Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Relaxational behavior of birefringence of aqueous carboxymethylcellulose under an alternating electric field at frequencies ranging from 0.1 Hz to 100 kHz

The d. c. component of birefringence of aqueous carboxymethylcellulose (CMC) under an a. c. electric field was measured at frequencies ranging from 0.1 Hz to 100 kHz. Three samples of different molecular weights were studied with varying degree of neutralization, polymer concentration and added salt concentration. The dispersion curve of birefringence consists of three relaxation bands,A, B andC in order of decreasing frequency. RelaxationB with a negative relaxation strength is ascribed to end-over-end rotation of almost rodlike CMC molecules. RelaxationA with a positive strength is attributed to the relaxation of electrical polarizability along the minor axis of molecule. RelaxationC possesses also a positive strength and is induced by clusters of CMC molecules.Dedicated to Prof. Dr. F. H. Müller.     

Gold-surface binding of molecular switches studied by M?ssbauer spectroscopy

The nonanuclear coordination compound [Mo^IV{(CN)Fe^III(3-methyl-saldptn)}₈]Cl₄ exhibits multiple spin transitions (3-methyl-saldptn = N,N′-bis(3′′-methyl-2′′-hydroxy-benzyliden)-1,7-diamino-4-azaheptane). This spin crossover cluster is bound via a self-assembled monolayer onto a two dimensional array gold surface. M?ssbauer spectroscopy indicates that the thermally and optically induced spin crossover of the compound is maintained. Thereby, the foundation for its potential practical application (e.g. in the field of information storage) was laid.     

Analysis of reaction products of cocaine and hydrogen peroxide by high-performance liquid chromatography/mass spectrometry

The change of chemical structure of cocaine in the presence of hydrogen peroxide, a main component of hair dye and decolorant treatments, was studied. High-performance liquid chromatography/mass spectrometry (LC/MS) was used for the separation and identification of cocaine derivatives. After a mixture of cocaine and hydrogen peroxide solutions was incubated at 39 degrees C (this temperature is commonly used when the hair is treated with hair dye or decolorant) for 24 h, six reaction products were detected by LC/MS. Two of them were ecgonine methyl ester and benzoylecgonine, which are metabolites of cocaine. The other reaction products were assumed to be ortho-, meta- and para-hydroxycocaines and dihydroxycocaine, in each of which the benzene ring was hydroxylated by the reaction. These five reaction products (except for dihydroxycocaine) were found immediately after mixing cocaine and hydrogen peroxide. Therefore, the above reaction products might be present in the hair of cocaine users that had treated their hair with hair dye or decolorant.     

Low-frequency and high-frequency relaxations in dynamic electric birefringence of poly(γ-benzyl-L-glutamate) in m-cresol

The dc component Δn of the electric birefringence of poly(γ-benzyl-L -glutamate) in m-cresol is measured under an ac electric field at frequencies from 0.5 Hz to 200 kHz for solutions covering the dilute and semidilute regions. The dispersion curve indicates that at low frequencies Δn decreases with increasing frequency (low-frequency relaxation). For high-molecular-weight polymers at high concentration, Δn becomes negative at high frequency and its absolute value decreases with further increase in frequency (high-frequency relaxation). A unified theory for the two relaxations is developed on the basis of a model in which, in the semidilute regime, the rodlike polymer is confined in a cage formed by neighboring polymers and the lifetime of the cage lies between relaxation times of the two relaxations. The low-frequency relaxation is ascribed to end-over-end rotation of the polymer and the high-frequency relaxation to the rotation within a limited angle in the cage. The dependences of relaxation parameters on polymer concentration and molecular weight are reasonably explained by the theory.     

Application of a self-sensing conductive probe for Si device imaging

For the evaluation of two-dimensional carrier profiles in semiconductor devices, we have developed a novel form of probe–sensor combined unit that uses an etched tungsten wire as a conductive probe, and commercially available quartz tuning fork as the force sensor. This unit has a self-sensing capability due to the piezoelectric effect of quartz tuning fork, thus obviating optical setup, and its conductivity is higher and more stable than that of conventional metal-coated Si cantilever. In addition, this probe–sensor combined unit is inexpensive and easy to use, when compared to the well-known optical methods of Si-based cantilever vibration detection system. Our scanning probe microscope using this probe–sensor combined unit is able to mapping the capacitive gradient signal (dC/dZ image) and internal damping of quartz tuning fork oscillation (dissipation image) while scanning the sample surface. In this letter, we show the results of visualization of the p–n junction locus of a Si metal–oxide–semiconductor field effect transistor in both dC/dZ and dissipation images.     

Biased and Unbiased Two-sided Wilcoxon Tests for Equal Sample Sizes

This paper answers the long-standing question of whether the two-sided Wilcoxon rank test for equal sample sizes is unbiased against a location parameter family of distributions by giving a counterexample. It is also shown that the nonrandomized two-sided Wilcoxon test for equal sample sizes with the least positive significance level is unbiased.     

Delineation of a p–n junction using dC/dX imagery produced by shear-mode scanning capacitance microscopy

Using a laterally oscillating all-metallic probe, a scanning capacitance microscope (SCM) has been used to yield an image of the spatial derivative of the local capacitance, dC/dX, where C and X are the local capacitance and the axis of the probe tip locus on the sample surface, respectively. Bias fields, except for the ultra-high-frequency fields used for sensing the capacitance, are not necessary to detect the dC/dX signal, which yields an image delineating clearly the depletion region due to the p–n junction. Simultaneously with the dC/dX image, the new SCM can give images of topography and dC/dV if an alternating field V is applied between the probe and sample. Received: 19 March 2001 / Accepted: 22 March 2001 / Published online: 27 June 2001     

Anomalous heat evolution of deuteron implanted al upon electron bombardment III - try to observe the nuclear d-d reaction

In previous papers, one of the authors (K. K.) has observed the anomalous melting of the surface layer of deuteron implanted Al, containing so-called "tunnel structures", on the electron bombardment in transmission electron microscope. In the present paper, we intended to observe the evidence of the d-d nuclear reaction, expecting neutron emission, associated with the melting phenomenon. However, the result was rather unexpected. The melting phenomenon was certainly observed under the same experimental conditions as before. But, in spite of the melting, neutron emission associated with the nuclear reaction was not observed. And, more unexpectedly, X-ray emission of energy less than roughly 400 v keV was observed when specimens with a bubble structure, which never showed melting, were bombarded with electron beams. Several conceivable mechanisms are discussed which, however, are all not convincing to explain the melting. The melting is attributed to some excess energy generation. The error estimation of the radiation measurements was undertaken.