, and dynamic light scattering techniques. Some physical-chemical properties (viscosity, surface tension, and colligative properties) of the aqueous solutions were also determined. Both classes of compounds behave quite similarly: in solution, three distinct species, namely a monomeric species, small and mobile aggregates, and large and stiff aggregates, are observed. The results give insight into a new class of aggregates, held together by pi-pi interactions, which show an unusual associative behavior in water.     

HPLC-MS characterization of cyclo-statherin Q-37, a specific cyclization product of human salivary statherin generated by transglutaminase 2

In the present study the analytical potential of HPLC-MS/MS was utilized for the structural characterization of a post-translational modification of statherin. Human salivary statherin (M(av)5380.0 +/- 0.3 Da) is transformed by the action of transglutaminase 2 into a cyclic derivative with an average molecular mass of 5363.0 +/- 0.3 Da. The intra-molecular bridge is generated by the loss of an ammonia molecule between the unique Ione-pair donating nucleophile Lys-6 and one acceptor among the seven glutamine residues of statherin. Digestion of the cyclic derivative with chymotrypsin, proteinase K, and carboxypeptidase Y, monitored by HPLC-electrospray ionization-ion trap-mass spectrometric analysis, demonstrated that cyclization involved almost specifically Gln-37 (> 95%), with the percentage of Gln-39 implicated in the cross-linkiing being less than 5%. The main derivative was named cyclostatherin Q37. Guineapig transglutaminase 2 showed high affinity for statherin in vitro (Km = 0.65 +/- 0.06 microM). Cyclo-statherin was detected in vivo by HPLC-electrospray ionization ion trap-mass spectrometry analysis of whole human saliva and it accounted for about 1% of total statherin. Detection of cyclo-statherin in whole saliva is suggestive of a putative role of this molecule in the formation of the "oral protein pellicle".     

Time-harmonic solution for acousto-elastic interaction with controllability and spectral elements

The classical way of solving the time-harmonic linear acousto-elastic wave problem is to discretize the equations with finite elements or finite differences. This approach leads to large-scale indefinite complex-valued linear systems. For these kinds of systems, it is difficult to construct efficient iterative solution methods. That is why we use an alternative approach and solve the time-harmonic problem by controlling the solution of the corresponding time dependent wave equation.In this paper, we use an unsymmetric formulation, where fluid-structure interaction is modeled as a coupling between pressure and displacement. The coupled problem is discretized in space domain with spectral elements and in time domain with central finite differences. After discretization, exact controllability problem is reformulated as a least-squares problem, which is solved by the conjugate gradient method.     

Reactions of 9-substituted guanines with bromomalondialdehyde in aqueous solution predominantly yield glyoxal-derived adducts

Reactions of 9-ethylguanine, 2'-deoxyguanosine and guanosine with bromomalondialdehyde in aqueous buffers over a wide pH-range were studied. The main products were isolated and characterized by (1)H and (13)C NMR and mass spectroscopy. The final products formed under acidic and basic conditions were different, but they shared the common feature of being derived from glyoxal. Among the 1 : 1 adducts, 1,N(2)-(trans-1,2-dihydroxyethano)guanine adduct (6) predominated at pH < 6 and N(2)-carboxymethylguanine adduct (10a,b) at pH > 7. In addition to these, an N(2)-(4,5-dihydroxy-1,3-dioxolan-2-yl)methylene adduct (11a,b) and an N(2)-carboxymethyl-1,N(2)-(trans-1,2-dihydroxyethano)guanine adduct (12) were obtained at pH 10. The results of kinetic experiments suggest that bromomalondialdehyde is significantly decomposed to formic acid and glycolaldehyde under the conditions required to obtain guanine adducts. Glycolaldehyde is oxidized to glyoxal, which then modifies the guanine base more readily than bromomalondialdehyde. Besides the glyoxal-derived adducts, 1,N(2)-ethenoguanine (5a-c) and N(2),3-ethenoguanine adducts (4a-c) were formed as minor products, and a transient accumulation of two unstable intermediates, tentatively identified as 1,N(2)-(1,2,2,3-tetrahydroxypropano)(8) and 1,N(2)-(2-formyl-1,2,3-trihydroxypropano)(9) adducts, was observed.     

Complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands

The complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) was studied in aqueous solution and in the solid state. The formation constants of [V(IV)O(taci)](2+), [V(IV)O(tdci)](2+), and [V(IV)(tdci)(2)](4+) and of the deprotonation product [V(IV)(tdci)(2)H(-)(1)](3+) were determined (25 degrees C, 0.1 M KNO(3)). Cyclic voltammetry measurements established a reversible one-electron transfer for the [V(IV)(tdci)(2)H(-)(m)]((4)(-)(m))/[V(III)(tdci)(2)H(-)(n)]((3)(-)(n)) couple (0 相似文献   

High-performance liquid chromatography-tandem mass spectrometry validation of medroxyprogesterone acetate in products of pork origin and serum

Different extraction and purification methods are described here to determine medroxyprogesterone acetate (MPA) in pork meat and serum. Spiked samples are investigated over the concentration range of MPA 0.5-20 ng/g. Pork meat tissues are subjected to extraction using organic solvent, and pork serum is simply diluted with acetate buffer. Clean-up is performed using solid-phase extraction on a C18 cartridge, and MPA is eluted with ethanol. Aliquots are injected into a high-performance liquid chromatography-mass spectrometry system. MPA content is determined on the basis of m/z 387-327 and 387-123 transitions.     

Dynamic MR imaging of brain tumors in low field using undersampled projection reconstruction

A new application of the projection reconstruction method was developed, enabling dynamic T(1)-weighted contrast-enhanced magnetic resonance image (MRI) of brain tumors in a low-field imager. Two undersampled projection reconstruction spin echo sequences were implemented in an open low-field (0.23-T) MR imager, one with 64 and another with 42 projections in [0,pi], repetition time 150 ms, echotime 15 ms, and six slices were used in both sequences. The possibility of using these sequences to image dynamic contrast enhancement of brain tumors was studied in laboratory experiments and in two patient cases, one with fibrotic and the other with meningothelial meningioma. The laboratory experiments showed a nearly linear response in signal intensity to the concentration of gadopentetate dimeglumine in purified water up to 1.25 mM. Increasing concentrations up to 5.0 mM did not significantly affect the signal intensity, though starting from 3.0 mM concentration T(2) shortening decreased intensities slightly. The patient cases showed results consistent with an earlier study performed in a high-field imager. The results show that the studied sequences can be used to follow dynamic contrast enhancement in a low-field imager.     

Students’ Activity in Computer-Supported Collaborative Problem Solving in Mathematics

The purpose of this study was to analyse secondary school students’ (N = 16) computer-supported collaborative mathematical problem solving. The problem addressed in the study was: What kinds of metacognitive processes appear during computer-supported collaborative learning in mathematics? Another aim of the study was to consider the applicability of networked learning in mathematics. The network-based learning environment Knowledge Forum (KF) was used to support students’ collaborative problem solving. The data consist of 188 posted computer notes, portfolio material such as notebooks, and observations. The computer notes were analysed through three stages of qualitative content analysis. The three stages were content analysis of computer notesin mathematical problem solving, content analysis of mathematical problem solving activity and content analysis of the students’ metacognitive activity. The results of the content analysis illustrate how networked discussions mediated mathematical knowledge and students’ questions, while the mathematical problem solving activity shows that the students co-regulate their thinking. The results of the content analysis of the students’ metacognitive activity revealed that the students use metacognitive knowledge and make metacognitive judgments and perform monitoring during networked discussions. In conclusion, the results of this study demonstrate that working with the networked technology contributes to the students’ use of their mathematical knowledge and stimulates them into making their thinking visible. The findings also show some metacognitive activity in the students’ computer-supported collaborative problem solving in mathematics.