Fast liquid chromatography–quadrupole-linear ion trap mass spectrometry for the analysis of pharmaceuticals and hormones in water resources

This paper presents the development of a fast multi-residue method for the determination of 49 pharmaceuticals and 6 metabolites from different therapeutic classes in water resources by means of Ultra-performance™ liquid chromatography (UPLC) coupled to tandem mass spectrometry. The use of the UPLC technology enabled all the 55 compounds to be separated chromatographically in less than 9 min (6.3 min positive mode and 2.7 min negative mode) and with a total analysis time of 18 min when considering column conditioning. Improved resolution, sensitivity and a reduction of matrix effects were obtained under these conditions. Unequivocal identification and quantification of the target compounds was also performed by using the dual acquisition modes of the hybrid triple quadrupole-linear ion trap (QqLIT) system. Triple quadrupole mode by means of selected reaction monitoring (SRM) was used for quantification, whilst a second SRM transition together with information-dependent analysis (IDA) experiments was used for confirmation. Additionally, one general, single solid-phase extraction (SPE) method was developed by using Oasis HLB cartridges. Quality parameters of the method in wastewaters were established obtaining a fast, robust, reproducible and cost-effective method for all the target pharmaceuticals. Finally, the optimized SPE-UPLC/QqLIT method was used for the analysis of the target compounds in wastewaters from Spain. Thirty-one out of fifty-five compounds were identified in the samples collected.     

Multiwalled carbon nanotubes covalently functionalized with poly(N‐vinylcarbazole) via RAFT polymerization: Synthesis and nonliner optical properties

The poly(N‐vinylcarbazole)‐grafted MWNTs (MWNT‐PVK) hybrid materials were synthesized in the presence of S‐1‐Dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate (DDAT)‐covalently functionalized multiwalled carbon nanotubes (MWNT‐DDAT) as reversible addition–fragmentation chain transfer (RAFT) agent. Incorporation of the PVK moieties onto the MWNTs surface can considerably improve the solubility and processability of MWNTs. For all MWNT‐PVK hybrid materials, they are soluble in some common organic solvents such as toluene, THF, chloroform, DMF and others. In contrast to the UV/Vis spectrum of DDAT‐PVK, which was synthesized by use of DDAT as RAFT agent under the same synthetic condition, in the visible region, the absorption spectrum of MWNT‐PVK exhibited a typical electronic absorption characteristics of solubilized carbon nanotubes, in which the absorbance decreases gradually in the range of 350–600 nm. At the same level of linear transmission the MWNT‐PVK with 79.2% PVK moieties in the material structure possesses best optical limiting performance in comparison with the other MWNT‐PVK composites, MWNTs and C₆₀. The significant NLO responses manifest the MWNT‐PVK materials suitable candidate for viable optical limiting devices. Light scattering, originating from the thermal‐induced microplasmas and/or microbubbles, is responsible for the optical limiting. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3161–3168, 2010     

Nanoelectrospray-based detection and sequencing of substoichiometric amounts of phosphopeptides in complex mixtures

A novel immobilized metal affinity chromatography (IMAC)-based protocol was successfully used for sample preparation prior to nanoelectrospray-based sequencing of phosphopeptides. In a first step, phosphorylated peptides are detected in an unseparated peptide mixture using precursor ion scanning in the negative ion mode on a triple-quadrupole mass spectrometer. Then the phosphorylated peptides are enriched by passing the sample over an IMAC column and sequenced in the positive ion mode. The IMAC-based enrichment allows the sequencing of phosphorylated peptides even if other, much more abundant, peptides are present at the same m/z value in the original mixture. Using this two-step approach, we are able to combine the simplicity, sensitivity and specificity of precursor ion scanning-based detection of phosphopeptides using the nanoelectrospray ion source with the ability to sequence phosphorylated peptides even if they are present in substoichiometric amounts.     

扫描速率对硅表面分子沉积膜纳米摩擦特性的影响

本研究小组曾简要报道过扫描速率对Au衬底表面分子沉积膜(MD)的纳米摩擦特性的影响[1],本文利用原子力显微镜(AFM)研究了硅表面、羟基化硅表面、氨丙基硅烷(aminopropylsilanized简称APS)化硅表面及硅衬底上磺化酞菁铜(CuT sPc)单层MD膜表面的摩擦力随针尖扫描速率变化的规律。1　实验方法1 1　仪器与试剂TMX2000型原子力显微镜(TopoMetrix公司)。甲苯、二甲苯、丙酮、无水乙醇、氯仿、浓硫酸、过氧化氢、浓盐酸(以上均为分析纯),3 氨丙基 三乙氧基硅烷(KH 550,ACROS产品),磺化酞菁铜(ALDRICH产品),去离子水(电阻率大于10…     

