Heat capacities and thermodynamic functions of p-chlorobenzoic acid

The heat capacities of p-chlorobenzoic acid were measured in the temperature range from 80 to 580 K by means of an automatic adiabatic calorimeter equipped with a small sample cell of internal volume of 7.4cm(3). The construction and procedures of the calorimetric system were described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on alpha-Al2O3. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.28 per cent, while the inaccuracy is within +/-0.40 per cent, compared with the recommended reference data in the whole experimental temperature range. A fusion transition at T = 512.280 K was found from the C-p-T curve of p-chlorobenzoic acid. The enthalpy and entropy of the phase transition, as well as the thermodynamic functions {G((T)) - G((298.15))}, {H-(T) - H-(298.15)} and {S-(T) - S-298.15}, were derived from the heat capacity data. The mass fraction purity of p-chlorobenzoic acid sample used in the present calorimetric study was determined to be 0.99935 by fraction melting approach. (C) 2002 Elsevier Science Ltd. All rights reserved.

Immobilized metal-ion chelating capillary microreactor for peptide mapping analysis of proteins by matrix assisted laser desorption/ionization-time of flight-mass spectrometry

Peptide mass mapping analysis, utilizing a regenerable enzyme microreactor with metal-ion chelated adsorption of enzyme, combined with matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) was developed. Different procedures from the conventional approaches were adopted to immobilize the chelator onto the silica supports, that is, the metal chelating agent of iminodiacetic acid (IDA) was reacted with glycidoxypropyltrimethoxysilane (GLYMO) before its immobilization onto the inner wall of the fused-silica capillary pretreated with NH4HF2. The metal ion of copper and subsequently enzyme was specifically adsorbed onto the surface to form the immobilized enzyme capillary microreactor, which was combined with MALDI-TOF-MS to apply for the mass mapping analysis of nL amounts of protein samples. The results revealed that the peptide mapping could routinely be generated from 0.5 pmol protein sample in 15 min at 50degreesC, even 20 fmol cytochrome c could be well digested and detected.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

Multiphoton ionization and ab initio calculation studies of pyridine-water mixed clusters using time of flight mass spectrometer

Multiphoton ionization of binary mixed clusters (C5H5N)(x)-(H2O)(y) at 532, 355 and 266 nm laser wavelengths has been investigated using TOF mass spectrometer. The experiments showed that almost all the products were protonated ions, At 532 and 355 nm, the products were mainly protonated pyridine clusters (C5H5N)(n)-H+, while at 266 nm, mixed binary cluster ions (C5H5N)(m)- (H2O)(n)-H+ appeared. It was found that the abundance of the [(C5H5N)(3)-H2O-H](+) ions was abnormally high. The calculation indicated that the ion [(C5H5N)(3)-H2O-H](+) is Of a kind of magic number structures with C-3v symmetry. A stepwise reaction mechanism is suggested that photoionization is followed by dissociation. (C) 2001 Elsevier Science B.V. All rights reserved.

Mass resolved MPI spectra of methyl iodide in the 430-490 nm region

The mass resolved multiphoton ionization (MPI) spectra of methyl iodide were obtained in the 430-490 nm region using a time-of-flight (TOF) mass spectrometer. They have the same vibrational structure, which testifies that the fragment species, in the wavelength region under study, are from the photodissociation of multiphoton ionized molecular parent ions. Some features in the spectra are identified as three-photon excitations to 6p and 7s Rydberg states of methyl iodide. Two new vibrational structures of some Rydberg states are observed. The mechanism of ionization and dissociation is also discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

Matrix-assisted laser desorption/ionization mass spectrometry using porous silicon and silica gel as matrix

Porous silicon powder and silica gel particles have been applied as inorganic matrices for the analysis of small molecules in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOFMS). In contrast to conventional MALDI-TOFMS, the signal interference of low-molecular analytes by the matrix has been eliminated. Almost no fragmentations of the analytes were observed. Effects of various factors, such as the particle and pore size, the suspending solution, and sample preparation procedures, on the intensity of mass spectra have been investigated. The pore structure of the inorganic matrix and penetration of the analytes into the pores must be optimized for effective desorption and ionization of the analytes. Matrices (DHB and HCCA) were covalently bound to silica gel for improvement of spectrum intensity. Copyright (C) 2001 John Wiley & Sons, Ltd.

