Hadamard transform capillary electrophoresis combined with absorption spectrometry

A novel injection device for applying absorption spectrometry to Hadamard transform (HT) capillary electrophoresis is described. A small hole, at the center part of the capillary, functions as an inlet port for the sample. The hole is immersed in a sample solution and the end of the capillary that is usually employed for sample introduction is immersed in a buffer solution. An ultraviolet absorption detector is placed between the sample injection port and the other end of the capillary filled with a buffer solution. A high potential is continuously applied between the injection port and the end of the capillary, which allows the sample solution to be introduced into the separation capillary. By application of a higher potential modulated according to a Hadamard code between both ends of the capillary, the buffer solution is injected into the separation capillary. In some preliminary experiments, this injection device was utilized to introduce a single sample segment into a capillary. As expected, a single peak was observed in the electropherogram for a sample containing a single component. This device was then employed for multiple sample injection in HT capillary electrophoresis. An 8-fold improvement in the S/N ratio was observed when the HT technique was used, in which a 255-order of a Hadamard matrix was used, as expected from theory. The present approach was also utilized for the sensitive detection of a sample comprised of multiple components.     

Fast Hadamard transform capillary electrophoresis for on-line, time-resolved chemical monitoring

We report a new approach for collecting and deconvoluting the data in Hadamard transform capillary electrophoresis, referred to as fast Hadamard transform capillary electrophoresis (fHTCE). Using fHTCE, total analysis times can be reduced by up to 48% per multiplexed separation compared to conventional Hadamard transform capillary electrophoresis (cHTCE) while providing comparable signal-to-noise ratio enhancements. In fHTCE, the sample is injected following a pseudorandom pulsing sequence derived from the first row of a simplex matrix (S-matrix) in contrast to cHTCE, which utilizes a sequence of twice the length. In addition to the temporal savings provided by fHTCE, a 50% reduction in sample consumption is also realized due to the decreased number of sample injections. We have applied fHTCE to the analysis of mixtures of neurotransmitters and related compounds to yield improved signal-to-noise ratios with a total analysis time under 10 s. In addition, we demonstrate the capability of fHTCE to perform time-resolved monitoring of changes in the concentration of model neurochemical compounds.     

Ultratrace analysis based on Hadamard transform capillary electrophoresis

Hadamard transform capillary electrophoresis, which is based on a multiple sample injection technique, was combined with laser-induced fluorometry and utilized in the determination of analytes at subpicomolar levels. The sensitivity was substantially improved by increasing the order, i.e., the number of elements, of the Hadamard matrix. In fact, the signal-to-noise ratio was enhanced 18-fold by the use of a matrix of order 2047. A feasibility study was carried out by computer simulation to study the detection of an average of less than a single molecule in a single injection volume. The signal peak was clearly observable even under conditions at which only 0.3 molecule is present in the volume. Thus, this approach is potentially useful for ultratrace analysis, in which conventional single-injection capillary electrophoresis cannot be applied.     

Hadamard transform capillary electrophoresis

This paper reports the first demonstration of a multiplex sample injection technique in capillary electrophoresis. The sample was injected into a capillary (effective length, 4 cm) as a pseudorandam Hadamard sequence by a photodegradation technique using a high-power gating laser, and the fluorescence signal, which was measured using a probe excitation beam, was decoded by an inverse Hadamard transformation. The signal-to-noise ratio was improved by a factor of 8, which was in good agreement with the theoretically predicted value of 8.02. This approach is potentially useful for the enhancement of the sensitivity by 3 orders of magnitude in high-resolution capillary electrophoresis, combined with fluorescence detection.     

Isoelectric focusing in a microfluidically defined electrophoresis channel

A new form of microchip isoelectric focusing that allows efficient coupling with pretreatment processes is reported. The sample is conveyed in a carrier ampholyte solution to the separation channel that is connected at both ends by two V-shaped lead channels, which supply electrode solutions to the connection point and complete the electrical connection to off-chip electrodes. The relatively high electric conductivity of the electrode solutions compared with that of the pH gradient enables focusing with a 2% loss of applied voltage at the electrodes using the lead channels. A glass microchip was constructed specifically for this configuration. The channel wall was coated with polydimethylacrylamide, and the IEF chip was operated in a chip holder equipped with on-chip connector valves. A plug of fluorescence-labeled peptide p I markers with p I values ranging from 3.64 to 9.56 with carrier ampholyte solution (pH 3-10) was introduced into the separation channel. When the plug reached the channel segment (24 mm in length) between the connection points with the electrolyte lead channels, isoelectric focusing was started after filling the lead channels with electrolyte solutions. The peptide markers were observed using scanning fluorescence detection. The entire range of the pH gradient was established in the segment after approximately 2 min. Isoelectric focusing of three consecutively injected sample plugs containing different p I markers was demonstrated.     

