Sequential oxidation/asymmetric aldol reaction of primary alcohols by resin-supported catalysts

The sequential reaction including alcohol oxidation by TEMPO/Cu system and the asymmetric aldol reaction by peptide catalysis was realized using resin-supported catalysts. The step of oxidizing primary alcohols to the corresponding aldehydes could be dramatically enhanced through the introduction of triglycyl peptide to supported TEMPO and the method of pre-adsorbing a Cu-complex into resin beads.     

Parallel Resampling in the Particle Filter

Modern parallel computing devices, such as the graphics processing unit (GPU), have gained significant traction in scientific and statistical computing. They are particularly well-suited to data-parallel algorithms such as the particle filter, or more generally sequential Monte Carlo (SMC), which are increasingly used in statistical inference. SMC methods carry a set of weighted particles through repeated propagation, weighting, and resampling steps. The propagation and weighting steps are straightforward to parallelize, as they require only independent operations on each particle. The resampling step is more difficult, as standard schemes require a collective operation, such as a sum, across particle weights. Focusing on this resampling step, we analyze two alternative schemes that do not involve a collective operation (Metropolis and rejection resamplers), and compare them to standard schemes (multinomial, stratified, and systematic resamplers). We find that, in certain circumstances, the alternative resamplers can perform significantly faster on a GPU, and to a lesser extent on a CPU, than the standard approaches. Moreover, in single precision, the standard approaches are numerically biased for upward of hundreds of thousands of particles, while the alternatives are not. This is particularly important given greater single- than double-precision throughput on modern devices, and the consequent temptation to use single precision with a greater number of particles. Finally, we provide auxiliary functions useful for implementation, such as for the permutation of ancestry vectors to enable in-place propagation. Supplementary materials are available online.     

An insight into the sequential order in 2D correlation spectroscopy using polymer transitions: Boltzmann Sigmoid,Gaussian Cumulative,Lorentz Cumulative,and Asymmetric Sigmoid. Findings in experiments and simulations

In this paper, we found the curves of infrared spectral intensity at specific wavenumbers of several polymer transitions can be accurately fitted by one of Boltzmann Sigmoid, Gaussian Cumulative, Lorentz Cumulative, or Asymmetric Sigmoid functions. These transitions include the melting of iPP, the Brill transition of PA66, the epoxy curing, the oxidation of SBS, and the melting of HDPE. These functions were obviously different from other important functions, which were earlier introduced into generalized 2D correlation spectroscopy, such as sinusoidal, exponential, and Lorentzian. The properties of the Boltzmann Sigmoid, Gaussian Cumulative, Lorentz Cumulative functions were studied using the simulated infrared spectra. The sequential order is only controlled by the parameter reflecting the center point location, while other parameter values have no relationship. The influences of the parameters in Asymmetric Sigmoid on the sequential order were also studied using the simulated IR spectra. Within the transition range, it was found the values of several waveform parameters co-determine the sequential order. We concluded that the MW2D or PCMW2D method should first be employed to determine a rational transition range before using 2D correlation infrared spectroscopy to study the mechanism of the polymer transitions. The clear physical meaning of the sequential order is the “earlier” or “later” of the transition points. As long as the experimental range (external perturbation) is wide enough and the data precision is good, the sequential order is absolutely reliable within the transition range. The results discussed throughout this paper have proven that the sequential order rules are absolutely correct. The content of the present study will solve the controversy on the sequential order rules to a large extent.     

The component counts of random functions

Consider functions $f:A\to A\cup C$, where A and C are disjoint finite sets. The weakly connected components of the digraph of such a function are cycles of rooted trees, as in random mappings, and isolated rooted trees. Let $n_1=|A|$ and $n_3=|C|$. When a function is chosen from all ${(n_1+n_3)}^{n_1}$ possibilities uniformly at random, then we find the following limiting behaviour as $n_1\to \infty$. If $n_3=o(n_1)$, then the size of the maximal mapping component goes to infinity almost surely; if $n_3～\gamma n_1$, $\gamma >0$ a constant, then process counting numbers of mapping components of different sizes converges; if $n_1=o(n_3)$, then the number of mapping components converges to 0 in probability. We get estimates on the size of the largest tree component which are of order $\log ?n_3$ when $n_3～\gamma n_1$ and constant when $n_3～n_1^{\alpha }$, $\alpha >1$. These results are similar to ones obtained previously for random injections, for which the weakly connected components are cycles and linear trees.     

Sequential injection immunoassay for human bone morphogenic protein-7 using an immunoreactor immobilized with anti-human bone morphogenic protein-7 antibody–CdSe/ZnS quantum dot conjugates

The detection of human bone morphogenic protein-7 (BMP-7) was achieved using a sequential injection immunoassay (SIIA) system. The SIIA system is based on the binding between BMP-7 and anti-human BMP-7 (AbBMP7)–CdSe/ZnS quantum dot (QD) conjugates immobilized onto a glass disk or an optical fiber, using fluorescence detection at excitation and emission wavelengths of 470 nm and 580 nm, respectively. The AbBMP7–QD conjugates were prepared by conjugating anti-human BMP-7 antibody (AbBMP7) to hydrophilic CdSe/ZnS core/shell quantum dots (QDs). The SIIA system was fully automated using software written in the LabVIEW™ development environment. The analytical performance of the SIIA system was characterized with a number of variables such as carrier flow rate and elution buffer. Under partially optimized operating conditions, the SIIA system had a linear calibration graph at up to 10.0 ng mL⁻¹ BMP-7 (R² ≥ 0.975) and a sample frequency of two samples per hour. The SIIA system with an optical fiber immunosensor was used to detect and quantify BMP-7 in spiked real samples obtained from a biological process with recoveries in the range of 95–102%.     

