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91.
Thiago G. Ramires Luiz R. Nakamura Ana J. Righetto Renan J. Carvalho Lucas A. Vieira Carlos A. B. Pereira 《Entropy (Basel, Switzerland)》2021,23(4)
This paper presents a discussion regarding regression models, especially those belonging to the location class. Our main motivation is that, with simple distributions having simple interpretations, in some cases, one gets better results than the ones obtained with overly complex distributions. For instance, with the reverse Gumbel (RG) distribution, it is possible to explain response variables by making use of the generalized additive models for location, scale, and shape (GAMLSS) framework, which allows the fitting of several parameters (characteristics) of the probabilistic distributions, like mean, mode, variance, and others. Three real data applications are used to compare several location models against the RG under the GAMLSS framework. The intention is to show that the use of a simple distribution (e.g., RG) based on a more sophisticated regression structure may be preferable than using a more complex location model. 相似文献
92.
Yee LD Craven JS Loza CL Schilling KA Ng NL Canagaratna MR Ziemann PJ Flagan RC Seinfeld JH 《The journal of physical chemistry. A》2012,116(24):6211-6230
The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes. 相似文献
93.
Ulusoy IS Scribano Y Benoit DM Tschetschetkin A Maurer N Koslowski B Ziemann P 《Physical chemistry chemical physics : PCCP》2011,13(2):612-618
Vibrational spectroscopy is a powerful tool to identify molecules and to characterise their chemical state. Inelastic electron tunnelling spectroscopy (IETS) combined with scanning tunnelling microscopy (STM) allows the application of vibrational analysis to a single molecule. Up to now, IETS was restricted to small species due to the complexity of vibration spectra for larger molecules. We extend the horizon of IETS for both experiment and theory by measuring the STM-IETS spectra of mercaptopyridine adsorbed on the (111) surface of gold and comparing it to theoretical spectra. Such complex spectra with more than 20 lines can be reliably determined and computed leading to completely new insights. Experimentally, the vibrational spectra exhibit a dependence on the specific adsorption site of the molecules. Theoretically, this dependence is only accessible if anharmonic contributions to the interaction potentials are included. These joint experimental and theoretical advances open new perspectives for structure determination of organic adlayers. 相似文献
94.
de Oliveira PR Viesser RV Guerrero PG Rittner R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(5):1599-1605
The analysis of concentration effects in the (1)H NMR data of cis-3-aminocyclohexanol (ACOL) showed that its diequatorial conformer changes from 60% at 0.01 mol L(-1) to 70% at 0.40 mol L(-1) in acetone-d(6). A similar increase was also observed for the diequatorial conformer of cis-3-N-methylaminocyclohexanol (MCOL), from 32% (CDCl(3) 0.01 mol L(-1)) to 55% (CDCl(3) 0.40 mol L(-1)). The increase in solvent basicity leads to a large stabilization effect for the diequatorial conformer of both compounds too. For ACOL, it changes from 47% (ΔG(eqeq-axax)=0.06 kcal mol(-1)) in CCl(4) to 93% (ΔG(eqeq-axax)=-1.53 kcal mol(-1)) in DMSO, while for MCOL it goes from 7% (ΔG(eqeq-axax)=1.54 kcal mol(-1)) in CCl(4) to 82% (ΔG(eqeq-axax)=-0.88 kcal mol(-1)) in pyridine-d(6). These results indicate that the intramolecular hydrogen bonds (IAHB) OH?N and NH?O stabilize the diaxial conformers of these compounds in a non-polar solvent. For cis-3-amino-1-methoxycyclohexane (ACNE) and cis-3-N-methylamino-1-methoxy-cyclohexane (MCNE) no changes were observed in equilibrium with the variation of solvent polarity. These results indicate for the first time that the IAHB NH?O is not strong enough to stabilize the diaxial conformer of these compounds and that the conformation equilibria of the cis isomers of compounds ACOL and MCOL are influenced only by the IAHB OH?N. Moreover, the presence of a secondary amino group (93% of diaxial conformer in CCl(4)) leads to an IAHB OH?N stronger than in primary and tertiary amino-derivatives (53 and 54% of diaxial conformer, respectively) for 1,3-disubstituted cyclohexanes. Values obtained from the theoretical data through the B3LYP functional are in agreement with the experimental results and indicate that the IAHB strength that influences the conformational equilibrium of these compounds is the IAHB OH?N. Thus, the IAHB NH?O do not stabilize the diaxial conformer of the cis isomer of compounds ACNE and MCNE showing that the diequatorial conformer will always be more stable than the diaxial conformer, independent of concentration or solvent. 相似文献
95.
96.
This study was designed to identify and quantify the carotenoids and phenolic compounds from annatto seeds using high performance liquid chromatography coupled to diode array and mass spectrometer detectors (HPLC-DAD-MS/MS). Furthermore, using response surface methodology, an optimized procedure for simultaneous extraction of these compounds was established. In addition to bixin, known to be the main carotenoid in annatto seeds, hypolaetin and a caffeoyl acid derivative were identified as the main phenolic compounds. The optimized procedure involved 15 extractions using acetone:methanol:water (50:40:10, v/v/v) as solvent, a solid-liquid ratio of 1:9 (m/v) and an extraction time of 5 min. Validation data indicated that the HPLC method proposed provided good linearity, sensitivity, procedure accuracy, system precision and suggested its suitability for the simultaneous analysis of phenolic compounds and carotenoids in annatto seeds. 相似文献
97.
98.
以2,6-二叔丁基-4-甲基苯酚(BHT)为自由基捕捉剂,研究了四(五氟化苯基)-六,七溴-卟啉氯化铁选择性催化氧化超临界丙烷为丙醇的反应机理.结果表明,添加少量的BHT能促进反应进行,过量的BHT则抑制反应进行.反应产物中除有丙基自由基外,还有异丙氧自由基及其他微量反应产物(如异己烷、正己烷、双丙基过氧化物)存在.超临界丙烷在催化剂的作用下形成更多的丙基自由基,进一步证明金属卟啉催化氧化超临界丙烷是链式自由基自氧化反应机理.对于其他微量反应产物如乙醇、乙酸和丙酸的存在,不能用链式自由基自氧化反应机理进行解释. 相似文献
99.
S. Gilb K. Hartl A. Kartouzian J. Peter U. Heiz H.-G. Boyen P. Ziemann 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(3):501-506
The optical properties of supported gold nanoparticles with sizes of 1.3 nm,
1.6 nm, 2.5 nm, and 2.9 nm have been studies by using cavity ring-down
spectroscopy in the photon energy range between 1.8 eV and 3.0 eV. The
obtained results show the possibility to obtain optical information of
nanoassembled materials with high sensitivity. The experimental findings are
compared to calculations using Mie-Drude theory. Whereas the broadening of
the surface plasmon resonance with decreasing size is well described by this
model, the observed blue-shift of the surface plasmon resonance contradicts
the predictions of the Mie-Drude theory. The latter effect can be explained
by the presence of a skin region with decreased polarizability typical for
coinage metal particles. Furthermore, it is found that the supported gold
nanoparticles are robust under ambient conditions, an important issue when
using these materials for optical applications. 相似文献
100.
Granular aluminium films were prepared by evaporation in an oxygen atmosphere. The oxygen content Co of the films was determined by Rutherford backscattering. The superconducting transition temperature Tc is measured as a function of the oxygen concentration. From the results the thickness of the oxide barriers is derived by applying a model of spherical granula. This model is confirmed by the observed linear dependence Tc α Co. 相似文献