直接斜率法复原矩阵误差分析

利用范数理论,对直接斜率法中的复原矩阵误差进行了理论分析,认为直接斜率法中的探测噪声和测试传递矩阵的电压矩阵是影响复原电压误差大小的主要因素.在61单元自适应光学系统中噪声相同的情况下,对用Hadamard模式和单位矩阵模式这两种模式得到复原矩阵的方法进行了仿真,并用这两个复原矩阵去校正像差,得到了两个残差波面.通过比较这两个残差波面,得出在相同的噪声条件下,用Hadamard模式得到的复原矩阵有较小误差.     

Applications of Hadamard transform to gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry

Successful application of the Hadamard transform (HT) technique to gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS) is described. Novel sample injection devices were developed to achieve multiple sample injections in both GC and LC instruments. Air pressure was controlled by an electromagnetic valve in GC, while a syringe pump and Tee connector were employed for the injection device in LC. Two well-known, abused drugs, 3,4-methylenedioxy-N-methylamphetamine (MDMA) and N, N-dimethyltryptamine (DMT), were employed as model samples. Both of the injection devices permitted precise successive injections, resulting in clearly modulated chromatograms encoded by Hadamard matrices. After inverse Hadamard transformation of the encoded chromatogram, the signal-to-noise (S/N) ratios of the signals were substantially improved compared with those expected from theoretical values. The S/N ratios were enhanced approximately 10-fold in HT-GC/MS and 6.8 in HT-LC/MS, using the matrices of 1023 and 511, respectively. The HT-GC/MS was successfully applied to the determination of MDMA in the urine sample of a suspect.     

Dual boundary element analysis using complex variables for potential problems with or without a degenerate boundary

The dual boundary element method in the real domain proposed by Hong and Chen in 1988 is extended to the complex variable dual boundary element method. This novel method can simplify the calculation for a hypersingular integral, and an exact integration for the influence coefficients is obtained. In addition, the Hadamard integral formula is obtained by taking the derivative of the Cauchy integral formula. The two equations (the Cauchy and Hadamard integral formula) constitute the basis for the complex variable dual boundary integral equations. After discretizing the two equations, the complex variable dual boundary element method is implemented. In determining the influence coefficients, the residue for a single-order pole in the Cauchy formula is extended to one of higher order in the Hadamard formula. In addition, the use of a simple solution and equilibrium condition is employed to check the influence matrices. To extract the finite part in the Hadamard formula, the extended residue theorem is employed. The role of the Hadamard integral formula is examined for the boundary value problems with a degenerate boundary. Finally, some numerical examples, including the potential flow with a sheet pile and the torsion problem for a cracked bar, are considered to verify the validity of the proposed formulation. The results are compared with those of real dual BEM and analytical solutions where available. A good agreement is obtained.     

Liquid-crystal-display projector-based modulation transfer function measurements of charge-coupled-device video camera systems

We demonstrate the ability to measure the system modulation transfer function (MTF) of both color and monochrome charge-coupled-device (CCD) video camera systems with a liquid-crystal-display (LCD) projector. Test matrices programmed to the LCD projector were chosen primarily to have a flat power spectral density (PSD) when averaged along one dimension. We explored several matrices and present results for a matrix produced with a random-number generator, a matrix of sequency-ordered Walsh functions, a pseudorandom Hadamard matrix, and a pseudorandom uniformly redundant array. All results are in agreement with expected filtering. The Walsh matrix and the Hadamard matrix show excellent agreement with the matrix from the random-number generator. We show that shift-variant effects between the LCD array and the CCD array can be kept small. This projector test method offers convenient measurement of the MTF of a low-cost video system. Such characterization is useful for an increasing number of machine vision applications and metrology applications.     

Solid-state digital micro-mirror array spectrometer for Hadamard transform measurements of glucose and lactate in aqueous solutions

A novel solid-state near-infrared spectrometer is presented based on a digital micro-mirror array device (DMD) that is well designed for Hadamard transform spectroscopy. This spectrometer is designed for the collection of transmission spectra over the C-H first overtone region of the near-infrared spectrum (6500-5500 cm(-1)). A spectral resolution of 2.2 nm (~11 cm(-1)) is realized by using a 25 μm diameter linear tungsten filament as the source. Such a thin filament reduces imaging aberrations into the micro-mirror array, thereby enhancing spectral resolution. After passing through the sample, the transmitted radiation is dispersed with a grating before being imaged onto the surface of the DMD. Hadamard transform masks are implemented through the DMD and the reflected light is monitored by a single-element photodiode detector. The analytical utility of this approach is demonstrated through the multivariate quantification of glucose and lactate in binary mixtures composed in an aqueous buffer solution. A signal-to-noise ratio of 35,000 is achieved through these aqueous samples, and the resulting quantitative measurements provide a standard error of prediction of 1.4 and 0.9 mM for glucose and lactate, respectively. The selectivity of the resulting calibration models is established by using both a pure component selectivity analysis as well as analysis of the net analyte signal for each component. These quantitative results from the DMD Hadamard transform spectrometer compare favorably to similar measurements performed with a commercial Fourier transform spectrometer.     