On-line simultaneous and rapid separation of anions and cations from a single sample using dual-capillary sequential injection-capillary electrophoresis

A novel capillary electrophoresis (CE) approach has been developed for the simultaneous rapid separation and identification of common environmental inorganic anions and cations from a single sample injection. The method utilised a sequential injection-capillary electrophoresis instrument (SI-CE) with capacitively-coupled contactless conductivity detection (C⁴D) constructed in-house from commercial-off-the-shelf components. Oppositely charged analytes from a single sample plug were simultaneously injected electrokinetically onto two separate capillaries for independent separation and detection. Injection was automated and may occur from a syringe or be directly coupled to an external source in a continuous manner. Software control enabled high sample throughput (17 runs per hour for the target analyte set) and the inclusion of an isolation valve allowed the separation capillaries to be flushed, increasing throughput by removing slow migrating species as well as improving repeatability. Various environmental and industrial samples (subjected only to filtering) were analysed in the laboratory with a 3 min analysis time which allowed the separation of 23 inorganic and small organic anions and cations. Finally, the system was applied to an extended automated analysis of Hobart Southern Water tap water for a period of 48 h. The overall repeatability of the migration times of a 14 analyte standard sample was less than 0.74% under laboratory conditions. LODs ranged from 5 to 61 μg L⁻¹. The combination of automation, high confidence of peak identification, and low limits of detection make this a useful system for the simultaneous identification of a range of common inorganic anions and cations for discrete or continuous monitoring applications.     

Determination of artificial sweeteners by capillary electrophoresis with contactless conductivity detection optimized by hydrodynamic pumping

The common sweeteners aspartame, cyclamate, saccharin and acesulfame K were determined by capillary electrophoresis with contactless conductivity detection. In order to obtain the best compromise between separation efficiency and analysis time hydrodynamic pumping was imposed during the electrophoresis run employing a sequential injection manifold based on a syringe pump. Band broadening was avoided by using capillaries of a narrow 10 μm internal diameter. The analyses were carried out in an aqueous running buffer consisting of 150 mM 2-(cyclohexylamino)ethanesulfonic acid and 400 mM tris(hydroxymethyl)aminomethane at pH 9.1 in order to render all analytes in the fully deprotonated anionic form. The use of surface modification to eliminate or reverse the electroosmotic flow was not necessary due to the superimposed bulk flow. The use of hydrodynamic pumping allowed easy optimization, either for fast separations (80 s) or low detection limits (6.5 μmol L⁻¹, 5.0 μmol L⁻¹, 4.0 μmol L⁻¹ and 3.8 μmol L⁻¹ for aspartame, cyclamate, saccharin and acesulfame K respectively, at a separation time of 190 s). The conditions for fast separations not only led to higher limits of detection but also to a narrower dynamic range. However, the settings can be changed readily between separations if needed. The four compounds were determined successfully in food samples.     

Determination of Benzocaine and Tricaine in Fish Fillets Using BIA with Amperometric Detection

A system based on batch injection analysis (BIA) associated with amperometric detection at screen‐printed carbon electrode was used for the precise and rapid quantification of the anesthetics compounds benzocaine and tricaine in fresh fish fillets. Along this study, the best conditions for the BIA‐amperometry system were stablished for the rapid determination of these compounds. The results obtained demonstrate that the proposed method is an interesting alternative to the chromatographic methods, once it allows to perform rapid analysis (more than 300 injections per hour) with low limits of detection (3.02×10⁻⁸ mol L⁻¹ for benzocaine and 3.19×10⁻⁸ mol L⁻¹ for tricaine), using just 80 μL of sample for each analysis. Furthermore, it was possible to obtain high repeatability for both compounds analyzed, demonstrating good performance. The simple sample preparation developed in this study drastically reduced the amount of fat in the fish extract, favoring precision, as shown by the results of the recovery studies of both anesthetics contained in the fish samples (values above 99 % for both analytes).     

流动注射-在线蒸馏法同时测定水样中挥发酚及氰化物

采用流动注射在线蒸馏法同时测定了水样中挥发酚及氰化物.结果表明：其线性范围在0-100μg/L时,均具有良好的线性关系,挥发酚和氰化物的方法检出限分别为1.2μg/L和1.0μg/L,精密度RSD均小于3％,挥发酚和氰化物平均回收率分别为90.6％和93.4％.     

溴新斯的明注射液的含量测定

采用紫外分光光度法测定溴新斯的明注射液中溴新斯的明的含量,测定波长为260nm.溴新斯的明浓度在150-400μg·mL^-1范围内与吸光度呈良好的线性关系,回归方程为：A=0.0016c-0.0173,r=0.9999（n=3）;平均回收率为100.08％,RSD为0.17％;日内精密度和日间精密度的RSD分别为0.53％ （n=5）和0.63％ （n=5）;测得3批样品的含量分别为99.86％、99.28％、99.61％;本品在24h内稳定.此方法操作简便、迅速,具有良好的精密度,适用于溴新斯的明注射液中溴新斯的明含量的测定.