Sustained off-resonance irradiation collision-induced dissociation of linear,substituted and cyclic polyesters using a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer

The fragment ions obtained from sustained off-resonance irradiation collision-induced dissociation of linear polyesters, substituted polyesters and cyclic polyesters have been characterized using a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer. Charge-induced and charge-remote fragmentation channels, together with the participation of other nucleophilic groups, are proposed for the substituted polyesters. The linear polyesters were found to fragment at equivalent positions along the polymer chain whereas, under the experimental conditions employed, the cyclic polyester produced a single fragment.     

Conformational effects on glycoside reactivity: study of the high reactive conformer of glucose

The effect of conformation on glycoside reactivity was investigated by studying the hydrolysis of a selection of 3,6-anhydroglucosides as models for glucose in the highly reactive (1)C(4) conformation. Methyl 3,6-anhydro-beta-D-glucopyranoside was found to hydrolyze 200-400 times faster than methyl glucosides in the (4)C(1) conformation, while methyl 3,6-anhydro-beta-D-galactopyranoside, which is in the B(1,4) conformation, was less reactive than methyl beta-D-galactopyranoside. Methyl (3,6-anhydro-beta-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranoside, methyl (3,6-anhydro-alpha-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranosyl-(1 --> 6)-alpha-D-glucopyranoside, and methyl (3,6-anhydro-beta-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranosyl-(1 --> 6)-alpha-D-glucopyranoside were prepared and found to react selectively at the anhydro residue. The finding that (1)C(4) conformers of glucosides are highly reactive species is in accordance with and supports previous results showing that axial OH groups are less electron withdrawing than equatorial OH groups.     

Subcellular imaging mass spectrometry of brain tissue

Imaging mass spectrometry provides both chemical information and the spatial distribution of each analyte detected. Here it is demonstrated how imaging mass spectrometry of tissue at subcellular resolution can be achieved by combining the high spatial resolution of secondary ion mass spectrometry (SIMS) with the sample preparation protocols of matrix-assisted laser desorption/ionization (MALDI). Despite mechanistic differences and sampling 10(5) times less material, matrix-enhanced (ME)-SIMS of tissue samples yields similar results to MALDI (up to m/z 2500), in agreement with previous studies on standard compounds. In this regard ME-SIMS represents an attractive alternative to polyatomic primary ions for increasing the molecular ion yield. ME-SIMS of whole organs and thin sections of the cerebral ganglia of Lymnaea stagnalis demonstrate the advantages of ME-SIMS for chemical imaging mass spectrometry. Subcellular distributions of cellular analytes are clearly obtained, and the matrix provides an in situ height map of the tissue, allowing the user to identify rapidly regions prone to topographical artifacts and to deconvolute topographical losses in mass resolution and signal-to-noise ratio.     

Colorimetric detection of Ricinus communis Agglutinin 120 using optimally presented carbohydrate-stabilised gold nanoparticles

Ricin is a toxic lectin which presents a potential security threat. Its rapid detection is highly desirable. Here we present a colorimetric bioassay based on the aggregation of carbohydrate-stabilised gold nanoparticles which has been used to detect Ricinus communis Agglutinin 120 (RCA(120)) - a ricin surrogate. To achieve a stable and robust sensing system the anchor chain length and the density of the assembled carbohydrates on the gold particle surface has been examined to determine the optimal coverage for maximal aggregation with both RCA(120) and Concanavalin A (Con A) lectins. Gold nanoparticles were stabilised with either a thiolated galactose derivative (9-mercapto-3,6-diaoxaoctyl-beta-d-galactoside) or a thiolated mannose derivative (9-merapto-3,6-dioxaoctyl-alpha-d-mannoside), for RCA(120) and Con A respectively, diluted in each instance with varying ratios of a thiolated triethylene glycol derivative. Aggregation was induced with the respective cognate lectin with the reaction monitored by UV-visible spectrophotometry. The results obtained show that a particle surface with at least 7.5% galactose is required for aggregation with RCA(120) and 6% mannose coverage is required for aggregation with Con A. For each lectin the sensitivity of the assay could be controlled by adjustment of the carbohydrate density on the gold nanoparticles, but with differing results. Maximal aggregation with Con A was achieved with a monolayer consisting of 100% mannose, whereas for RCA(120) maximal aggregation occurred with 70% coverage of galactose. The limit of detection for RCA(120) using the optimally presented galactose-stabilised nanoparticles was 9 nM.     

B,O-chelated azadipyrromethenes as near-IR probes

Complementary synthetic routes to a new class of near-IR fluorophores are described. These allow facile access (four synthetic steps) to the core fluorophore and substituted derivatives with emissions between 740 and 780 nm in good quantum yields.     

Automated,feature-based image alignment for high-resolution imaging mass spectrometry of large biological samples

High-resolution imaging mass spectrometry of large biological samples is the goal of several research groups. In mosaic imaging, the most common method, the large sample is divided into a mosaic of small areas that are then analyzed with high resolution. Here we present an automated alignment routine that uses principal component analysis to reduce the uncorrelated noise in the imaging datasets, which previously obstructed automated image alignment. An additional signal quality metric ensures that only those regions with sufficient signal quality are considered. We demonstrate that this algorithm provides superior alignment performance than manual stitching and can be used to automatically align large imaging mass spectrometry datasets comprising many individual mosaic tiles.     

Continuous flow nanoparticle concentration using alternating current‐electroosmotic flow

Achieving real‐time detection of environmental pathogens such as viruses and bacterial spores requires detectors with both rapid action and a suitable detection threshold. However, most biosensors have detection limits of an order of magnitude or more above the potential infection threshold, limiting their usefulness. This can be improved through the use of automated sample preparation techniques such as preconcentration. In this paper, we describe the use of AC electroosmosis to concentrate nanoparticles from a continuous flow. Electrodes at an optimized angle across a flow cell, and energized by a 1 kHz signal, were used to push nanoparticles to one side of a flow cell, and to extract the resulting stream with a high particle concentration from that side of the flow cell. A simple model of the behavior of particles in the flow cell has been developed, which shows good agreement with experimental results. The method indicates potential for higher concentration factors through cascading devices.     

非平衡态/不可逆过程的热力学理论(Ⅱ)

<正> 7 解的唯一性 如果不考虑非平衡态和不可逆性,则等能密度理论中的基本命题与经典弹性理论中的在形式上完全相同。无论整个系统的动能是大还是小,图6中(sumform)_o上的面力T_i和在(sumform)_c和在的位移u_i将始终在空间坐标系x_i和时刻i下给出。与一般力学中相同,必须知道有关位移u_i及其时间导数的初始条件。它们的影响则可通过(38)和(39)向等能面转化,从而得到