Room-Temperature Near-Infrared Metastable Species Measured by Phase-Sensitive Lock-in and Fourier Transform Techniques

An ultrasensitive detecting system coupled with either a lock-in or Fourier transform technique has been used to detect near-infrared (1000-2500 nm) metastable species in room temperature solutions. These species include O₂(¹Δ_g), O₂(¹σ⁺_g), the solvent induced satellite peak of molecular singlet oxygen (¹Δ_g) emission, and the triplet state of bis(triisobutylsiloxy)silicon-2,-3-naphthalocyanine (SilNC). Using the O₂(¹Δ_g) emission in benzene as a standard, the quantum yield and radiative decay rate of SiINC triplet state have been determined. Depending on types of spectral acquisition, special techniques such as phase-distinguishing and step scan capabilities were utilized. Their advantages and disadvantages are discussed.     

Application of Elimination Voltammetry to the Resolution of Adenine and Cytosine Signals in Oligonucleotides. I. Homo‐oligodeoxynucleotides dA9 and dC9

Elimination voltammetry with linear scan (EVLS) has been applied to the resolution of reduction signals of adenine and cytosine in short synthetic homo‐oligodeoxynucleotides (dA₉ and dC₉). In comparison with the common electrochemical methods (linear sweep, differential pulse, and square‐wave voltammetry) EVLS enables one to resolve the overlapped signals by using the function which eliminates the charging and kinetic currents (I_c, I_k) and conserves the diffusion current (I_d). For the adsorbed electroactive substance, this elimination function gives a good readable peak‐counterpeak which has successfully been utilized to the analysis of overlapped reduction signals of adenine and cytosine on hanging mercury drop electrode (HMDE). The height and potential of signals studied were affected by the dC₉/dA₉ ratio, the time of accumulation, the stirring speed during the adsorption, and pH. Our results showed that EVLS in connection with the adsorption procedure is a useful tool for qualitative and quantitative studies of short oligonucleotides.     

利用傅里叶红外显微化学图像系统鉴定书写与盖章的先后顺序

采用傅里叶变换红外显微化学图像系统并结合面扫描和反射模式对书写与盖章的先后顺序进行了无损、快速鉴定,结果表明先盖章后写字的红外谱图中墨水的特征峰吸收明显,先写字后盖章的红外谱图中印油的特征峰吸收明显。该法具有快速、准确、客观和不损坏样品等特点。     

深紫外准分子激光实时曝光剂量控制算法研究

提出了一种面向步进扫描投影光刻机的深紫外准分子激光实时曝光剂量控制算法。通过建立扫描曝光过程的抽象模型并分析准分子激光器单脉冲能量波动特性,提出采用闭环反馈控制进行实时调节,着重研究了抑制单脉冲能量超调和随机波动的有效算法。在一台波长为193 nm、重复频率为4 kHz、单脉冲能量为5 mJ的ArF准分子激光器上进行了实验研究。结果表明,当脉冲个数仅为20时算法控制下的剂量精度即可达0.89%,不但满足亚微米光刻越来越严的剂量要求,而且有助于提高光刻机生产效率和激光器使用效率。     

卤化银微晶的含碘结构的测定

用超薄切片法及X-射线线扫描法研究了半个碘溴化银微晶中碘的成层分布,结果与预想的碘的分布相一致。横扫过薄样品的X-射线线扫描提供了一个比较准确的测定含有不同碘量成层结构的技术。这有助于我们改进碘溴化银乳剂的制备。文章还讨论了在该种工作条件下,X-射线源的空间分辨率和超薄切片的厚度。 利用这种方法,把一种商用多层彩色片做超薄切片,用X-射线线扫描法直接对超薄切片中卤化银微晶的断面扫描,得到了各个轧剂层中的卤化银微晶的含碘结构。     

放疗3D剂量验证系统中光场相机点扩散函数获取

基于闪烁光场成像的放疗新型3D剂量测量中,需利用点扩散函数将每一个二维平面的真实闪烁光数据从重叠图像中提取出来.利用刀口法,结合光场数字重聚焦以及聚焦测距法,实验获取光场相机不同重聚焦位置处的点扩散函数,并给出棋盘格标定板在参数α=0.6时的重聚焦面聚焦在α=0.7位置处的高斯离焦点扩散函数表达式,研究光场相机点扩散函...