A modification of the successive projections algorithm for spectral variable selection in the presence of unknown interferents

This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process. The advantages of this new approach are demonstrated in two analytical problems, namely (1) ultraviolet–visible spectrometric determination of tartrazine, allure red and sunset yellow in aqueous solutions under the interference of erythrosine, and (2) near-infrared spectrometric determination of ethanol in gasoline under the interference of toluene. In these case studies, the performance of conventional MLR-SPA models is substantially degraded by the presence of the interferent. This problem is circumvented by applying the proposed Adaptive MLR-SPA approach, which results in prediction errors smaller than those obtained by three other multivariate calibration techniques, namely stepwise regression, full-spectrum partial-least-squares (PLS) and PLS with variables selected by a genetic algorithm. An inspection of the variable selection results reveals that the Adaptive approach successfully avoids spectral regions in which the interference is more intense.     

Potential energy curve for ring-opening reactions: comparison between broken-symmetry and multireference coupled cluster methods

The spin-unrestricted Hartree-Fock (UHF)-based coupled cluster singles and doubles (UHF-CCSD) and Mukherjee's state-specific multireference CCSD (MkCCSD) methods are applied to four ring-opening reactions. The spin-restricted Hartree-Fock (RHF)-based CCSD (RHF-CCSD) calculations are also performed for comparison. In the case of the UHF-CCSD method, an approximate spin-projection (AP) method is applied to the broken-symmetry (BS) singlet solution to remove the spin contamination effect. For potential energy curves (PECs) of all reactions presented in this study, the results of RHF-CCSD and UHF-CCSD are substantially different from those of MkCCSD, while the results after the AP method (AP-UCCSD) reproduce the MkCCSD results well. It strongly suggests that the spin contamination effect should be removed by the AP correction even at the UHF-CCSD level to predict reliable energetics of these reactions.     

Properties of ionic liquids containing silver(I) or protic alkylethylenediamine cations with a bis(trifluoromethanesulfonyl)amide anion

Ionic liquids of an N-alkylethylenediamine-silver(I) complex cation (alkyl=hexyl, 2-ethylhexyl, and octyl) or a protic N-alkylethylenediaminium cation (alkyl=butyl, hexyl, 2-ethylhexyl, octyl, decyl, and dodecyl) with a bis(trifluoromethanesulfonyl)amide counter anion (Ag-ILs and PILs, respectively) were prepared and their physicochemical properties were investigated. The trend of solidification decreased in the order octyl?hexyl>2-ethylhexyl for the Ag-ILs, and butyl>dodecyl>decyl>octyl>hexyl?2-ethylhexyl for the PILs. The diffusion coefficients of the cations indicated stronger intermolecular interactions in PILs than in the Ag-ILs because of hydrogen-bonding networks, and it has been revealed that the intermolecular interactions increase in the order, hexyl相似文献   

Second Harmonic Generation in Bis Typed Organic Compounds

In systematic research on a series of new nonlinear organic materials, we found that Bis (4-nitrophenoxy) methane (BNPM) showed a large intensity of second harmonic light, which was 4.4 times as large as that of urea crystal by powder technique and easily crystallized from a solution. The crystal structure of BNPM, obtained by the X-ray diffraction method, was orthorhombic, space group P2₁2₁2 (point group 222), with unit-sell dimension a = 10.205 Å; b = 12.854 Å; c = 4.8822 Å. In addition, we found that the absorption edge of BNPM was 430 nm with a 0.9-mm-thick crystal, and we observed the second harmonic light with BNPM single crystal at the wavelength of 1064 nm and in the range from 906 nm to 990 nm.     

A simple method for counting the number of trapped ions in an ion trap

A technique is proposed for injection-seeding control of tunable lasers. It is based on a combination of successive external injection and intracavity self-injection of radiation when the active medium is pumped by dual-step pulses. The technique is tested both experimentally (in the case of Nd:YAG-laser-pumped pulsed dye lasers) and numerically, using a model developed by us. Full conversion of the broadband spectrum into the injected line is achieved for an output energy greater by a factor of about 50 than that managed by means of the traditional injection-seeding technique under identical conditions.     

Corelationship between local structure and water purifying ability of iron-containing waste glasses

A relationship between the structure and water purifying ability of waste glass prepared from household garbage and Fe₂O₃ was examined by ⁵⁷Fe-Mössbauer and induced coupled plasma (ICP) measurements. From the Debye temperature of waste glass, Fe^II proved to be loosely bound in the glass network as a network modifier. Dissolution amount of Fe^III into artificial drain can be controlled from 0.14 to 0.35 mg/l by changing the Fe₂O₃ content. It proved that chemical oxygen demand (COD) decreases in proportion to the content of Fe^III, indicating that iron causes decomposition of organic and phosphorus compounds.     

Measurement of Principal-Stress Directions from Photoelastic Experiment Using Generalized Phase-Shift Method

A generalized phase-shift method is developed for automatic measurement of principal-stress directions in the whole field of a model from photoelastic experiments. This method uses a set of light intensities obtained from the rotation of polaroids in dark-field plane polariscopes at each point. To investigate the accuracy of the measurement, time-series light intensity curves with different noise and different numbers of data which constitute the curves are used in computer simulation. The error of the measurement of the principal-stress directions obtained by the method is not greatly affected by noise when the number of data exceeds 50. This method is applied to a circular disk subjected to a concentrated load. The principal-stress directions obtained by the method are found to be in good agreement with the theory.Presented at 1996 International Workshop on Interferometry (IWI ‘96), August 27–29, Saitama, Japan.     

Synthetic studies of the cyclic depsipeptides bearing the 3-amino-6-hydroxy-2-piperidone (Ahp) unit. Total synthesis of the proposed structure of micropeptin T-20

The first total synthesis of a cyclic depsipeptide possessing the 3-amino-6-hydroxy-2-piperidone (Ahp) unit was successfully achieved in a convergent manner by the oxidative construction of the Ahp unit at the later stage of the synthesis. This synthetic work provides data indicating that the structure of the target Ahp-depsipeptide, micropeptin T-20, should be re-examined.