Rapid screening of aqueous chemical warfare agent degradation products: ambient pressure ion mobility mass spectrometry

The use of electrospray ionization ambient pressure ion mobility spectrometry with an orthogonal reflector time-of-flight mass spectrometer to analyze chemical warfare (CW) degradation products from aqueous environmental samples has been demonstrated. Certified reference materials of analytical standards for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention treaty verification were used in this study. A combination of six G/V-type nerve and four S-type vesicant related CW agent degradation products were separated with baseline resolution by this instrumental technique. Analytical figures of merit for each CW degradation product were determined. In some cases, reduced mobility constants (K0) have been reported for the first time. linear response ranges for the selected CW degradation products were found to be generally approximately 2 orders of magnitude, where the overall dynamic response ranges were found to extend to 4 orders of magnitude. Limits of detection for five of the nine chemical products tested were found to be less than 1 ppm. To demonstrate the potential of this instrumental method with complex mixtures, four CW degradation products were separated and detected from a spiked Palouse River water sample in less than 1 min. Finally, a homologous series of n-alkylamines were used as baseline reference standards, producing a mobility/mass trend line to which the CW degradation products could be compared. Comparison of these products in this manner is expected to reduce the number of false positive/negative responses.     

Numerical methods for optimal control problems appearing in model validation of dynamic processes with application to dynamic robot calibration

Parameter estimation and optimal design of experiments are important steps in establishing models that reproduce a given process quantitatively correctly. The methods for parameter estimation and optimum experimental design are being more and more often applied in industry. The realization of methods in industrial practice shows however, that in order to use the complete potential of nonlinear optimum experimental design, we have to deal with several mathematical challenges. This article presents very effective algorithms for design of optimal experiments in dynamic systems and preliminary numerical results for dynamic robot calibration.     

Computer models for identifying instrumental citations in the biomedical literature

The most popular method for evaluating the quality of a scientific publication is citation count. This metric assumes that a citation is a positive indicator of the quality of the cited work. This assumption is not always true since citations serve many purposes. As a result, citation count is an indirect and imprecise measure of impact. If instrumental citations could be reliably distinguished from non-instrumental ones, this would readily improve the performance of existing citation-based metrics by excluding the non-instrumental citations. A citation was operationally defined as instrumental if either of the following was true: the hypothesis of the citing work was motivated by the cited work, or the citing work could not have been executed without the cited work. This work investigated the feasibility of developing computer models for automatically classifying citations as instrumental or non-instrumental. Instrumental citations were manually labeled, and machine learning models were trained on a combination of content and bibliometric features. The experimental results indicate that models based on content and bibliometric features are able to automatically classify instrumental citations with high predictivity (AUC = 0.86). Additional experiments using independent hold out data and prospective validation show that the models are generalizeable and can handle unseen cases. This work demonstrates that it is feasible to train computer models to automatically identify instrumental citations.     

Mass spectrometric analysis of DNA mixtures: instrumental effects responsible for decreased sensitivity with increasing mass

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has demonstrated great potential to replace gel electrophoresis for DNA sequence analysis. A current limitation in this method is, however, the decreased sensitivity with increasing mass of DNA molecules. In the present study, instrumental effects on the mass analysis of DNA molecules were investigated quantitatively using an equimolar DNA mixture. It is shown that detection efficiency, detector saturation, and ion beam divergence account for the entirety of the observed falloff in signal intensity with increasing mass. Although the present study focused upon the analysis of DNA mixtures, the instrumental effects observed apply equally to other macromolecular mixtures (e.g., proteins, polymers).     

Digital signal processing for step-scan phase and electrochemical potential double-modulation Fourier transform infrared spectrometry

Step-scan double-modulation (phase and electrochemical potential) Fourier transform infrared (FT-IR) spectrometry provides both spectroscopic and dynamic information about faradaic reactions. Recently introduced digital signal processing (DSP) can be used, instead of two lock-in amplifiers, for the optical signal demodulation at two modulation frequencies. In order to establish the merits of double-modulation FT-IR spectrometry with DSP, spectro-electrochemical experiments are performed in the attenuated total reflection configuration and with the commonly used ferri/ferrocyanide redox couple. Because of a large potential drop associated with the uncompensated resistance, a satisfactory signal-to-noise ratio for the alternating current (ac) optical measurements is obtained only with the employment of positive feedback compensation. In this arrangement, the amplitude of electrochemical modulation is sufficiently large to convert a significant fraction of the reduced form to the oxidized form and back to the reduced form. Large amplitude ac voltammetry demonstrates that the phase of faradaic admittance at the formal potential is approximately 45 degrees at 2.00 Hz. In addition, these experiments allow for calculation of the interfacial ac potential. This variable is needed for the normalization of the in-phase and the quadrature spectra in order to overcome the problem associated with the iR(u) drop. Because of the integral relationship between the faradaic current and the electromodulation reflectance coefficient, the phases of electromodulation reflectance coefficient with respect to the interfacial ac potential are expected to be -45 degrees and 135 degrees for the reduced and oxidized forms, respectively. However, dynamic information from double-modulation FT-IR spectrometry is available only if demodulation at the electrochemical potential modulation frequency is performed with respect to a defined phase. Because of an undefined demodulation phase implemented in the current version of DSP software, step-scan double-modulation FT-IR spectrometry with DSP is suitable only to provide spectroscopic information. In order to overcome this limitation, the demodulation of the ac optical signal at the electrochemical modulation frequency must be synchronized in phase with the ac potential modulation applied to the electrochemical cell.     

