Incorporation of CdS Nanoparticles Formed in Reverse Micelles into Mesoporous Silica

The incorporation of CdS nanoparticles, prepared in reverse micellar systems, into thiol-modified mesoporous silica, such as FM41 (functionalized MCM-41) and FM48 (functionalized MCM-48), has been investigated. The nanoparticles were immobilized in the mesopores via the incorporation of water droplets of the reverse micelles. A particle-sieving effect for FM41 having large (L-FM41, 3.8 nm) and medium (M-FM41, 3.6 nm) pore size was observed, in that the incorporation of the CdS nanoparticles was decreased with increasing particle size and with decreasing pore size of the FM41. Chemical vapor deposition treatment employed to narrow the mesopores of the CdS-FM41 enhanced the stability of CdS nanoparticles against heat treatment. The CdS-FM41 composites demonstrated photocatalytic activity for H(2) generation from 2-propanol aqueous solution, the better photocatalytic activity being obtained with the larger pore size for CdS-L-FM41. Copyright 2001 Academic Press.     

A double-functionalized cyclen with carbamoyl and dansyl groups (cyclen = 1,4,7,10-tetraazacyclododecane): a selective fluorescent probe for Y(3+) and La(3+).

A cyclen (=1,4,7,10-tetraazacyclododecane) doubly functionalized with three carbamoylmethyl groups and one dansylaminoethyl (dansyl = 2-(5-(dimethylamino)-1-naphthalenesulfonyl) group (L(2) = 1-(2-(5-(dimethylamino)-1-naphthalenesulfonylamido)ethyl)-4,7,10-tris(carbamoylmethyl)-cyclen) was synthesized and characterized. Potentiometrtic pH titration and UV spectrophotometric titration of L(2) served to determine deprotonation of the pendant dansylamide (L(2) --> H(-1)L(2)) with a pK(a) value of 10.6, while the fluorometric titration disclosed a pK(a) value of 8.8 +/- 0.2, which was assigned to the dansyl deprotonation in the excited state. The 1:1 M(3+)-H(-1)L(2) complexation constants (log K(app) = 6.0 for Y(3+) and 5.2 for La(3+), where K(app)(M-H(-1)L(2)) = [M(3+)-H(-1)L(2)]/[M(3+)](free)[L(2)](free) (M(-1)) at pH 7.4) were determined by potentiometric pH titration and UV and fluorescence spectrophotometric titrations (excitation at 335 nm and emission at 520 nm) in aqueous solution (with I = 0.1 (NaNO(3))) and 25 degrees C. The X-ray structure analysis of the Y(3+)-H(-1)L complex showed nine-coordinated Y(3+) with four nitrogens of cyclen, three carbamoyl oxygens, and the deprotonated nitrogen and a sulfonyl oxygen of the dansylamide. The crystal data are as follow: formula C(28)H(49)N(11)O(13.5)SY (Y(3+)-H(-1)L(2) x 2(NO(3)(-)) x 2.5H(2)O), M(r) = 876.73, monoclinic, space group P2(1)/n (No. 14), a = 18.912(3) A, b = 17.042(3) A, c = 24.318(4) A, beta = 95.99(1) degrees, V = 7794(2) A(3), Z = 8, R1 = 0.099. Upon M(3+)-H(-1)L(2) complexation, the dansyl fluorescence greatly increased (8.6 and 3.8 times for Y(3+) and La(3+), respectively) in aqueous solution at pH 7.4. Other lanthanide ions also yielded Ln(3+)-H(-1)L(2) complexes with similar K(app) values, although all the dansyl fluorescences were weakly quenched. On the other hand, zinc(II) formed only a 1:1 Zn(2+)-L(2) complex at neutral pH with negligible fluorescence change. The X-ray crystal structure of the Zn(2+)-L(2) complex confirmed the pendant dansylamide being noncoordinating. The crystal data are as follow: formula C(28)H(51)N(11)O(14)SZn (Zn(2+)-L(2) x 2(NO(3)(-)) x 3H(2)O), M(r) = 863.22, monoclinic, space group C2/n (No. 15), a = 35.361(1) A, b = 13.7298(5) A, c = 18.5998(6) A, beta = 119.073(2) degrees, V = 7892.3(5) A(3), Z = 8, R1 = 0.084. Other divalent metal ions did not interact with L(2) at all (e.g., Mg(2+) and Ca(2+)) or interacted with L(2) with the dansyl fluorescence quenched (e.g., Cu(2+)).     

