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121.
A method for the racemization of pipecoloxylidide with a ruthenium catalyst has been developed. This racemization method can be implemented in an integrated process that combines the separation of two enantiomers with racemization of the undesired enantiomer. 相似文献
122.
Lisa Y. Wu 《Tetrahedron letters》2010,51(2):402-403
Magnesium bis(monoperoxyphthalate) hexahydrate (MMPP) was found to be an effective reagent for the oxidation of various α-amino acid esters to the corresponding α-oximino acid esters. This transformation could be completed under mild conditions within 2.5 h using 1.1 equiv of MMPP in THF. Clean oximino esters were obtained after quenching and extracting the reaction from sodium thiosulfate solution. The O-phosphorylated derivative of 2-oximinoglutarate exhibited slow binding inhibitory potency for the metallopeptidase prostate-specific membrane antigen (PSMA) with an IC50 value of 58 nM. 相似文献
123.
Francesca Speroni Lisa Elviri Maria Careri Alessandro Mangia 《Analytical and bioanalytical chemistry》2010,397(7):3035-3042
An innovative enzyme-linked immunosorbent assay (ELISA) format based on antibody-coated magnetic micro-particles (MPs) for
the sensitive detection of Ara h3/4 allergen in food is described. The immunosupport is suspended in the incubation solutions
and the MPs with the captured allergen can be easily harvested on a magnet, separated from the solutions, and washed using
an easy-to-use, fast and selective approach that allows its detection and quantification. Two differently coated MPs, ProteinA-Pn-b
and MP-NH2-PAMAM G 1.5 -Pn-b immunosupports, were tested. The functionalization of the MPs with PAMAM-sodium carboxylate dendrimers
elicits a major stability on the immunoglobulin activity resulting in a threefold enhancement of the analytical sensitivity
for the assay with respect to a ProteinA immobilization. Validation was carried out on two different matrices: corn flakes
and biscuits. In the case of MP-NH2-PAMAM G 1.5 -Pn-b immunosupport, limit of detection was found to be 0.2 mg peanuts/kg matrix in both matrices; the linear
response range was demonstrated from 2.5 to 15 mg peanuts/kg matrix by performing statistical tests (homoscedasticity and
Mandel fitting tests). Good accuracy and recovery (>80 ± 2%) were obtained. Different food samples were tested and the results
were compared with those obtained with a commercially available ELISA kit. The results obtained in this work demonstrated
the applicability of the immunomagnetic ELISA methods on real samples and the possibility to perform the assay with significantly
reduced reagent and sample consumption. 相似文献
124.
Giorgini E Conti C Ferraris P Sabbatini S Tosi G Rubini C Vaccari L Gioacchini G Carnevali O 《Analytical and bioanalytical chemistry》2010,398(7-8):3063-3072
The aim of this study was to verify the effects of probiotic Lactobacillus rhamnosus on zebrafish oocyte maturation using FPA (focal plane array) FTIR imaging together with specific biochemical assays (SDS-PAGE, real-time PCR and enzymatic assay). Oocyte growth is prevalently due to a vitellogenic process which consists of the hepatic synthesis of vitellogenin and its selective uptake during maturation. The administration of L. rhamnosus IMC 501 for 10 days induced chemical changes to oocyte composition, promoting the maturation process. Some interesting biochemical features, linked to protein secondary structure (amide I band) and to phospholipidic and glucidic patterns, were detailed by vibrational analysis. The spectroscopic results were supported by the early increase of the lysosomal enzyme involved in the final oocyte maturation, the cathepsin L. This enzyme increases during follicle maturation, with the highest levels in class IV oocytes. In treated females, class III oocytes showed higher cathepsin L gene expression and enzymatic activity, with levels comparable to class IV oocytes isolated from controls; this can be related to the proteolytic cleavage of the higher molecular mass yolk protein components, as evidenced by SDS-PAGE. 相似文献
125.
Thomas J. Bruno Lisa S. OttTara M. Lovestead Marcia L. Huber 《Journal of chromatography. A》2010,1217(16):2703-2715
The analysis of complex fluids such as crude oils, fuels, vegetable oils and mixed waste streams poses significant challenges arising primarily from the multiplicity of components, the different properties of the components (polarity, polarizability, etc.) and matrix properties. We have recently introduced an analytical strategy that simplifies many of these analyses, and provides the added potential of linking compositional information with physical property information. This aspect can be used to facilitate equation of state development for the complex fluids. In addition to chemical characterization, the approach provides the ability to calculate thermodynamic properties for such complex heterogeneous streams. The technique is based on the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. The analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin layer chromatography, FTIR, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. By far, the most widely used analytical technique we have used with the ADC is gas chromatography. This has enabled us to study finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oils streams (used automotive and transformer oils). In this special issue of the Journal of Chromatography, specifically dedicated to extraction technologies, we describe the essential features of the advanced distillation curve metrology as an analytical strategy for complex fluids. 相似文献
126.
