The development and application of guidance on equipment qualification of analytical instruments

 This paper describes the development of guidance for the equipment qualification (EQ) of analytical instruments. EQ is a formal process that provides documented evidence that an instrument is fit for its intended purpose and kept in a state of maintenance and calibration consistent with its use.     

A hybrid DQ/LMQRBF-DQ approach for numerical solution of Poisson-type and Burger’s equations in irregular domain

Differential quadrature (DQ) is an efficient and accurate numerical method for solving partial differential equations (PDEs). However, it can only be used in regular domains in its conventional form. Local multiquadric radial basis function-based differential quadrature (LMQRBF-DQ) is a mesh free method being applicable to irregular geometry and allowing simple imposition of any complex boundary condition. Implementation of the latter numerical scheme imposes high computational cost due to the necessity of numerous matrix inversions. It also suffers from sensitivity to shape parameter(s). This paper presents a new method through coupling the conventional DQ and LMQRBF-DQ to solve PDEs. For this purpose, the computational domain is divided into a few rectangular shapes and some irregular shapes. In such a domain decomposition process, a high percentage of the computational domain will be covered by regular shapes thus taking advantage of conventional DQM eliminating the need to implement Local RBF-DQ over the entire domain but only on a portion of it. By this method, we have the advantages of DQ like simplicity, high accuracy, and low computational cost and the advantages of LMQRBF-DQ like mesh free and Dirac’s delta function properties. We demonstrate the effectiveness of the proposed methodology using Poisson and Burgers’ equations.     

固相萃取净化-超高效液相色谱-高分辨质谱法测定尿液中百草枯和敌草快残留

尿液样品中百草枯(PQ)和敌草快(DQ)的检测是理化检验工作的难点。PQ和DQ具有分子极性大和水溶性好等特点,常规反相色谱柱难以保留;现有文献方法多采用亲水相互作用色谱法(HILIC)进行保留,但文献方法需采用高浓度缓冲盐作为流动相,增加了质谱仪的污染。基于上述问题,研究建立了弱阳离子交换(WCX)固相萃取净化-超高效液相色谱-高分辨质谱法(UPLC-HRMS)快速准确测定尿液样品中PQ和DQ残留的检测方法。尿液样品经混合磷酸盐缓冲液(pH=6.86)稀释和WCX固相萃取净化后,在Syncronis HILIC色谱柱(100 mm×2.1 mm, 1.7 μm)上进行梯度洗脱分离,采用正离子电喷雾离子化模式(ESI⁺)和一级全扫描-数据依赖二级质谱扫描模式(Full mass-ddMS²)进行定量分析。研究通过对色谱条件的不断优化,将HILIC模式下流动相中甲酸铵缓冲盐的浓度降低至10 mmol/L,并系统优化了样品前处理过程中影响PQ和DQ准确性的因素。在最优条件下,PQ和DQ线性关系良好(r²>0.998),在4个加标水平下(1.0、20.0、100.0和200.0 μg/L), PQ和DQ的平均加标回收率分别为85.8%~101%和80.3%~86.9%,精密度(RSD)分别为0.8%~5.1%和0.9%~4.2%。方法的检出限(S/N≥3)和定量限(S/N≥10)分别为0.2 μg/L和0.6 μg/L。将建立的方法用于中毒病人临床治疗过程尿液中DQ含量的跟踪监测。该方法具有快速、简便、灵敏和准确等优点,适用于临床中毒病例尿液样品中PQ和DQ的检测。     

Measurement of Magnitude and Sign of Heteronuclear Coupling Constants in Transition Metal Complexes

Sets of specifically tailored E.COSY-type correlation experiments and double-quantum/zero-quantum (DQ/ZQ) experiments are presented which enable the determination of sign and size of small heteronuclear coupling constants across the metal center of transition metal complexes. For the octahedrally coordinated complexes, [Ru(TPM)(H)(CO)(PPh₃)]⁺[BF₄]⁻(1) and [Ir(TPM)(H)(CO)(CO₂CH₃)]⁺[BF₄]⁻(2), 14 of 15 and 15 of 15 possible two-bond scalar coupling constants across the metal center were measured, respectively, using¹⁵N and¹⁵N/¹³C enriched samples (TPM = tris(1-pyrazolyl)methane)). The reduced coupling constants²K_X-M-Y= 4π²²J/(hγ_Xγ_Y) were found to be positive when the coupled nuclei X and Y weretranswith respect to the metal center, and negative when the coupled nuclei were incisposition. The validity of this sign rule was verified forJ_CC,J_NN,J_PN,J_PC,J_CN,J_HP,J_HC, andJ_HNcouplings. Idiosyncracies associated with 2D NMR spectra for the sign determination of coupling constants with¹⁵N which lead to corrections for the signs ofJ_HN,J_PN, andJ_CNcouplings reported previously are discussed.     