ESTIMATION OF AN INDEX OF HYDROPHOBICITY OF DNA INTERIOR USING 5-METHOXYPSORALEN AS A FLUORESCENT PROBE

The index of hydrophobicity of DNA interior was estimated by measuring fluorescence spectra of psoralen derivatives associated with DNA. The environment around 5-MOP associated with DNA was as hydrophobic (D_k = 34) as methanol, suggesting that the molecules reside at the space between the base-pairs in B-form DNA. This is also true for 8-MOP. Thus, planar and aromatic molecules of 5- and 8-MOP are more stable in the interior of DNA than in aqueous medium due to hydrophobic affinity.     

Tumor cell detection method using complement-mediated cytolytic reaction and imaging sensor system

A novel tumor-detection system consisting of complementmediated cytolytic reaction and an image processing system was developed for the simple and rapid determination of tumor cells. The present system consists of a CCD image sensor, image memory board, personal computer, and microscope. When monoclonal antibody 3C4, which is specific to the guinea pig hepatoma L-10, was added to cell suspension, only L-10 cytolysis occurred. Cytolysis caused a decrease in brightness of the cells observed by phase-contrast microscopy. The phase contrast image of the cells before cytolysis was converted to a digitalized signal and stored in computer memory. After cytolysis, a brightness threshold above that of lysed cells was subtracted from the digitalized signal and compared to the signal stored before reaction. L-10 cells in mixed cell suspension were determined specifically by the system. Measurement time was only 2 sec and overall time, including reaction time, was approximately 30 min. Since this method does not require a cell washing process, automation of the whole system is possible.     

Comparisons of elemental concentrations in hair of the inhabitants of heavy metal polluted areas with those of normal Japanese

Human hair collected from the mercury, arsenic and cadmium polluted areas has been analysed by instrumental neutron activation method. The concentrations of 27 elements were compared with those of normal Japanese. Correlation coefficients of logarithmic concentrations between the elements were calculated and their significance levels were determined. Factor contribution and factor loadings of the elements were calculated for each factor by making use of principal component analysis. The factor score of each sample was also calculated for each factor to examine the effects of the contamination by heavy metals on individuals.     

A study of hepato-biliary and alimentary scintigrams using a triple tracer method

In order to evaluate the gastric emptying and postprandial mixing of bile with food, the scintigraphies of hepatobiliary and gastrointestinal tracts by using three different kinds of radioisotopes were performed simultaneously (99mTc-E.HIDA for hepatobiliary scintigraphy, 111In-DTPA containing orange juice and 131I-albumin containing scrambled egg for gastrointestinal scintigraphy). This method was available for observation of gastric emptying of liquid and solid foods and also examination of the mixing effect of bile and food quantitatively.     

Fast determination of thyroid stimulating hormone in human blood serum without chemical preprocessing by using infrared spectroscopy and least squares support vector machines

The least squares support vector machines (LS-SVM) was used to model infrared spectral data for TSH hormone secreted by thyroid, which regulates the basal metabolic rate. This model was used for direct estimation of the content of TSH in blood serum samples, and the results were comparable with those obtained with the conventional analytical method based on chemoluminescence methodology. Excellent agreement was observed between the conventional method and the newly developed calibration model based in analysis of spectral data with LS-SVM. The latter has clear advantages, because it is fast and requires no reagent once the measurements were done directly in the serum by using a simple mid-infrared spectrometer in the ATR mode. An important advantage observed in this calibration method based on LS-SVM is the remarkable capacity to avoid overfitting in the model-building step, that is, the developed method is highly robust.     

Mesoscopic structure and properties of liquid crystalline mesophase pitch and its transformation into carbon fiber

The history and present state of the art in the chemistry of mesophase pitch, which is an important precursor for carbon fiber and other high-performance industrial carbons, are reviewed relative to their structural properties. The structural concepts in both microscopic and macroscopic views are summarized in terms of the sp(2) carbon hexagonal plane as a basic unit common to graphitic materials, its planar stacking in clusters, and cluster assembly into microdomains and domains, the latter of which reflect the isochromatic unit of optical anisotropy. Such a series of structural units is described in a semiquantitative manner corresponding to the same units of graphitic materials, although the size and stacking height of the hexagonal planes (graphitic sheets) are very different. Mesophase pitch is a liquid crystal material whose basic structural concepts are maintained in the temperature range of 250 to 350 degrees C. The melt flow and thermal properties are related to its micro- and mesoscopic structure. The structure of mesophase-pitch-based carbon fiber of high tensile strength, modulus, and thermal conductivity has been formed through spinning, and has inherited the same structural concepts of mesophase pitch. Stabilization settles the structure in successive heat treatments up to 3000 degrees C. Carbonization and graphitization enable growth of the hexagonal planes and their stacking into units of graphite. Such growth is governed and controlled by the alignment of micro- and mesoscopic structures in the mesophase pitch, which define the derived carbon materials as nanostructural materials. Their properties are controlled by the nanoscopic units that are expected to behave as nanomaterials when appropriately isolated or handled.