A bicarbonate buffer-based extraction method for the simultaneous analysis of five nut allergens (Ana o 2, cashew-nut; Cor a 9, hazelnut; Pru 1, almond; Ara h3/4, peanut; Jug r 4, walnut) in cereals and biscuits using liquid chromatography-electrospray-linear ion trap-tandem mass spectrometry (LC-ESI-LIT-MS(2)) was developed and validated. The method was based on our earlier published LC-MS(2)-based method in a research frame aimed at the identification and determination of hidden allergens in foods by using selective biomarker peptides. A C18 particle-packed column and a silica-based C18 monolithic column were compared in terms of chromatographic performances, such as peak shape, resolution, analysis time and selectivity. The C18 particle-packed column exhibited better performances and was further used for method development and validation. By operating under MS(2) selected reaction monitoring (SRM) acquisition mode, linearity, limits of detection (LOD) and quantitation, trueness and precision were evaluated on breakfast samples enriched with a mix of the five nuts. Good linearity of the matrix matched-calibration curves was obtained and detection limit values generally varied from 14 to 55 mg nut/kg matrix. Recoveries were in the 76±4% to 94±3% range with RSD <15%. The capabilities of LIT to perform MS(n) fragmentation was exploited to improve selectivity of the analysis, and the LC-(SRM) MS(2) method was compared in terms of LOD, linearity, precision and accuracy with a LC-(SRM) MS(3) method. Finally, both the LC-MS(2) and LC-MS(3) methods were successfully applied to the analysis of nut traces in commercially available breakfast cereals and biscuits. 相似文献
127.
Beliefs influencing students’ mathematical learning and problem solving are structured and intertwined with larger affective and cognitive structures. This theoretical article explores a psychological concept we term an engagement structure, with which beliefs are intertwined. Engagement structures are idealized, hypothetical constructs, analogous in many ways to cognitive structures. They describe complex “in the moment” affective and social interactions as students work on conceptually challenging mathematics. We present engagement structures in a self-contained way, paying special attention to their theoretical justification and relation to other constructs. We suggest how beliefs are characteristically woven into their fabric and influence their activation. The research is based on continuing studies of middle school students in inner-city classrooms in the USA. 相似文献
128.
Sanders LD Zobel BH Freyman RL Keen R 《The Journal of the Acoustical Society of America》2011,129(1):301-309
To gain information from complex auditory scenes, it is necessary to determine which of the many loudness, pitch, and timbre changes originate from a single source. Grouping sound into sources based on spatial information is complicated by reverberant energy bouncing off multiple surfaces and reaching the ears from directions other than the source's location. The ability to localize sounds despite these echoes has been explored with the precedence effect: Identical sounds presented from two locations with a short stimulus onset asynchrony (e.g., 1-5 ms) are perceived as a single source with a location dominated by the lead sound. Importantly, echo thresholds, the shortest onset asynchrony at which a listener reports hearing the lag sound as a separate source about half of the time, can be manipulated by presenting sound pairs in contexts. Event-related brain potentials elicited by physically identical sounds in contexts that resulted in listeners reporting either one or two sources were compared. Sound pairs perceived as two sources elicited a larger anterior negativity 100-250 ms after onset, previously termed the object-related negativity, and a larger posterior positivity 250-500 ms. These results indicate that the models of room acoustics listeners form based on recent experience with the spatiotemporal properties of sound modulate perceptual as well as later higher-level processing. 相似文献
129.
Partridge SC Singer L Sun R Wilmes LJ Klifa CS Lehman CD Hylton NM 《Magnetic resonance imaging》2011,29(9):1215-1221
Promising recent investigations have shown that breast malignancies exhibit restricted diffusion on diffusion-weighted imaging (DWI) and may be distinguished from normal tissue and benign lesions in the breast based on differences in apparent diffusion coefficient (ADC) values. In this study, we assessed the influence of intravoxel fat signal on breast diffusion measures by comparing ADC values obtained using a diffusion-weighted single shot fast spin-echo sequence with and without fat suppression. The influence of breast density on ADC measures was also evaluated. ADC values were calculated for both tumor and normal fibroglandular tissue in a group of 21 women with diagnosed breast cancer. There were systematic underestimations of ADC for both tumor and normal breast tissue due to intravoxel contribution from fat signal on non–fat-suppressed DWI. This ADC underestimation was more pronounced for normal tissue values (mean difference=40%) than for tumors (mean difference=27%, P<.001) and was worse in women with low breast tissue density vs. those with extremely dense breasts (P<.05 for both tumor and normal tissue). Tumor conspicuity measured by contrast-to-noise ratio was significantly higher on ADC maps created with fat suppression and was not significantly associated with breast density. In summary, robust fat suppression is important for accurate breast ADC measures and optimal lesion conspicuity on DWI. 相似文献
130.
Let p r (n) denote the number of r-component multipartitions of n, and let S γ,λ be the space spanned by η(24z) γ ?(24z), where η(z) is the Dedekind’s eta function and ?(z) is a holomorphic modular form in \(M_{\lambda}(\mathrm{SL}_{2}(\mathbb{Z}))\) . In this paper, we show that the generating function of \(p_{r}(\frac{m^{k} n +r}{24})\) with respect to n is congruent to a function in the space S γ,λ modulo m k . As special cases, this relation leads to many well known congruences including the Ramanujan congruences of p(n) modulo 5,7,11 and Gandhi’s congruences of p 2(n) modulo 5 and p 8(n) modulo 11. Furthermore, using the invariance property of S γ,λ under the Hecke operator \(T_{\ell^{2}}\) , we obtain two classes of congruences pertaining to the m k -adic property of p r (n). 相似文献