Parent and neutral loss monitoring on a quadrupole ion trap mass spectrometer: screening of acylcarnitines in complex mixtures

A novel and practical technique for performing both parent and neutral loss (P&NL) monitoring experiments on a quadrupole ion trap mass spectrometer is presented. This technique is capable of performing scans analogous to the parent and neutral loss scans routinely applied on tandem-in-space instruments and allows for the screening of a sample to detect analytes of a specific compound class on a chromatographic time-scale. Acylcarnitines were chosen as the model compound class to demonstrate the analytical utility of P&NL monitoring because of their amenability to electrospray ionization (ESI), their unique and informative MS/MS fragmentation pattern, and their importance in biological functions. The [M + H]+ ions of all acylcarnitines dissociate to produce neutral losses of 59 and 161 amu and common product ions at m/z 60, 85, and 144. Both the neutral loss monitoring of 59 amu and the parent ion monitoring of m/z 85 are shown to be capable of identifying acylcarnitine [M + H]+ ions in a synthetic mixture and spiked pig plasma. The neutral loss monitoring of 59 amu is successful in detecting acylcarnitines in an unspiked pig plasma sample.     

Response to fertilization and nutrient deficiency diagnostics in peach palm in Central Amazonia

Peach palm (Bactris gasipaes Kunth) is increasingly grown in the tropics for its heart-of-palm and fruit. Determining fertilization response and diagnosing nutrient status in peach palm may require methods that consider the particularities in nutrient acquisition and recycling of perennial crops. Responses to nutrient additions, and the diagnostic value of soil and foliar analyses were examined in three field experiments with three-year old peach palm stands on Oxisols in Central Amazonia. To diagnose P-deficiency levels in soils, samples from 0–5 cm and 5–20 cm depth were analyzed for available P by different methods (Mehlich-1, Mehlich-3 and Modified Olsen). The second and fifth leaves were analyzed to assess N, P and K deficiencies. Field experiments involved several combinations of N (from 0 to 225 kg ha^–1 yr^–1), K (from 0 to 225 kg ha^–1 yr^–1) and P (from 0 to 59 kg ha^–1 yr^–1). Palms on control plots (unfertilized) and those receiving 225 kg ha^–1 yr^–1 N and 2 Mg ha^–1 of lime yielded between 4 and 19% of the maximum growth which was obtained with N, P and K applications. In one of the experiments, yield of heart-of-palm was positively related to N additions at the lowest levels of P (8.6 kg ha^–1 yr^–1) and K (60 kg ha^–1 yr^–1) additions. In one experiment, critical leaf N level was 2.5% for the second leaf and 2.2% for the fifth leaf. Some growth responses to P additions at constant N and K levels were observed (e.g., 797 kg ha^–1 yr^–1 of heart-of-palm with 39.3 kg ha^–1 yr^–1 of applied P, and 632 kg ha^–1 yr^–1 of heart-of-palm with 10.9 kg ha^–1 yr^–1 of applied P in one experiment, and 2334 kg ha^–1 yr^–1 of heart-of-palm with 39.3 kg ha^–1 yr^–1 of P and 1257 kg ha^–1 yr^–1 of heart-of-palm with 19.7 kg ha^–1 yr^–1 of P in another trial). In the experiment for fruit production from peach palm, total plant height did not respond to P additions between 19.7 and 59 kg ha^–1 yr^–1 and K additions between 75 and 225 kg ha^–1 yr^–1. Leaf P levels were found to be above the proposed critical levels of 0.23% for the third leaf and 0.16% for the fifth leaf. Plants in this experiment, however, showed evident symptoms of Mg deficiency, which was associated with a steep gradient of increasing Mg concentration from the fifth leaf to the second leaf. Standard leaf diagnostic methods in most cases proved less useful to show plant N and P status and growth responses to N and P additions. Soil P determined by common extractions was in general too variable for prediction of growth.     

x86架构丰富联网汽车中的交互体验

引言 随着Web服务、内容和应用的日益普及,包括汽车制造商以及服务和内容提供商在内的众多厂商都迎来了巨大的商机.汽车制造商可以借此提供开放的信息娱乐平台,使之以多种方式连接到互联网,并在平台硬件的支持下高效、灵活而安全地运行最新、最完善的Web应用.本文主要讲述了x86平台架构如何为用户带来丰富的交互式驾驶体验,而这是非PC兼容型平台难以实现的.     