Interfacial Tension Measurement With an Optofluidic Sensor

This paper reports a novel optofluidic sensor for measuring dynamic interfacial tensions. The field of optofluidics utilizes both microfluidics and micro-optics. Thus, our sensor consists of a microfluidic network and an optical detection system. The sensor is able to measure both surface tension and liquid/liquid interfacial tension. In the case of surface tension measurement, the liquid sample is introduced into a main channel, while air is injected through a T-junction. In the case of liquid/liquid interfacial tension measurement, a second immiscible liquid such as oil is introduced into a main channel, while the sample liquid is injected through the T-junction. The formation frequency of the microbubbles or microdroplets is a function of the interfacial tension between the two phases. This frequency can be measured easily by optical detection. Measurements were carried out for aqueous solutions with different concentrations of the ionic surfactant cetyl trimethyl ammonium bromide (CTAB). The actual interfacial tensions of these solutions were calibrated with a commercial tensiometer (FTA200, First Ten Angstrom). The measurement results show a clear relation between the interfacial tension and the formation frequency. Furthermore, our sensor can be used to identify the critical micelle concentration (CMC) of a surfactant. The sensor potentially allows the use of a minute amount of sample compared to the relatively large amount required for existing commercial systems     

Synthesis of Hadamard transformers by use of multimode interference optical waveguides

We propose a synthesis method of optical Hadamard transformer using multimode interference (MMI) couplers. By using the signal transfer matrix of 2 x 2, 4 x 4, and 8 x 8 MMI couplers, we show that sum and difference units of input signals can be synthesized. An interchange unit of two signals can also be synthesized. One synthesis method of Hadamard transformers is a combination of only 2 x 2 units, and the other is a combination of N x N(N > or = 4) units as well as 2 x 2 units. The design examples of operation units are shown, and the size and the output power of Hadamard transformers are estimated.     

Fiber-based polarization-sensitive Mueller matrix optical coherence tomography with continuous source polarization modulation

We report on a new configuration of fiber-based polarization-sensitive Mueller matrix optical coherence tomography that permits the acquisition of the round-trip Jones matrix of a biological sample using only one light source and a single depth scan. In this new configuration, a polarization modulator is used in the source arm to continuously modulate the incident polarization state for both the reference and the sample arms. The Jones matrix of the sample can be calculated from the two frequency terms in the two detection channels. The first term is modulated by the carrier frequency, which is determined by the longitudinal scanning mechanism, whereas the other term is modulated by the beat frequency between the carrier frequency and the second harmonic of the modulation frequency of the polarization modulator. One important feature of this system is that, for the first time to our knowledge, the Jones matrix of the sample can be calculated with a single detection channel and a single measurement when diattenuation is negligible. The system was successfully tested by imaging both standard polarization elements and biological samples.     

Speckle reduction using orthogonal arrays in laser projectors

We propose using a two-level (-1 and +1 as variables) orthogonal array (OA) to generate a binary phase diffuser for speckle reduction in laser projection displays. Compared with the Hadamard matrix, the diffuser generated from OA is more flexible. The speckle contrast ratio (CR) when introducing the binary phase diffuser at an intermediate image plane within the projector is calculated, and the minimum speckle CR can be achieved by finite step change of the diffuser patterns. With Kronecker algebra, the two-dimensional diffuser can also be replaced by two one-dimensional diffusers with the same function, and it can be implemented into the laser projector electronically and easily.     

Microfluidic sensor for dynamic surface tension measurement

A novel microfluidic sensor for measuring dynamic gas-liquid interfacial tension is reported. The device consists of a microfluidic chip with a microchannel network and an optical detection system. The sample is introduced into a main channel, while air is injected through a T-junction. Owing to the fixed flow rate ratio used for the sensor, surface tension is the only parameter determining bubble formation frequency, which can be measured by optical detection. Although the bubble is represented by a pulse in the output signal, the formation frequency is simply the frequency of the output signal. Measurements were carried out for aqueous solutions with different concentrations of the ionic surfactant cetyl trimethyl ammonium bromide. Surface tensions of these solutions were calibrated with a commercial tensiometer. The measurement results show a clear relationship between surface tension and formation frequency. The sensor can be used to identify the critical micelle concentration of the surfactant. The sensor potentially allows the use of a minute amount of sample compared with the relatively large amount required for existing commercial systems.     

