Electrospray ionization stability and concentration sensitivity in capillary electrophoresis-mass spectrometry using a flow-through microvial interface

Concentration sensitivity is a key performance indicator for analytical techniques including for capillary electrophoresis-mass spectrometry (CE–MS) with electrospray ionization (ESI). In this study, a flow-through microvial interface was used to couple CE with MS and improve the ESI stability and detection sensitivity. By infusing a peptide mixture through the interface into an MS detector at a typical flow rate for CE-MS analysis, the spatial region near the interface was mapped for MS signal intensity. When the sprayer tip was within a 6 × 6.5 × 5 mm region in front of the MS inlet, the ESI was stable with no significant loss of signal intensity for ions with m/z 239. Finite element simulations showed that the average electric field strength at the emitter tip did not change significantly with minor changes in emitter tip location. Experiments were conducted with four different mass spectrometer platforms coupled to CE via the flow-through microvial interface. Key performance indicators, that is, limit of detection (LOD) and linearity of calibration curves were measured for nine amino acids and five peptides. Inter- and intraday reproducibility were also tested. The results were shown to be suitable for quantification when internal standards were used.     

Instrumental requirements for the detection of electron beam-induced object excitations at the single atom level in high-resolution transmission electron microscopy

This contribution touches on essential requirements for instrument stability and resolution that allows operating advanced electron microscopes at the edge to technological capabilities. They enable the detection of single atoms and their dynamic behavior on a length scale of picometers in real time. It is understood that the observed atom dynamic is intimately linked to the relaxation and thermalization of electron beam-induced sample excitation. Resulting contrast fluctuations are beam current dependent and largely contribute to a contrast mismatch between experiments and theory if not considered. If explored, they open the possibility to study functional behavior of nanocrystals and single molecules at the atomic level in real time.     

鲁棒PDF控制策略在永磁同步电机系统中的设计及仿真

对电机控制系统的经典反馈设计方案是建立在简化的受控对象模型基础之上,而实际模型参数的变化会引起控制系统性能的改变。本文针对实际应用的永磁同步电机,为了保证电机控制系统的强鲁棒性,通过对其系统灵敏度的理论推导,给出了一种新的控制器参数设计方法。该设计方法以系统灵敏度为评价指标来度量系统的鲁棒性,结合应用于二阶控制对象的伪微分反馈控制器结构,来削弱控制对象参数值的改变对控制系统性能的影响。并建立了精确的永磁同步电机仿真模型,将该方法应用于其速度控制。仿真结果表明在该控制方案下,在永磁同步电机的转动惯量和定子电阻值变化时具有较小超调量变化(小于4%)的响应特性。同时与普通PID控制对比分析,验证了用该方案设计的PMSM调速系统具有较高的抗参数变化的鲁棒性。     

基于光纤锥级联结构的湿度传感器

提出了一种基于普通单模光纤粗锥级联结构的马赫-曾德尔干涉湿度传感器.将两根单模光纤对芯熔融成一个粗锥,并依次级联,形成光纤锥-单模光纤-光纤锥-单模光纤-光纤锥结构.外界环境湿度、温度的改变使传感器的纤芯基模和包层模的光程差发生改变,引起传感器干涉光谱发生变化.通过监测干涉谱波长和能量的变化实现对外界物理量的测量.实验结果表明,当空气中湿度在35~95%RH范围内变化时,传感器的湿度灵敏度为-0.065dB/%RH,线性度为0.997;当温度在30~80℃范围内变化时传感器的温度灵敏度为69.4pm/℃,线性度为0.998.该传感器可以避免温湿度的交叉影响,实现单参量的同时在线区分测量.     

Application of sol–gel TiO2 film for an extended-gate H+ ion-sensitive field-effect transistor

In this study, a sol–gel TiO₂ thin film has been spin-coated on a commercial ITO glass substrate as the extended-gate field effect transistor (EGFET) for hydrogen ion sensing. The as-deposited films are further annealed at various temperatures (T_a) under ambient atmosphere. It is found that the bi-layer structure of TiO₂/ITO EGFET exhibits good linear sensitivity from pH 1 to 11. Anatase TiO₂ appeared as early as T_a = 200 °C and a brookite (121) diffraction evolved at T_a = 500 °C. No prominent influence on the surface fine structures could be found at higher T_a. Due to the reduction or disappearance of the surface hydroxyl groups on TiO₂, the sensitivities of the TiO₂/ITO pH-EGFET device are rapidly reduced. However, the influence of the conductivity decay for ITO substrates annealed at high T_a could not be excluded. A maximum sensitivity 61.44 mV/pH is achieved as T_a = 300 °C.The bi-layer structure of TiO₂/ITO exhibits better long-term stability than the traditional ITO sensing membranes. In addition, the asymmetric hysteresis is more significant in alkaline buffer solutions, which could be explained by a site-binding model because the diffusion of H⁺ ions into the buried sites of the sensing film is more rapid than that of OH⁻ ions.     

