Liquid chromatography with diode array detection and multivariate curve resolution for the selective and sensitive quantification of estrogens in natural waters

Following the green analytical chemistry principles, an efficient strategy involving second-order data provided by liquid chromatography (LC) with diode array detection (DAD) was applied for the simultaneous determination of estriol, 17β-estradiol, 17α-ethinylestradiol and estrone in natural water samples. After a simple pre-concentration step, LC–DAD matrix data were rapidly obtained (in less than 5 min) with a chromatographic system operating isocratically. Applying a second-order calibration algorithm based on multivariate curve resolution with alternating least-squares (MCR-ALS), successful resolution was achieved in the presence of sample constituents that strongly coelute with the analytes. The flexibility of this multivariate model allowed the quantification of the four estrogens in tap, mineral, underground and river water samples. Limits of detection in the range between 3 and 13 ng L⁻¹, and relative prediction errors from 2 to 11% were achieved.     

Direct determination of free bilirubin in serum at sub-nanomolar levels

Direct analysis of free bilirubin in human and animal blood serum samples is reported for the first time. A state-of-the-art system comprised of newly developed high-performance liquid chromatography (HPLC) on reverse-phase (RP) C18 support coupled with thermal lens spectrometric detection (TLS), based on excitation at λ = 457.9 nm by an argon laser was used for this purpose. This HPLC-TLS method enabled a baseline separation of all three structural isomers of bilirubin (XIII-α, IX-α and III-α) and the respective degradation products in isocratic mode in fewer than 7 min. The method excels in ultra-high sensitivity with limit of detection (LOD) and limit of quantitation (LOQ) of 90 pM and 250 pM, respectively. Moreover, this method also affords high precision and accuracy, with correlation coefficients R² > 0.997 over a broad linear range (0.250–150 nM) and R² = 0.9998 in a concentration range of clinical interest (0.500–25 nM). The method's boosted sensitivity enabled to streamline sample preparation to just one serum ultrafiltration step, which made qualitative evaluation of sample preparation possible for the first time. The performance of the HPLC-TLS method was assessed to have 20-fold enhanced sensitivity when compared to a comparable method incorporating HPLC coupled with diode array detector (DAD), which is also a novel method by itself, and could be applied for free bilirubin determination in patients with elevated bilirubin levels.     

Ultrasensitive electrochemical immunosensors for multiplexed determination using mesoporous platinum nanoparticles as nonenzymatic labels

An ultrasensitive multiplexed immunoassay method was developed at a disposable immunosensor array using mesoporous platinum nanoparticles (M-Pt NPs) as nonenzymatic labels. M-Pt NPs were prepared by ultrasonic method and employed to label the secondary antibody (Ab₂) for signal amplification. The immunosensor array was constructed by covalently immobilizing capture antibody (Ab₁) on graphene modified screen printed carbon electrodes (SPECs). After the sandwich-type immunoreactions, the M-Pt-Ab₂ was bound to immunosensor surface to catalyze the electro-reduction of H₂O₂ reaction, which produced detectable signals for readout of analytes. Using breast cancer related panel of tumor markers (CA125, CA153 and CEA) as model analytes, this method showed wide linear ranges of over 4 orders of magnitude with the detection limits of 0.002 U mL⁻¹, 0.001 U mL⁻¹ and 7.0 pg mL⁻¹ for CA125, CA153 and CEA, respectively. The disposable immunosensor array possessed excellent clinical value in cancer screening as well as convenient point of care diagnostics.     

P分之一Riordan矩阵及恒等式构造

For an integer p≥2 we construct vertical and horizontal one-pth Riordan arrays from a Riordan array.When p=2 one-pth Riordan arrays are reduced to well known half Riordan arrays.The generating functions of the A-sequences of vertical and horizontal one-pth Riordan arrays are found.The vertical and horizontal one-pth Riordan arrays provide an approach to construct many identities.They can also be used to verify some well known identities readily.     

