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71.
Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions. 相似文献
72.
M. G. Ezernitskaya B. V. Lokshin T. Yu. Orlova V. N. Setkina V. I. Shilnikov S. Nunziante Cesaro 《Russian Chemical Bulletin》1994,43(11):1841-1845
FTIR spectra have been studied for staircase cyclopentadienyl complexes containing two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO)2Fe-CpmMn(CO)3 (1), Cp(CO)2Fe-CpmFe(CO)2CH2Ph (2), Cp(CO)2Fe-Cpm(CO)2Fe-CpmMn(CO)3 (3), Cp(CO)2Mo-Cpm(CO)2Fe-CpmMn(CO)3 (4), Cp(CO)3W-Cpm(CO)2Fe-CpmMn(CO)3 (5), Cp(CO)2Fe-Cpm(CO)2Fe-BmCr(CO)3 (6), Cr(CO)3Bm-CpmFe(CO)2CH2Ph (7), where Cp = 5-C5H5, Cpm = 15-C5H4, Bm = 16-C6H5. Temperature-dependent FTIR spectra were measured inn-pentane solutions over a wide temperature range and in the low-temperature solid matrices of argon and nitrogen. Rotamers, formed due to rotation about the metal-carbon -bond, were found in solutions and matrices. A molecular mechanics calculation of1 proved the possibility of such rotation.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1952–1956, November, 1994.The authors are grateful to the Russian Foundation for Basic Research (project code No 93-03-18592) and to the International Science Foundation (project code No MEQ000). 相似文献
73.
《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2553-2557
Photolysis of 2-nitrobenzyl methyl ether in Ar and N2 matrices at 12 K generated an intermediate with λmax at 430 nm, and which was itself photolabile at 430–460 nm. Matrix IR spectra, as well as the UV-visible absorption, were obtained for this species. An analogous intermediate had previously been observed in flash-photolysis studies of 2-nitrobenzyl 4-cyanophenyl ether, and had been assigned an o-quinonoid structure on the basis of its kinetic behaviour and the position of its UV-visible absorption. In the matrix studies with 2-nitrobenzyl methyl ether, the IR spectra confirmed the o-quinonoid structure. 相似文献
74.
溶液成膜的温度对聚对苯二甲酸乙二酯结晶度的影响 总被引:1,自引:2,他引:1
<正> 用溶液成膜是制备聚合物薄膜的常用方法之一。但是溶液成膜的条件,如成膜温度,溶液浓度等对半结晶聚合物结晶度的影响研究报道较少。制备聚对苯二甲酸乙二酯(PET)非晶态薄膜通常使用熔融热压其后淬火的方法。由于PET在熔点附近易于降解,在薄膜中产生气泡,因而很难制备较大面积的均一厚度的薄膜,如在拉伸试验中所需 相似文献
75.
It was recently found that typical Chromatographic carrier gases such as argon or nitrogen could be used in a modified flame photometric detector for general or selective determination of eluted molecules. The detector was powered not by a flame but by a radioactively stimulated, mild discharge. The luminescence arose from the second positive system of nitrogen (in argon), and various emissions from aroyl-containing molecules (in nitrogen).This study describes experiments that take away not only the flame but also the discharge: The energy that produces the luminescence is derived solely from the beta decay of63Ni. Because of this low power input, the sensitivity of the present beta-driven photometric detector (-PD) is limited to about 25 ppm of nitrogen (in argon), and to about 5 pg/s for benzaldehyde and other well-responding aroyl compounds (in nitrogen). In accordance with mechanisms postulated earlier, other types of molecules do not produce significant responses in the absence of an electrical field.Material taken from doctoral thesis 相似文献
76.
Studies of the vibrational spectra of matrix-isolated M+NO
3
–
ion pairs have been extended to glassy aprotic solvents. The deuterated form of the solvents DMSO, THF, and ACN have windows through the 7- nitrate ionv
3(e) mode infrared region, so it was possible to clearly observe the splitting of the degeneracy of this mode,v
3, produced by the contacting, but solvated, alkali metal cation. Primary attention has been directed to the extent to which this splitting is reduced relative to the argon matrix values. This reduction, which reflects electron-density transfer from the solvating molecules to the ion pairs, is comparable to that observed for H2O and NH3 matrices as the splitting is reduced to 20–35% of the argon-matrix values. The extent of reduction ofv
3 for the different solvents has been related to Gutmann's donicity number scale with the correlation holding well for solvent molecules of comparable size, DMSO, THF and DMF, but breaking down for the smaller linear ACN, apparently because of more molecules in the cation solvation sphere. The matrix data have also been used, through comparison with spectra for saturated liquid solutions of Li+NO
3
–
, to show that the contact ion pair is the dominant species in liquid THF and ACN, whereas the ions are largely solvent separated in DMSO. 相似文献
77.
B. L. Tumanskii V. V. Bashilov N. N. Bubnov S. P. Solodovnikov V. I. Sokolov 《Russian Chemical Bulletin》1994,43(5):884-886
Using ESR spectroscopy, the reaction of P(O)(OPri)2 phosphoryl radicals with C60ML2 (M=Pd, Pt) was studied and the spin-adducts formed were shown to be unstable under the reaction conditions. The 5-addition of Pt(PPh3)4 to the dimer of phosphorylfullerenyl radicals results in metal-containing dimers (RO)2(O)PL2MC60-C60ML2P(O)(OR)2, which dissociate when exposed to visible light to afford C60ML2P(O)(OR)2 radicals; ML2 in these complexes is located in different positions in relation to the radical center. As a result, the ESR spectra contain the superposition of at least five signals of radicals that differ in HFS constants andg-factors.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 938–940, May, 1994.The present work was supported by the Russian Foundation for Basic Research (Projects 93-03-18725 and 93-03-4101). 相似文献
78.
The gas-phase electronic absorption spectra of (6-C6R6)2Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3dz2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO. 相似文献
79.
John F. Callan A. P. De Silva R. C. Mulrooney B. Mc Caughan 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):257-262
Summary This review highlights recent advances in the use of quantum dots (QD’s) as luminescent sensors. The bulk of the study concentrates
on systems that possess organic ligands bound to the surface of QD’s. These ligands vary from low molecular weight thiols
to larger molecules such as maltose binding protein. All have one thing in common: when a target analyte binds to the ligand/receptor,
a perturbation of the system occurs, that registers itself as a change in the luminescence intensity of the QD. Two main mechanisms
are prevalent in controlling the luminescent intensity in such systems. The first is Photoinduced Electron Transfer (PET)
and the second energy transfer. This review looks at current sensors that operate by using these mechanisms. Two component
systems are also investigated where a quencher is first added to a solution of the QD, followed by addition of the target
analyte that interacts with the quencher to influence the luminescence intensity. 相似文献
80.
Unicyclic Graphs with Minimal Energy 总被引:7,自引:0,他引:7
Yaoping Hou 《Journal of mathematical chemistry》2001,29(3):163-168
If G is a graph and 1,2,...,
n
are its eigenvalues, then the energy of G is defined as E(G)=|1|+|2|++|
n
|. Let S
n
3 be the graph obtained from the star graph with n vertices by adding an edge. In this paper we prove that S
n
3 is the unique minimal energy graph among all unicyclic graphs with n vertices (n6). 相似文献