On-line electrochemistry/thermospray/tandem mass spectrometry as a new approach to the study of redox reactions: the oxidation of uric acid

The electrochemical oxidation pathway of uric acid was determined by on-line electrochemistry/thermospray/tandem mass spectrometry. Intermediates and products formed as a result of electrooxidation were monitored as the electrode potential was varied. Several reaction intermediates have been identified and characterized by tandem mass spectrometry. The tandem mass spectrometric results provide convincing evidence that the primary intermediate produced during the electrooxidation of uric acid has a quinonoid diimine structure. The results indicate that once formed via electrooxidation, the primary intermediate can follow three distinct reaction pathways to produce the identified final products. The final electrochemical oxidation products observed in these studies were urea, CO2, alloxan, alloxan monohydrate, allantoin, 5-hydroxyhydantoin-5-carboxamide, and parabanic acid. The solution reactions that follow the initial electron transfer at the electrode are affected by the vaporizer tip temperature of the thermospray probe. In particular, it was found that at different tip temperatures either hydrolysis or ammonolysis reactions of the initial electrochemical oxidation products can occur. Most importantly, the results show that the on-line combination of electrochemistry with thermospray/tandem mass spectrometry provides otherwise difficult to obtain information about redox and associated chemical reactions of biological molecules such as the structure of reaction intermediates and products, as well as providing insight into reaction pathways.     

System R: A Relational Data Base Management System

A relational approach makes this experimental data base management system unusually easy to install and use. Some of the decisions made in System R design in order to enhance usability also offer major bonuses in other areas.     

A wafer-scale 3-D circuit integration technology

The rationale and development of a wafer-scale three-dimensional (3-D) integrated circuit technology are described. The essential elements of the 3-D technology are integrated circuit fabrication on silicon-on-insulator wafers, precision wafer-wafer alignment using an in-house-developed alignment system, low-temperature wafer-wafer bonding to transfer and stack active circuit layers, and interconnection of the circuit layers with dense-vertical connections with sub-/spl Omega/ 3-D via resistances. The 3-D integration process is described as well as the properties of the four enabling technologies. The wafer-scale 3-D technology imposes constraints on the placement of the first lithographic level in a wafer-stepper process. Control of wafer distortion and wafer bow is required to achieve submicrometer vertical vias. Three-tier digital and analog 3-D circuits were designed and fabricated. The performance characteristics of a 3-D ring oscillator, a 1024 /spl times/ 1024 visible imager with an 8-/spl mu/m pixel pitch, and a 64 /spl times/ 64 Geiger-mode laser radar chip are described.     

Quantitative tandem mass spectrometric imaging of endogenous acetyl-L-carnitine from piglet brain tissue using an internal standard

Matrix-assisted laser desorption/ionization (MALDI) based mass spectrometric imaging (MSI) is increasingly being used as an analytical tool to evaluate the molecular makeup of tissue samples. From the direct analysis of a tissue section, the physical integrity of sample is preserved; thus, spatial information of a compound's distribution may be determined. One limitation of the technique, however, has been the inability to determine the absolute concentration from a tissue sample. Here we report the development of a quantitative MSI technique in which the distribution of acetyl-L-carnitine (AC) in a piglet brain sample is quantified with MALDI MSI. An isotopically labeled internal standard was applied uniformly beneath the tissue section, and wide-isolation tandem mass spectrometry was performed. Normalizing the analyte ion signal by the internal standard ion signal resulted in significant improvements in MS images, signal reproducibility, and calibration curve linearity. From the improved MS images, the concentration of AC was determined and plotted producing a concentration-scaled image of the distribution of AC in the piglet brain section.