全文获取类型
收费全文 | 245篇 |
免费 | 6篇 |
专业分类
化学 | 158篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 25篇 |
物理学 | 64篇 |
出版年
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 5篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2015年 | 3篇 |
2014年 | 4篇 |
2013年 | 10篇 |
2012年 | 9篇 |
2011年 | 9篇 |
2010年 | 2篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 12篇 |
2006年 | 12篇 |
2005年 | 8篇 |
2004年 | 11篇 |
2003年 | 6篇 |
2002年 | 2篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 12篇 |
1993年 | 4篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 7篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1965年 | 2篇 |
1964年 | 3篇 |
1963年 | 3篇 |
1932年 | 2篇 |
1928年 | 1篇 |
1914年 | 1篇 |
排序方式: 共有251条查询结果,搜索用时 15 毫秒
91.
Goodwin JA Coor JL Kavanagh DF Sabbagh M Howard JW Adamec JR Parmley DJ Tarsis EM Kurtikyan TS Hovhannisyan AA Desrochers PJ Standard JM 《Inorganic chemistry》2008,47(17):7852-7862
Complexes of the (nitro)( meso-tetrakis(2- N-methylpyridyl)porphyinato)cobalt(III) cation, [LCoTMpyP(2)(NO 2)] (4+), in which L = water or ethanol have been immobilized through ionic attraction within Nafion films (Naf). These immobilized six-coordinate species, [LCoTMPyP(2)(NO 2)/Naf], have been found to catalyze the oxidation of triphenylphosphine in ethanol solution by dioxygen, therefore retaining the capacity to activate dioxygen catalytically without an additional reducing agent as was previously observed in nonaqueous solution for the non-ionic (nitro)cobalt porphyrin analogs. Heating these immobilized six-coordinate species under vacuum conditions results in the formation of the five-coordinate nitro derivatives, [CoTMPyP(2)(NO 2)/Naf] at 85 degrees C and [CoTMPyP(2)/Naf] at 110 degrees C. The catalytic oxidation of gas-phase cyclohexene with O 2 is supported only by the resulting immobilized five-coordinate nitro complex as was previously seen with the corresponding solution-phase catalyst in dichloromethane solution. The simultaneous catalytic oxidation of triphenylphosphine and cyclohexene with O 2 in the presence of the Nafion-bound six-coordinate ethanol nitro complex is also observed; however, this process is not seen for the CoTPP derivative in dichloromethane solution. The oxidation reactions do not occur with unmodified Nafion film or with Nafion-supported [BrCo(III)TmpyP]/Naf or [Co(II)TmpyP]/Naf, indicating the necessity for the nitro/nitrosyl ligand in the oxidation mechanism. The existence of a second reactive intermediate is indicated because the two simultaneous oxidation reactions depend on two distinct oxygen atom-transfer steps having different reactivity. The absence of homogeneous cyclohexene oxidation by the six-coordinate (H 2O)CoTPP(NO 2) derivatives in the presence of Ph 3P and O 2 in dichloromethane solution indicates that the second reactive intermediate is lost by an unidentified route only in solution, implying that the immobilization of it in Nafion allows it to react with cyclohexene. Although direct observation of this species has not been achieved, a comparitive DFT study of likely intermediates in several catalytic oxidation mechanisms at the BP 6-31G* level supports the possibility that this intermediate is a peroxynitro species on the basis of relative thermodynamic accessibility. The alternate intermediates evaluated include the reduced cobalt(II) porphyrin, the dioxygen adduct cobalt(III)-O 2 (-), the oxidized cobalt(II) pi-cation radical, and the nitrito complex, cobalt(III)-ONO. 相似文献
92.
