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Philip M. Keil Ademola Soyemi Kilian Weisser Prof. Tibor Szilvási Prof. Christian Limberg Dr. Terrance J. Hadlington 《Angewandte Chemie (International ed. in English)》2023,62(19):e202381961
The open-shell cationic stannylene-iron(0) complex 4 ( 4 =[PhiPDippSn⋅Fe⋅IPr]+; PhiPDipp={[Ph2PCH2Si(iPr)2](Dipp)N}; Dipp=2,6-iPr2C6H3; IPr=[(Dipp)NC(H)]2C:) cooperatively and reversibly cleaves dihydrogen at the Sn−Fe interface under mild conditions (1.5 bar, 298 K), in forming bridging hydrido-complex 6 . The One-electron oreduction of the related GeII−Fe0 complex 3 leads to oxidative addition of one C−P linkage of the PhiPDipp ligand in an intermediary Fe−I complex, leading to FeI phosphide species 7 . One-electron reduction reaction of 4 gives access to the iron(−I) ferrato-stannylene, 8 , giving evidence for the transient formation of such a species in the reduction of 3 . The covalently bound tin(II)-iron(−I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe−I in this unique d9-iron complex. 相似文献
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We have demonstrated simultaneous correction for the optical interference of skin and fat in tissue spectra by using a two-distance fiber-optic probe. We obtained the correction by orthogonalizing the spectra collected at a long source-detector distance (SD) to the spectra collected at a short SD and mapped to the long SD space. The method was validated in tissuelike three-layer phantoms as well as preliminarily in human tissue. After the correction, a partial-least-squares model of the phantoms showed enhanced prediction performance. 相似文献
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M. L. Myrick O. Soyemi H. Li L. Zhang D. Eastwood 《Analytical and bioanalytical chemistry》2001,369(3-4):351-355
Recent reports from our laboratory have described a method for all-optical multivariate chemometric prediction from optical
spectroscopy. The concept behind this optical approach is that a spectral pattern (a regression vector) can be encoded into
the spectrum of an optical filter. The key element of these measurement schemes is the multivariate optical element (MOE),
a multiwavelength interference-based spectral discriminator that is tied to the regression vector of a particular measurement.
The fabrication of these MOEs is a complex operation that requires precise techniques. However, to date, no quantitative means
of determining the allowable design/ manufacturing errors for MOEs has existed. The purpose of the present report is to show
how the spectroscopy of a sample is used to define the accuracy with which MOEs must be designed and manufactured. We conclude
this report with a general treatment of spectral tolerance and a worked example. The worked example is based on actual experimental
measurements. We show how the spectral bandpass is defined operationally in a real problem, and how the statistics of the
theoretical regression vector influence both the bandpass and the minimum tolerances. In the experimental example, we demonstrate
that tolerances range continuously between 1 (totally tolerant) to approximately 10–3 (0.1% T) in this problem.
Received: 21 August 2000 / Revised: 30 October 2000 / Accepted: 4 November 2000 相似文献
4.
Myrick ML Soyemi O Li H Zhang L Eastwood D 《Fresenius' Journal of Analytical Chemistry》2001,369(3-4):351-355
Recent reports from our laboratory have described a method for all-optical multivariate chemometric prediction from optical spectroscopy. The concept behind this optical approach is that a spectral pattern (a regression vector) can be encoded into the spectrum of an optical filter. The key element of these measurement schemes is the multivariate optical element (MOE), a multiwavelength interference-based spectral discriminator that is tied to the regression vector of a particular measurement. The fabrication of these MOEs is a complex operation that requires precise techniques. However, to date, no quantitative means of determining the allowable design/ manufacturing errors for MOEs has existed. The purpose of the present report is to show how the spectroscopy of a sample is used to define the accuracy with which MOEs must be designed and manufactured. We conclude this report with a general treatment of spectral tolerance and a worked example. The worked example is based on actual experimental measurements. We show how the spectral bandpass is defined operationally in a real problem, and how the statistics of the theoretical regression vector influence both the bandpass and the minimum tolerances. In the experimental example, we demonstrate that tolerances range continuously between 1 (totally tolerant) to approximately 10(-3) (0.1% T) in this problem. 相似文献
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Soyemi OO Busch MA Busch KW 《Journal of chemical information and computer sciences》2000,40(5):1093-1100
"Real-time" chemometrics as envisioned by the union of instrument control, data acquisition, and chemometric analysis with a single software platform can provide substantial benefits to manufacturing concerns that require process control. Some of these benefits include faster generation of information and improved quality control. This paper describes a series of chemometric routines written in LabVIEW and demonstrates their use in predicting six properties of diesel fuel. In particular, near-infrared spectral data were used to predict the boiling point at 50% recovery, cetane number, density, freezing temperature, total aromatics, and viscosity for a series of diesel fuels. 相似文献
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Iterative target transformation factor analysis (ITTFA) was used to determine the spectra of the individual species generated during the oxidative p-doping of films of poly(para-phenyleneethynylene) (PPE). UV-visible spectra of PPE films on transparent electrodes were obtained in-situ during an anodic sweep. ITTFA identified 4 species present during the oxidation, which we assign as neutral polymer, polaron species, bipolaron species, and a species formed by further bipolaron reaction. The region of electrochemical stability for each of these species was identified and their potential-dependent profiles were obtained. This work is the first deconvolution of conjugated polymer spectroelectrochemistry. 相似文献
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