Efficacious Anticancer Drug Delivery Mediated by a pH‐Sensitive Self‐Assembly of a Conserved Tripeptide Derived from Tyrosine Kinase NGF Receptor

We present herein a short tripeptide sequence (Lys–Phe–Gly or KFG) that is situated in the juxtamembrane region of the tyrosine kinase nerve growth factor (Trk NGF) receptors. KFG self‐assembles in water and shows a reversible and concentration‐dependent switching of nanostructures from nanospheres (vesicles) to nanotubes, as evidenced by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. The morphology change was associated with a transition in the secondary structure. The tripeptide vesicles have inner aqueous compartments and are stable at pH 7.4 but rupture rapidly at pH≈6. The pH‐sensitive response of the vesicles was exploited for the delivery of a chemotherapeutic anticancer drug, doxorubicin, which resulted in enhanced cytotoxicity for both drug‐sensitive and drug‐resistant cells. Efficient intracellular release of the drug was confirmed by fluorescence‐activated cell sorting analysis, fluorescence microscopy, and confocal microscopy.     

疏水改性pH响应型智能水凝胶P(HEMA-NaAA-DiAC16)的制备及其溶胀性能

以二烯丙基胺和1-溴代十六烷为原料合成了疏水单体N,N-二烯丙基正十六烷胺(DiAC16),用FTIR、1H NMR 和元素分析对其进行了表征。 以2-羟基甲基丙烯酸乙酯(HEMA)、丙烯酸(AA)和N,N-二烯丙基正十六烷胺为共聚单体,N,N′-亚甲基双丙烯酰胺(BIS)为交联剂,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸铵-四甲基乙二胺(TMEDA)为引发体系,制得的疏水改性智能水凝胶P(HEMA-NaAA-DiAC16)具有pH敏感特性。 研究了DiAC16、NaAA、BIS用量及pH值和离子强度等因素对水凝胶P(HEMA-NaAA-DiAC16)溶胀性能的影响。 结果表明,凝胶在水中的平衡溶胀率(为78.9～163.91),随DiAC16、BIS用量的增加和NaAA用量的减少而减少,n值(一般在0.5~1.0之间)随DiAC16、NaAA和BIS用量的增加而增加,为非Fickian扩散。 水凝胶的吸水溶胀是放热过程,ΔHm在-2.09～-3.64 kJ/mol,ΔHm的绝对值随DiAC16用量的减少、NaAA用量和BIS用量的增加而增大,聚合物与水的亲和力逐渐增强。 随离子强度的增强,平衡溶胀率下降。     

Strain rate sensitivity of polyurea coatings: Viscous and elastic contributions

Polyurea, a reaction product of isocyanates and an amine blend has been reported to be highly strain rate sensitive, which responds in its own unique way when subjected to increasing strain rates. The amine blend comprise of a long chain amine, forming the soft segments, chain extender, which brings the urea linkages closer and a crosslinker, which serves as a chemical bond between the chains. In this work, we attempt to tune the viscous contribution in polyurea, by increasing crosslinking density, while keeping the amount of chain extender more or less constant. The viscoelastic behavior and its effect on the time dependant behavior was established by extensive dynamic studies. Quasi-static tests and Split Hopkinson testing was performed over large deformation rates (10⁻⁴ to 10³ s⁻¹). It was observed that polyureas with larger viscous contribution (tan δ), were capable of exhibiting larger strain rate sensitivity.     

Amphibious sensor of temperature and refractive index based on D-shaped photonic crystal fibre filled with liquid crystal

ABSTRACT

A D-shaped photonic crystal fibre filled with liquid crystal was demonstrated as an amphibious sensor for detection of both temperature and refractive index, when combined with plasma materials. Specifically, the optical component is implanted into a complete optical system ensuring modulation of the external electric field. When the refractive index of the external solution changes from 1.0 to 1.6, the y-polarised mode has a loss spectrum with a wavelength sensitivity of up to 2275 nm/RIU, and the corresponding amplitude sensitivity is ?88.2RIU^?1. When the perceived temperature changes from 15°C to 50°C, the temperature of the sensor is correspondingly expressed as the maximum wavelength sensitivity of 9.09 nm/°C and the amplitude sensitivity of ?0.311°C^?1. In addition, the actual micro-operation processes have been studied in detail, such as polishing depth, coating thickness and coating method. This provides practical ideas for real-time sensing analysis that requires harsh environments.     

Nitro-, Cyano-, and Methylfuroxans,and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.