65 resultados para cyclotron resonance
Resumo:
A general mass spectrometry technique for the characterization of alkanethiol-modified surfaces is presented. Alkanethiol self-assembled onto a gold surface (in this case, peptides were attached to the gold surface via a thiolate bond) was reductively desorbed in 0.05 M KOH in the presence of octadecyl-derivatized silica gel. The peptide adsorbed onto the silica gel, whereupon it could be filtered, washed to remove any salts, and then eluted using a mixture of 4:1 v/v methanol/water. The eluant containing the peptide was injected into a Fourier transform ion-cyclotron resonance mass spectrometer (FTICR/MS) via electrospray ionization. The spectrum showed no fragmentation of the peptide, demonstrating the gentleness of the technique. This simple procedure is not limited to FTICR/MS and could be adapted to other mass spectrometers.
Resumo:
The synthesis and complete characterisation of the fluorescent ligand, 4-acridinol-1-sulphonic acid (the acridine analogue of 8-quinolinol-5-sulfonic acid) is described. Using a judicious array of nuclear magnetic resonance spectroscopy experiments, the structural elucidation and full assignment of all proton and carbon chemical shifts were afforded. The 4-acridinol-1-sulphonic acid was found to behave in a similar manner to 8-quinolinol-5-sulphonic acid, forming fluorescent complexes with magnesium(II) and zinc(II). The uncorrected emission maxima for the metal–acridinol complexes were found to be at around 620 nm compared to 505 nm for the respective quinolinol complexes. Unfortunately, preliminary spectrofluorimetric analytical figures of merit revealed that the detection limits of the new acridinol metal complexes were one and a half orders of magnitude poorer than those attained with the corresponding quinolinol ligand. However, in contrast to 8-quinolinol-5-sulphonic acid, the 4-acridinol-1-sulphonic acid ligand showed considerable selectivity for magnesium(II) and zinc(II) over aluminium(III).
Resumo:
A simple model peroxyoxalate chemiluminescence system was monitored directly across a range of temperatures (from −80 to +20 °C) using 13C nuclear magnetic resonance spectroscopy. These experiments were made possible by the utilisation of 13C doubly labelled oxalyl chloride, which was reacted with anhydrous hydrogen peroxide in dry tetrahydrofuran. Ab initio quantum calculations were also performed to estimate the 13C nuclear magnetic resonance (NMR) shift of the most commonly postulated key intermediate 1,2-dioxetanedione and this data, in concert with the spectroscopic evidence, confirmed its presence during the reaction.
Resumo:
Proton nuclear magnetic resonance spectroscopy (NMR) has shown the potential for being a valuable tool in monitoring a commercial fermentation. In this preliminary study, a suite of organic analytes including ethanol, fructose, glucose, methanol, glycerol, malic acid, tartaric acid, succinic acid, acetic acid and lactic acid were simultaneously determined during the fermentation. Data collection and analysis using chemometric algorithms aided the understanding of key processes including the effects of seeding a wine with bacteria for malo-lactic fermentation.
Resumo:
Background: Diagnosis of patellar tendinopathy is based primarily on clinical examination; however, it is commonplace to image the patellar tendon for diagnosis confirmation, with the imaging modalities of choice being magnetic resonance imaging (MRI) and ultrasonography (US). The comparative accuracy of these modalities has not been established.
Hypothesis: Magnetic resonance imaging and US have good (>80%) accuracy and show substantial agreement in confirming clinically diagnosed patellar tendinopathy.
Study Design: Cohort study (diagnosis); Level of evidence, 2.
Methods: Magnetic resonance imaging and US (gray scale [GS-US] and color Doppler [CD-US]) features of 30 participants with clinically diagnosed patellar tendinopathy and 33 activity-matched, asymptomatic participants were prospectively compared. Accuracy, sensitivity, specificity, positive and negative predictive values, and the likelihood of positive and negative test results were determined for each technique.
Results: The accuracy of MRI, GS-US, and CD-US was 70%, 83%, and 83%, respectively (P = .04; MRI vs GS-US). The likelihood of positive MRI, GS-US, and CD-US was 3.1, 4.8, and 11.6, respectively. The MRI and GS-US had equivalent specificity (82% vs 82%; P = 1.00); however, the sensitivity of GS-US was greater than MRI (87% vs 57%; P = .01). Sensitivity (70% vs 87%; P = .06) and specificity (94% vs 82%; P = .10) did not differ between CD-US and GS-US.
Conclusions: Ultrasonography was more accurate than MRI in confirming clinically diagnosed patellar tendinopathy. GS-US and CD-US may represent the best combination for confirming clinically diagnosed patellar tendinopathy because GS-US had the greatest sensitivity, while a positive CD-US test result indicated a strong likelihood an individual was symptomatic.
Confirmation of SGIp1: endophilin interaction using bioluminescence resonance energy transfer (BRET)
Resumo:
We reported 11B nuclear magnetic resonance studies of boron nitride (BN) nanotubes prepared by mechano-thermal route. The NMR lineshape obtained at 192.493 MHz (14.7 T) was fitted with two Gaussian functions, and the 11B nuclear magnetization relaxations were satisfied with the stretched–exponential function, exp[-(tlT1)(D+1)/6] (D: space dimension) at all temperatures. In addition, the temperature dependence of spin–lattice relaxation rates was well described by Ti-1 = aT (a: constant, T: temperature) and could be understood in terms of direct phonon process. All the 11BNMR results were explained by considering the inhomogeneous distribution of the paramagnetic metal catalysts, such as α-Fe, Fe–N, and Fe2 B, that were incorporated during the process of high-energy ball milling of boron powder and be synthesized during subsequent thermal annealing. X-ray powder diffraction as well as electron paramagnetic resonance (EPR) on BN nanotubes were also conducted and the results obtained supported these conclusions.