On-line recalibration of spectral measurements using metabolite injections and dynamic orthogonal projection

Spectrometers are enjoying increasing popularity in bioprocess monitoring due to their non-invasiveness and in situ sterilizability. Their on-line applicability and high measurement frequency create an interesting opportunity for process control and optimization tasks. However, building and maintaining a robust calibration model for the on-line estimation of key variables of interest (e.g., concentrations of selected metabolites) is time consuming and costly. One of the main drawbacks of using infrared (IR) spectrometers on-line is that IR spectra are compromised by both long-term drifts and short-term sudden shifts due to instrumental effects or process shifts that might be unseen during calibration. The effect of instrumental drifts can normally be reduced by referencing the measurements against a background solution, but this option is difficult to implement for single-beam instruments due to sterility issues. In this work, in order to maintain the robustness of calibration models for single-beam IR and to increase resistance to process and instrumental drifts, planned spikes of small amounts of analytes were injected periodically into the monitored medium. The corresponding measured difference spectra were scaled-up and used as reference measurements for updating the calibration model in real time based on dynamic orthogonal projection (DOP). Applying this technique led to a noticeable decrease in the standard error of prediction of metabolite concentrations monitored during an anaerobic fermentation of the yeast Saccharomyces cerevisiae.     

Experimental upgrades of membrane introduction mass spectrometry for water and air analysis

Some improvements to the membrane introduction mass spectrometry (MIMS) technique, resulting in low-ppt detection limits for volatile organohalogen compounds (CX) in water (namely, chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride) and low-microgram per cubic meter detection limits for benzene, toluene, ethylbenzene, and xylenes (BTEX) in gaseous samples, are shown. A static MIMS configuration was compared to a dynamic one, the former requiring longer time to obtain the analytical response. A cryotrapping preconcentration step is introduced and linearity of response, mixture effects, and detection limits are presented. The instrumental setup consists of a hollow fiber silicone membrane, a water or air container, a cryofocusing trap based on Tenax adsorbent, a Peltier cell, and a Varian ion trap benchtop mass spectrometer is described. This instrumental setup, which we named membrane extraction trap focusing mass spectrometry, allowed the detection of CX in water at a concentration as low as 8 ppt and of benzene in air at 0.1 microg/m3. The whole assembly shows great potential for on-site routine monitoring of drinking water resources and urban and indoor air under current EU and Italian regulations.     

Bulk Raman analysis of pharmaceutical tablets

We compare and contrast two Raman collection geometries, backscattering and transmission, to identify their potential for monitoring the bulk chemical composition of turbid media. The experiments performed on pharmaceutical tablets confirm the expected strong bias of the backscattering Raman collection towards surface layers of the probed sample. However, this bias is largely absent with the transmission geometry, exhibiting gross insensitivity to the depth of impurities within the sample. The results are supported by Monte-Carlo simulations. The applicability of transmission geometry to tablets without any thinning is possible because of long migration times of Raman photons in non-absorbing powder media. The absolute measured intensity of the Raman signal was only 12 times lower in transmission geometry compared with backscattering geometry for a standard paracetamol tablet with a thickness of 3.9 mm. This makes detection relatively straightforward, and detectable Raman signals were observed even after propagation through three paracetamol tablets. Given its properties and instrumental simplicity, the transmission method is particularly well suited to the on-line analysis of bulk content of tablets in pharmaceutical applications.     

Nanoparticles for two-photon photodynamic therapy in living cells

We describe here a nontoxic two-photon photodynamic nanoparticle platform and its cellular application. We demonstrate that the dye's potential toxicity can be circumvented by its permanent encapsulation into a biocompatible nanoparticle polymer matrix; this was examined by dye leaching experiments and confirmed by cell uptake experiments. Infrared two-photon nanoplatform phototoxicity was demonstrated for rat C6 glioma cells, while the controls showed no dark toxicity for these living cells.     

Biological scanning electrochemical microscopy and its application to live cell studies

Progress in instrumental design continues to pave the way for high-resolution, real-time electrochemical measurements with living cells.     