面向谐振式微光学陀螺应用的球形谐振腔DQ乘积优化

基于谐振式光学陀螺高灵敏度、低成本与微型化的发展需求, 为了实现高灵敏度的谐振式微光机电陀螺, 提出了以集成光学微谐振腔领域里高Q值、大直径谐振腔的制作为目标, 应用方向为谐振式光学陀螺的球形光学微谐振腔核心敏感单元. 在实验中以氢火焰作为热源采用熔融法制备球形光学微谐振腔. 通过调节氢气的流量控制氢火焰热源面积, 制备了不同直径(300-2200 μm)的球形谐振腔, 分析了球形谐振腔Q 值、DQ乘积、陀螺灵敏度与谐振腔直径D的对应关系及其原因, 获得了最优参数的面向谐振式光学陀螺的球形谐振腔敏感单元. D=1260 μm时, 球腔品质因数 Q=7.18×10⁷, 得到的最优陀螺灵敏度约为10°/h, 满足商业级应用的需求, 为芯片级、高精度、低成本的新型谐振式光学微腔陀螺的研究奠定了实验基础.     

Homonuclear SQ-DQ correlations in solids: applications of the broadband BaBa scheme to reveal 31P-31P spatial correlations in two-, three-, four-, and five-spin systems

In this paper, we report on the use and limitations of the popular double‐quantum recoupling sequence back‐to‐back in studies of ³¹P‐³¹P spatial proximities in Pd‐phosphine complexes at medium field (9.38 T) under the conditions of fast MAS. The effects of internuclear distances in different spin systems and the impact of isotropic chemical shift and chemical shift anisotropy (CSA) offsets on the detectibility of SQ‐DQ correlations were of particular interest to us. Selected model compounds with these requirements in mind were synthesized. By optimization of the excitation times of SQ‐DQ correlations up to 4.6 Å could be obtained even in four‐spin systems; however, certain long‐range correlations may be weak or missing. Although under fast MAS, CSA values up to 270 ppm are well tolerated, in multi‐spin systems in cases of isotropic chemical shift offsets larger than 50 ppm, the DQ coherences cannot be properly excited. Copyright © 2011 John Wiley & Sons, Ltd.     

三种测量橡胶交联密度的核磁共振方法比较

核磁共振（NMR）技术已经成为测量橡胶交联密度的一种常用技术手段．该文探讨了用于测量橡胶交联密度的三种NMR方法：¹H双量子（DQ）NMR、¹H Hahn回波和¹H CPMG回波,讨论了这些方法测量值差异的来源．在此基础上进一步研究了¹H CPMG回波方法中回波时间对测量值的影响,探讨了改善¹H CPMG回波方法的方案．     

Cryogenic Q-band (35GHz) probehead featuring large excitation microwave fields for pulse and continuous wave electron paramagnetic resonance spectroscopy: performance and applications

The construction and performance of a Q-band (35GHz) cryogenic probehead for pulse electron paramagnetic resonance and continuous wave electron paramagnetic resonance measurements with down-scaled loop gap resonators (LGRs) is presented. The advantage of the LGR in comparison to TE(012) resonators lies in the large B(1) microwave (mw) fields that can be generated with moderate input mw power. We demonstrated with several examples that this allows optimal performance for double-quantum electron coherence, HYSCORE, and hyperfine decoupling experiments employing matched and high turning angle mw pulses with high B(1)-fields. It is also demonstrated that with very low excitation power (i.e. 10-40 mW), B(1)-fields in LGRs are still sufficient to allow short mw pulses and thus experiments such as HYSCORE with high-spin systems to be performed with good sensitivity. A sensitivity factor Lambda(rs) of LGRs with different diameters and lengths is introduced in order to compare the sensitivity of different resonant structures. The electromagnetic field distribution, the B(1)-field homogeneity, the E(1)-field strength, and the microwave coupling between wave guide and LGRs are investigated by electromagnetic field calculations. The advantage and application range using LGRs for small sample diameters is discussed.     

基于WDQ法的粘弹性输流管道稳定性分析

在微分求积法（DQ法）基础上,根据多分辨分析理论,以尺度函数为基础构造插值基函数,形成小波微分求积法（WDQ法）,用该方法研究了简支Kelvin型粘弹性输流管道的稳定性问题,给出了不同参数下管道复频率随内部流速的变化关系,分析了外部流速对Kelvin型粘弹性输流管道在不同延滞时间下的振动特性及稳定性的影响。