Resumo:
Further consideration has been given to the reaction pathway of a model peroxyoxalate chemiluminescence system. Again utilising doubly labelled oxalyl chloride and anhydrous hydrogen peroxide, 2D EXSY 13C nuclear magnetic resonance (NMR) spectroscopy experiments allowed for the characterisation of unknown products and key intermediate species on the dark side of the peroxyoxalate chemiluminescence reaction. Exchange spectroscopy afforded elucidation of a scheme comprised of two distinct mechanistic pathways, one of which contributes to chemiluminescence. 13C NMR experiments carried out at varied reagent molar ratios demonstrated that excess amounts of hydrogen peroxide favoured formation of 1,2-dioxetanedione: the intermediate that, upon thermolysis, has been long thought to interact with a fluorophore to produce light.
Resumo:
The benefit of impact-loading activity for bone strength depends on whether the additional bone mineral content (BMC) accrued at loaded sites is due to an increased bone size, volumetric bone mineral density (vBMD) or both. Using magnetic resonance imaging (MRI) and dual energy X-ray absorptiometry (DXA), the aim of this study was to characterize the geometric changes of the dominant radius in response to long-term tennis playing and to assess the influence of muscle forces on bone tissue by investigating the muscle–bone relationship. Twenty tennis players (10 men and 10 women, mean age: 23.1 ± 4.7 years, with 14.3 ± 3.4 years of playing) were recruited. The total bone volume, cortical volume, sub-cortical volume and muscle volume were measured at both distal radii by MRI. BMC was assessed by DXA and was divided by the total bone volume to derive vBMD. Grip strength was evaluated with a dynamometer. Significant side-to-side differences (P < 0.0001) were found in muscle volume (+9.7%), grip strength (+13.3%), BMC (+13.5%), total bone volume (+10.3%) and sub-cortical volume (+20.6%), but not in cortical volume (+2.6%, ns). The asymmetry in total bone volume explained 75% of the variance in BMC asymmetry (P < 0.0001). vBMD was slightly higher on the dominant side (+3.3%, P < 0.05). Grip strength and muscle volume correlated with all bone variables (except vBMD) on both sides (r = 0.48–0.86, P < 0.05–0.0001) but the asymmetries in muscle parameters did not correlate with those in bone parameters. After adjustment for muscle volume or grip strength, BMC was still greater on the dominant side. This study showed that the greater BMC induced by long-term tennis playing at the dominant radius was associated to a marked increase in bone size and a slight improvement in volumetric BMD, thereby improving bone strength. In addition to the muscle contractions, other mechanical stimuli seemed to exert a direct effect on bone tissue, contributing to the specific bone response to tennis playing.
Resumo:
Pre- and early puberty seem to be the most opportune times for exercise to improve bone strength in girls, but few studies have addressed this issue in boys. This study investigated the site-, surface-, and maturity-specific exercise-induced changes in bone mass and geometry in young boys. The osteogenic effects of loading were analyzed by comparing the playing and nonplaying humeri of 43 male pre-, peri-, and postpubertal competitive tennis players 10-19 yr of age. Total bone area, medullary area, and cortical area were determined at the mid (40-50%) and distal humerus (60-70%) of both arms using MRI. Humeral bone mass (BMC) was derived from a whole body DXA scan. In prepubertal boys, BMC was 17% greater in the playing compared with nonplaying arm (p < 0.001), which was accompanied by a 12-21% greater cortical area, because of greater periosteal expansion than medullary expansion at the midhumerus and periosteal expansion associated with medullary contraction at the distal humerus. Compared with prepuberty, the side-to-side differences in BMC (27%) and cortical area (20-33%) were greater in peripuberty (p < 0.01). No differences were found between peri- and postpuberty despite longer playing history in the postpubertal players.The osteogenic response to loading was greater in peri- compared with prepubertal boys, which is in contrast with our previous findings in girls and may be caused by differences in training history. This suggests that the window of opportunity to improve bone mass and size through exercise may be longer in boys than in girls.
Resumo:
Few would deny the importance of the mother in the care of her infant, but her relevance, her resonance and the indelible traces she leaves in the psyche of the developing individual and which thereafter accompanies and influences the life course is investigated in this psychoanalytically informed study.
Resumo:
Surface based analytical tools have gained more importance for rapid, sensitive and label-free monitoring of molecular recognition events. Surface plasmon resonance (SPR) has played a prominent role in real time monitoring of surface binding events. SPR is increasing its significance especially for the study of ultrathin dielectric layer. This paper investigates the role of thin films of gold, silver and aluminium for protein detection in SPR biosensors. It is shown that the sensitivity, which is indicated by the shift of plasmon dip, is not linearly related to the thickness of protein but quadratic over a specific range. The approach involves a plot of a reflectivity curve as a function of the angle of incidence.