Calibration of an audio-frequency ion trap mass spectrometer

A method for calibration of an audio-frequency (AF) ion trap mass spectrometer is described. The method is proposed to surmount the obstacle that there is a lack of a proper calibrant for mass spectrometers in the mass-to-charge ratio (m/z) range of 10(6) to 10(10). To calibrate such mass spectra, we determine the point of ejection, q(eject), on the stability diagram of the ion trap operated in a mass-selective axial instability mode. This is accomplished by measuring the radial secular frequencies (and therefore, the m/z value) of a single trapped particle using a light scattering method, followed by monitoring the action of particle ejection in real time to obtain the q(eject). A delayed ejection with q(eject) = 0.949 +/- 0.004 is found at a trap driving frequency of Ohm/2pi = 200-600Hz. Theoretical analysis for the origin of the delayed ejection indicates that the delay is predominantly resulted from the existence of multipole components in the fields due to trap imperfections. Inclusion of -3% of the octopole with respect to the basic quadrupole field can satisfactorily account for our observations. An m/z accuracy approaching 0.1% is attainable after proper calibration of the AF ion trap mass spectrometer. (Int J Mass Spectrom 214 (2002) 63-73) (C) 2002 Elsevier Science B.V. All rights reserved.

A method for the analysis of low-mass molecules by MALDI-TOF mass spectrometry

We report a novel method termed matrix suppressed laser desorption/ionization to improve the analysis of low-mass molecules by MALDI-TOF mass spectrometry. In this method, the surfactant of cetrimonium bromide (CTAB) is added to the conventional matrix of alpha-cyano-4-hydroxycinnamic acid solution to prepare the MALDI samples. During the MALDI process, the presence of CTAB could substantially or even completely suppress the matrix-related ion background. As a result, very clean mass spectra can be routinely obtained in the low-mass range. In addition, the presence of CTAB can significantly improve the mass resolution of low-mass molecules. It is seen that high-quality spectra were routinely obtained at a matrix/CTAB ratio of 1000:1. This method has been successfully used to analyze a variety of low-mass molecules.

Determination of Point of Zero Charge of Tunisian Kaolinites by Potentiometric and Mass Titration Methods

This paper deals with determining points of zero charge of natural and Na+-saturated mineral kaolinites using two methods: (1) acid-base potentiometric titration was employed to obtain the adsorption of H+ and OH- on amphoteric surfaces in solutions of varying ionic strengths in order to determinate graphically the point of zero net proton charge (PZNPC) defined equally as point of zero salt effect (PZSE); (2) mass titration curve at different electrolyte concentrations in order to estimate PZNPCs by interpolation and to compare with those determined by potentiometric titrations. The two methods involved points of zero charge approximately similar for the two kaolinites between 6.5-7.8, comparable to those reported previously and were in the range expected for these clay minerals. The comparison of potentiometric surface titration curves obtained at 25 °C and those published in the literature reveals significant discrepancies both in the shape and in the pH of PZNPCs values.

On Combining Morphological Component Analysis and Concentric Morphology Model for Mammographic Mass Detection

Mammographic mass detection is an important task for the early diagnosis of breast cancer. However, it is difficult to distinguish masses from normal regions because of their abundant morphological characteristics and ambiguous margins. To improve the mass detection performance, it is essential to effectively preprocess mammogram to preserve both the intensity distribution and morphological characteristics of regions. In this paper, morphological component analysis is first introduced to decompose a mammogram into a piecewise-smooth component and a texture component. The former is utilized in our detection scheme as it effectively suppresses both structural noises and effects of blood vessels. Then, we propose two novel concentric layer criteria to detect different types of suspicious regions in a mammogram. The combination is evaluated based on the Digital Database for Screening Mammography, where 100 malignant cases and 50 benign cases are utilized. The sensitivity of the proposed scheme is 99% in malignant, 88% in benign, and 95.3% in all types of cases. The results show that the proposed detection scheme achieves satisfactory detection performance and preferable compromises between sensitivity and false positive rates.

Mass transfer resistance in the production of high impact polypropylene

Mass transfer resistance in the production of high impact polypropylene (hiPP) produced by a two-stage slurry/gas polymerization was investigated by field-emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. It is found that the formation of ethylene-propylene copolymer (EPR) phases in polypropylene (iPP) particle produced in the first stage slurry polymerization exhibits a developing process from exterior to interior