Rybolt TR Wells CE Thomas HE Goodwin CM Blakely JL Turner JD 《Journal of colloid and interface science》2008,325(1):282-286
Gas-solid chromatography was used to determine B(2s) (gas-solid virial coefficient) values for 12 alkanes (10 branched and 2 cyclic) interacting with a carbon powder (Carbopack B, Supelco). B(2s) values were determined by multiple size variant injections within the temperature range of 393 to 623 K with each alkane measured at 5 or 6 different temperatures. The temperature variations of the gas-solid virial coefficients were used to find the experimental adsorption energy or binding energy values (E( *)) for each alkane. A molecular mechanics based, rough-surface model was used to calculate the molecule-surface binding energy (E(cal)( *)) using augmented MM2 parameters. The surface model consisted of three parallel graphene layers with each layer containing 127 interconnected benzene rings and two separated nanostructures each containing 17 benzene rings arranged in a linear strip. As the parallel nanostructures are moved closer together, the surface roughness increases and molecule-surface interactions are enhanced. A comparison of the experimental and calculated binding energies showed excellent agreement with an average difference of 3.8%. Linear regressions of E( *) versus E(cal)( *) for the current data set and a combined current and prior alkane data set both gave excellent correlations. For the combined data set with 18 linear, branched and cyclic alkanes; a linear regression of E( *)=0.9848E(cal)( *) and r(2)=0.976 was obtained. The results indicate that alkane-surface binding energies may be calculated from MM2 parameters for some gas-solid systems. 相似文献
93.
Low-temperature interaction of nitrogen base ligands with layered Co(TTP)(NO) (TTP = meso-tetratolylporphyrinato dianion) as well as its toluene solution leads to the formation of the first six-coordinate species of the general formula (B)Co(TTP)(NO) (where B = piperidine and pyridine). The nu(NO) stretching bands of these species appear at lower frequencies compared with the five-coordinate nitrosyl derivative and depend on the nature of the trans axial ligand. The equilibrium constants and enthalpies of formation of these new species are determined. Fairly stable at low-temperature conditions in the solid state, they slowly dissociate the nitrogen base ligands upon warming to restore the five-coordinate nitrosyl complex Co(TTP)(NO). 相似文献
94.
Ultra-performance liquid chromatography (UPLC) combined with mass spectrometric detection (MS) is used successfully in the bioanalysis of small molecule drug candidates in plasma. UPLC-MS is shown to increase sample throughput by reducing run times over 3-fold, without compromising analytical sensitivity or analyte resolution. The technique is demonstrated to be practical and robust on a commercially available ultra-high pressure system when injecting extracts of plasma and has also shown to be a technique that can be used effectively on a conventional high-performance liquid chromatography system fitted with short columns (相似文献
95.
Conrad A. P. Goodwin Fabrizio Ortu Daniel Reta 《International journal of quantum chemistry》2020,120(14):e26248
The fluid synergy between experimentalists and theoreticians has, for decades, led to a deeper understanding of the processes that govern single-molecule magnets. This approach has allowed for the establishment of proven design criteria for the control of magnetic properties through molecular architecture and the development of new magnetic measurement techniques and innovative computational methodologies. Here, we give an account of the experimental and theoretical joint endeavor carried out as part of the synthesis group led by David Mills and the computational/theoretical team led by Nicholas Chilton, together with colleagues in synthetic f-element chemistry and magnetism at the University of Manchester. In addition, we provide a personal perspective on collaborative work in molecular magnetism and how such collaborations are essential for advancing the field further. 相似文献
96.