氧压机正常启停控制程序改进

总结2#23500m3/h空分设备氧压机因仪控电气故障造成的无法正常启停电机现象,分析故障原因,对仪控逻辑和通用设备控制模块程序进行了优化,杜绝了因可能的误操作而造成的重大事故。     

Polyurethanes as potential substrates for sub-retinal retinal pigment epithelial cell transplantation

Transplantation of cultured retinal pigment epithelial (RPE) cells under the failing macular is a potential treatment for age related macular degeneration. An important step in the development of this procedure is the identification of a suitable membrane on which to grow and transplant the cells. This paper evaluates the potential of using polyurethanes in this application since they possess several of the required properties, such as, flexibility, robustness, biostability and good biocompatiblilty although their hydrophobicity can limit cell adhesion. Three commercially available polyether urethanes (Pellethane, Tecoflex and Zytar) were evaluated in terms of their wettability using dynamic contact angle analysis and their ability to support a monolayer of functioning RPE cells (ARPE-19) . Furthermore Pellethane and Tecoflex were treated with a simple air plasma treatment and analysed as above. In the "as received condition" only a few RPE cells attached to the Pellethane and Tecoflex and remained clumped. RPE cells grew to confluence on the Zytar substrate by 7 days without further surface modification. Air gas plasma treatment of both Pellethane and Tecoflex increased the wettability of the surfaces and this resulted in the growth of a monolayer of well-spread RPE cells on both materials. Morphologically these cells grew with a normal 'cobblestone' phenotype. These results demonstrate the potential of these polyurethanes for this application.     

Velocity measurement of particles flowing in a microfluidic chip using Shah convolution Fourier transform detection

A noninvasive radiative technique, based on Shah convolution Fourier transform detection, for velocity measurement of particles in fluid flows in a microfluidic chip, is presented. It boasts a simpler instrumental setup and optical alignment than existing measurement methods and a wide dynamic range of velocities measurable. A glass-PDMS microchip with a layer of patterned Cr to provide multiple detection windows which are 40 microns wide and 70 microns apart is employed. The velocities of fluorescent microspheres, which were electrokinetically driven in the channel of the microfluidic chip, were determined. The effects of increasing the number of detection windows and sampling period were investigated. This technique could have wide applications, ranging from the determination of the velocity of particles in pressure-driven flow to the measurement of electrophoretic mobilities of single biological cells.     

A Modeling View of Breakthrough Innovation

Abstract

In this article we present a dynamic modeling framework, which facilitates an evaluation of a breakthrough innovation. One of the powerful aspects of this framework is its robustness. This process helps identify directions that increase the probability for finding possible breakthrough ideas and eventually products. This framework facilitates the initial evaluation of individual projects and also has value in evaluating accepted projects as they progress. Lastly, this framework is instrumental in the critical “go, no-go” decision, which inevitably happens somewhere along the line for most revolutionary products.     

负荷传感器试验的柔性加荷方法

通过对负荷传感器负荷特性检测实验中叠置加荷方式工作过程的力学分析，提出了柔性加荷的概念，指出准确的载荷控制取决于传感器加载系统结构刚度和施力装置能够实现的位移准确程度，给出了减小系统刚度的技术方法及设计计算公式，并通过试验验证了柔性加荷理论和技术方法的可行性与有效性。在负荷传感器的负荷特性试验中，采用该方法具有试验工作效率高、保证试验测量精度、容易实施和生产成本低的效果。     

Topological Models of the Flow and Kinetics of Coagulation‐Crystallization Structure Formation of Disperse Systems

This paper analyzes the processes of structure formation of disperse systems under dynamic and static conditions in terms of synergetics and the theory of catastrophes. The efficiency of using these methodological approaches together with adopted instrumental methods of investigating the properties of structured dispersions is shown.     

Immune algorithm with dynamic environments and its application to greenhouse control

A novel immune algorithm with dynamic environments (IADE), suitable for time-varying single-objective optimization problems with the static or variable dimension of design space, is proposed based on the immune response principle. Several immune operators, relying upon the functions or metaphors of somatic maturation, immune memory and immune cells, are designed to adapt the changing environment and track the location of the optimum. Especially, the environmental recognition rule and memory pool are established to speed up to search the optimum of the environment. Several algorithms reported are participated in comparison against IADE through using theoretical test problems and a practical greenhouse control problem. Preliminary experiments show that IADE can not only obtain great superiority, but also track rapidly time-varying environments. Comparative analysis illustrates IADE’s potential value.     

Time-resolved Fourier transform infrared spectroscopic imaging

Fourier transform infrared (FT-IR) imaging allows simultaneous spectral characterization of large spatial areas due to its multichannel detection advantage. The acquisition of large amounts of data in the multichannel configuration results, however, in a poor temporal resolution of sequentially acquired data sets, which limits the examination of dynamic processes to processes that have characteristic time scales of the order of minutes. Here, we introduce the concept and instrumental details of a time-resolved infrared spectroscopic imaging modality that permits the examination of repetitive dynamic processes whose half-lives are of the order of milli-seconds. As an illustration of this implementation of step-scan FT-IR imaging, we examine the molecular responses to external electric-field perturbations of a microscopically heterogeneous polymer-liquid crystal composite. Analysis of the spectroscopic data using conventional univariate and generalized two-dimensional (2D) correlation methods emphasizes an additional capability for accessing of simultaneous spatial and temporal chemical measurements of molecular dynamic processes.     

Instrumental implementation of a neuronlike generator with spiking and bursting dynamics based on a phase-locked loop

An instrumental model of a neuron based on a phase-locked loop with a bandpass filter in the control loop is proposed. The main constructive elements of the system are described. The existence of different dynamic modes that are qualitatively similar to the spiking and bursting neuron dynamics has been experimentally demonstrated.