窄带快照式多光谱成像色彩还原方法

由于兼具光谱分辨和空间分辨能力, 快照式窄带多光谱成像在资源遥感、精准农业、医疗检测等领域将有广泛应用。由于该方法使用窄带成像来提高光谱分辨率及图像对比度,所获得的图像是灰度信息,失去了场景的色彩信息,不便专家对图像鉴别、评价与赏析。已有的色彩还原算法主要针对光谱波段带宽较宽或者多个波段叠加基本覆盖整个可见光谱范围等两种光谱成像仪,不适合窄带多光谱成像方法的色彩还原。该研究适合于快照式窄带多光谱成像的色彩还原方法,提出建立窄带多光谱彩色相机的概念。首先,提出两种窄带多光谱色彩还原方法：(1)基于CIE色度系统三刺激值色的,(2)基于贝尔阵列插值算法的;其次,分别应用两种算法还原快照式窄带多光谱相机所获得的植物、手臂及宫颈组织等三种代表性场景窄带多光谱灰度图像;之后,计算并比较表征两种算法所得的代表性场景彩色图像的均值、方差、熵及梯度等表征图像质量的参数数值,确定出适合快照式窄带多光谱成像的色彩还原方法;最后,对所确定的色彩还原算法进行色偏校正。实验结果表明,基于CIE三刺激值色彩还原方法比贝尔阵列插值法更适用于窄带多光谱成像颜色复原。配合使用CIE三刺激值色彩还原方法及灰度图象校正算法,从窄带光谱成像所获得的植物、手臂皮肤及宫颈组织的灰度图像所还原出的近彩色图像逼近物体真实色彩,满足人眼观察习惯。介绍了仅覆盖可见光光谱范围30%的窄带多光谱图像进行色彩还原的方法,该方法证明快照式窄带多光谱成像可以兼具光谱分辨能力,同时保持可供人主观辨识的色彩信息。所提出实现快照式窄带多光谱彩色成像的方法,有望设计不同于传统RGB相机的彩色相机实施方案。     

Helmholtz-pair transmit coil with integrated receive array for high-resolution MRI of trabecular bone in the distal tibia at 7T

A Helmholtz-pair local transmit RF coil with an integrated four-element receive array RF coil and foot immobilization platform was designed and constructed for imaging the distal tibia in a whole-body 7T MRI scanner. Simulations and measurements of the B(1) field distribution of the transmit coil are described, along with SAR considerations for operation at 7T. Results of imaging the trabecular bone of three volunteers at 1.5T, 3T and 7T are presented, using identical 1.5T and 3T versions of the 7T four-element receive array. The spatially registered images reveal improved visibility for individual trabeculae and show average gains in SNR of 2.8× and 4.9× for imaging at 7T compared to 3T and 1.5T, respectively. The results thus display an approximately linear dependence of SNR with field strength and enable the practical utility of 7T scanners for micro-MRI of trabecular bone.     

ρ~-混合序列的H～jeck-Rènyi型不等式及其应用

利用ρ-混合序列的Rosenthal型最大值不等式,得到了ρ-混合随机变量序列的Hájeck-Rènyi型不等式,三级数定理和Chung型强大数律,所得结果达到了独立时一致的结果.     

单次多水平正交试验中效应的显著性检验

方差分析自试验设计诞生以来一直是用于分析试验中各因子是否显著的统计方法,对于正交试验设计而言其更是唯一的分析方法.然而,当正交表各列放满了被考虑的各个因子及其交互作用并且各条件组合下只能进行一次试验时,方差分析中的误差项将恒等于0,从而方差分析不再能用于对此试验设计的分析.对此,本文针对使用多水平完备正交表的单次正交试验,提出了一种新的统计分析方法.示例表明:本文提出的检验法不仅解决了方差分析无法胜任的问题,而且在表头设计有空白列从而方差分析仍能实施时,其比方差分析具有更大的局部功效.     

Crosstalk image intensity reduction for color holograms by using reference beam coded with multicolored aperture array filter

The analytical form for the reconstructed field of a hologram illuminated by a reference beam coded with a multicolored aperture array filter is derived. Experiments showed that the colored aperture array filter improved the quality of the reconstructed image by reducing the intensity of crosstalk images. Some parameters of the aperture array configuration that influence image quality were investigated. This technique presented here can be applied to full-color holographic displays and dot matrix holographic printers, etc.     

Propagation-invariant hollow beams with hexagonal symmetry

Based on the interference of six symmetric beams, we introduce a new way to produce propagation-invariant hollow beams with hexagonal symmetry. The hollow beams have a dark center and hexagonal shape. They can be optical vortices, radially or azimuthally polarized beams. The results of simulation demonstrate the feasibility of this method.