Milman G Barnes AJ Schwope DM Schwilke EW Goodwin RS Kelly DL Gorelick DA Huestis MA 《Analytical and bioanalytical chemistry》2011,401(2):599-607
Oral fluid (OF) is an increasingly accepted matrix for drug testing programs, but questions remain about its usefulness for
monitoring cannabinoids. Expectorated OF specimens (n = 360) were obtained from 10 adult daily cannabis smokers before, during, and after 37 20-mg oral Δ9-tetrahydrocannabinol (THC) doses over 9 days to characterize cannabinoid disposition in this matrix. Specimens were extracted
and analyzed by gas chromatography–mass spectrometry with electron-impact ionization for THC, 11-hydroxy-THC, cannabidiol,
and cannabinol, and negative chemical ionization for 11-nor-9-carboxy-THC (THCCOOH). Linear ranges for THC, 11-hydroxy-THC,
and cannabidiol were 0.25–50 ng/mL; cannabinol 1–50 ng/mL; and THCCOOH 5–500 pg/mL. THCCOOH was the most prevalent analyte
in 344 specimens (96.9%), with concentrations up to 1,390.3 pg/mL. 11-hydroxy-THC, cannabidiol, and cannabinol were detected
in 1, 1, and 3 specimens, respectively. THC was detected in only 13.8% of specimens. The highest THC concentrations were obtained
at admission (median 1.4 ng/mL, range 0.3–113.6) from previously self-administered smoked cannabis. A total of 2.5 and 3.7%
of specimens were THC-positive at the recommended Substance Abuse and Mental Health Services Administration (2 ng/mL) and
Driving Under the Influence of Drugs, Alcohol and Medicines (DRUID) (1 ng/mL) confirmation cutoffs, respectively. THC is currently
the only analyte for monitoring cannabis exposure in OF; however, these data indicate chronic therapeutic oral THC administration
and illicit oral THC use are unlikely to be identified with current guidelines. Measurement of THCCOOH may improve the detection
and interpretation of OF cannabinoid tests and minimize the possibility of OF contamination from passive inhalation of cannabis
smoke. 相似文献
97.
98.
Ciucci F Chueh WC Goodwin DG Haile SM 《Physical chemistry chemical physics : PCCP》2011,13(6):2121-2135
A two-dimensional, small-bias model has been developed for describing transport through a mixed ionic and electronic conductor (MIEC) with electrochemically-active surfaces, a system of particular relevance to solid oxide fuel cells. Utilizing the h-adaptive finite-element method, we solve the electrochemical potential and flux for both ionic and electronic species in the MIEC, taking the transport properties of Sm(0.15)Ce(0.85)O(1.925-δ) (SDC15). In addition to the ionic flux that flows between the two sides of the cell, there are two types of electronic fluxes: (1) cross-plane current that flows in the same general direction as the ionic current, and (2) in-plane current that flows between the catalytically-active MIEC surface and the metal current collectors. From an evaluation of these fluxes, the macroscopic interfacial resistance is decomposed into an electrochemical reaction resistance and an electron diffusion-drift resistance, the latter associated with the in-plane electronic current. Analysis of the experimental data for the interfacial resistance for hydrogen electro-oxidation on SDC15 having either Pt or Au current collectors (W. Lai and S. M. Haile, J. Am. Ceram. Soc., 2005, 88, 2979-2997; W. C. Chueh, W. Lai and S. M. Haile, Solid State Ionics, 2008, 179, 1036-1041) indicates that surface reaction rather than electron migration is the overall rate-limiting step, and suggests furthermore that the surface reaction rate, which has not been directly measured in the literature, scales with pO2(-1/4). The penetration depth for the in-plane electronic current is estimated at 0.6 μm for the experimental conditions of interest to SDC15, and is found to attain a value as high as 4 μm within the broader range of computational conditions. 相似文献
99.
Forensic DNA profiling uses a series of commercial kits that co‐amplify several loci in one reaction; the products of the PCR are fluorescently labelled and analysed using CE. Before CE, an aliquot of the PCR is mixed with formamide and an internal lane size standard. Using the SGM Plus amplification kit, we have developed two internal non‐amplified controls of 80 bp and 380 bp that are labelled with ROX fluorescent dye and added to the PCR. Combined with two internal amplification controls of 90 bp and 410 bp, they provide additional controls for the PCR, electrokinetic injection, and CE and also function as an internal size standard. 相似文献
100.
A highest weight theory for a finite W-algebra $U(\mathfrak{g},e)$ was developed in Brundan et al. (Int. Math. Res. Not. 15:rnn051, 2008). This leads to a strategy for classifying the irreducible finite dimensional $U(\mathfrak{g},e)$ -modules. The highest weight theory depends on the choice of a parabolic subalgebra of $\mathfrak{g}$ leading to different parameterizations of the finite dimensional irreducible $U(\mathfrak{g},e)$ -modules. We explain how to construct an isomorphism preserving bijection between the parameterizing sets for different choices of parabolic subalgebra when $\mathfrak{g}$ is of type A, or when $\mathfrak{g}$ is of types C or D and e is an even multiplicity nilpotent element. 相似文献