Some identities for fundamental solutions and their applications to weakly-singular boundary element formulations

Some integral identities for the fundamental solutions of potential and elastostatic problems are established in this paper. With these identities it is shown that the conventional boundary integral equation (BIE), which is generally expressed in terms of singular integrals in the sense of the Cauchy principal value (CPV), and the derivative BIE, which is similarly expressed in terms of hypersingular integrals in the sense of the Hadamard finite-part (HFP), can both be written as weakly-singular integral equations in a systematic approach. Discretization of the weakly-singular BIE leads to the weakly-singular boundary element formulation equivalent to the method of using the rigid body displacement to determine the diagonal submatrices, which involve the CPV terms and the geometric matrix C, in the conventional BEM. The discretization of the weakly-singular derivative BIE possesses a similar feature, i.e. no CPV and HFP are involved. All these suggest that the practice of calculating CPV or HFP (for boundary integrals) and the geometric matrix C, either analytically or numerically, is unnecessary in the BEM. The approach developed in this paper is applicable to other problems such as plate bending, acoustics and elastodynamics.     

Evaluation of Kromoscopy: resolution of glucose and urea

Kromoscopy involves the transmission of a broad band of electromagnetic radiation through the sample of interest. The transmitted light is collected and divided evenly into four detector channels with complementary bandpass functions. This optical configuration provides high signal-to-noise ratios that are ideal for analytical measurements. The molecular basis of the four-channel response is critical, because it directly influences selectivity of the measurement and, therefore, the feasibility of applications in complex sample matrices. Selectivity of the Kromoscopic signal is demonstrated by resolution of glucose and urea with four channels of information collected over the 800-1300-nm near-infrared spectral region. Analysis of the individual channel responses indicates that the displacement of water from the optical path by the dissolution of solute is a major component of the Kromoscopic measurement in this spectral region. Nevertheless, significant differences are observed in channel responses for glucose and urea. A three-dimensional vector plot of the data highlights these differences and reveals unique vector directions for glucose and urea. This difference in direction of the response vectors represents the principal basis for distinguishing glucose and urea dissolved in aqueous solutions.     

Finite element simulation of pinched pressure-driven flow injection in microchannels

A pinched pressure-driven flow injection on a microchip is numerically simulated in order to optimize the relative values of the operational parameters. The geometry studied is a two-dimensional rectangular channel featuring a cross-junction with a large depth-over-width ratio. The hydrodynamic and convection-diffusion equations are solved for the two steps of the process: first, the sample solution is pinched into the transversal channel (injection channel), and then it is injected into the longitudinal one (separation channel), where the time evolution of the concentration is analyzed for different types of the detectors. Electroosmotic flow calculations have also been performed and have shown a good agreement with literature. The results for pressure-driven flow point out that the shape of the detection signal is strongly dependent on the velocity in the separation channel and on the position of the detection probes. The so-called double-humped peak, caused by the parabolic flow profile at high driving flow rate is analyzed. A tight pinch greatly decreases the amount of injected sample and, consequently, the signal sensitivity without increasing its quality. A proper pullback of the sample during the separation process can decrease the tailing due to the sample leakage from the injection channel. Although a high sample pullback causes a considerable decrease in the signal sensitivity, it also greatly enhances the peak resolution. Finally, it is shown that a wider injection channel with high sample pullback ensures an improved signal sensitivity with good resolution.     

Organized media for fluorescence analysis of complex samples: comparison of bile salt and conventional detergent micelles in coal liquids.

Accurate quantitative determinations are often difficult to obtain from fluorescence analysis of complex samples due to sample matrix effects and intermolecular interactions between solutes. Organized media can be used to minimize these unwanted processes without physical separation or extraction of the analytes from the sample matrix by isolating the analyte molecules in a uniform microenvironment within the sample. The advantages of bile salt micellar media over conventional detergent micelles are demonstrated for analysis of coal liquids. The bile salt media is shown to increase the sensitivity and dynamic range of fluorescence measurements relative to simple ethanolic solutions, without promoting gound-state and excited-state interactions that occur in the detergent micellar media.     

Statistical Optimization of a Controlled Release Formulation Obtained by a Double Compression Process: Application of an Hadamard Matrix and a Factorial Design

A formulation containing an antiinflammatory agent (diclofenac sodium), two inert matrices (ethylcellulose and polyvinyl chloride) and two lubricants (magnesium stearate and talc) was optimized by a double compression process

In a first stage, preliminary trials were performed in order to study the effect of lubricants added before and after precompression

An Hadamard matrix H(8) was applied to estimate the main effects of four parameters: applied force at the upper punch (UPF) during precompression, particle size range after grinding, UPF during the final compression and concentration of ethylcellulose added before the final compression

Following the Hadamard matrix, a factorial design 2² was built. The complete linear models were fitted by regression for each response reflecting the compression behaviour and dissolution kinetics

In an optimal point, the validation was carried out with the area under the dissolution curve, being the major response to be optimized

The dissolution curves were well fitted by the Weibull distribution