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21.
Terhi Oja Petri Tähtinen Nadine Dreiack Pekka Mäntsälä Jarmo Niemi Mikko Metsä-Ketelä Karel D. Klika 《Tetrahedron: Asymmetry》2012,23(9):670-682
Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of 1H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties. 相似文献
22.
Esa Kokko Anneli Malmberg Petri Lehmus Barbro Lfgren Jukka V. Seppl 《Journal of polymer science. Part A, Polymer chemistry》2000,38(2):376-388
A study was made on the effects of polymerization conditions on the long‐chain branching, molecular weight, and end‐group types of polyethene produced with the metallocene‐catalyst systems Et[Ind]2ZrCl2/MAO, Et[IndH4]2ZrCl2/MAO, and (n‐BuCp)2ZrCl2/MAO. Long‐chain branching in the polyethenes, as measured by dynamic rheometry, depended heavily on the catalyst and polymerization conditions. In a semibatch flow reactor, the level of branching in the polyethenes produced with Et[Ind]2ZrCl2/MAO increased as the ethene concentration decreased or the polymerization time increased. The introduction of hydrogen or comonomer suppressed branching. Under similar polymerization conditions, the two other catalyst systems, (n‐BuCp)2ZrCl2/MAO and Et[IndH4]2ZrCl2/MAO, produced linear or only slightly branched polyethene. On the basis of an end‐group analysis by FTIR and molecular weight analysis by GPC, we concluded that a chain transfer to ethene was the prevailing termination mechanism with Et[Ind]2ZrCl2/MAO at 80 °C in toluene. For the other catalyst systems, β‐H elimination dominated at low ethene concentrations. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 376–388, 2000 相似文献
23.
Isoniemi E Khriachtchev L Makkonen M Räsänen M 《The journal of physical chemistry. A》2006,110(40):11479-11487
Photolysis (193 nm) of propiolic acid (HCCCOOH) was studied with Fourier transform infrared spectroscopy in noble-gas (Ar, Kr, and Xe) solid matrixes. The photolysis products were assigned using ab initio quantum chemistry calculations. The novel higher-energy conformer of propiolic acid was efficiently formed upon UV irradiation, and it decayed back to the ground-state conformer on a time scale of approximately 10 min by tunneling of the hydrogen atom through the torsional energy barrier. In addition, the photolysis produced a number of matrix-isolated 1:1 molecular complexes such as HCCH...CO2, HCCOH...CO, and H2O...C3O. The HCCH...CO2 complex dominated among the photolysis products, and the computations suggested a parallel geometry of this complex characterized by an interaction energy of -9.6 kJ/mol. The HCCOH...CO complex also formed efficiently, but its concentration was strongly limited by its light-induced decomposition. In this complex, the most probable geometry was found to feature the interaction of carbon monoxide with the OH group via the carbon atom, and the computational interaction energy was determined to be -18.3 kJ/mol. The formation of the strong H2O...C3O complex (interaction energy -21 kJ/mol) was less efficient, which might be due to the inefficiency of the involved radical reaction. 相似文献
24.
Direct Photocatalysis for Organic Synthesis by Using Plasmonic‐Metal Nanoparticles Irradiated with Visible Light 下载免费PDF全文
Recent advances in direct‐use plasmonic‐metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible‐light irradiation have attracted great interest. Plasmonic‐metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic‐metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light‐excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic‐metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation. 相似文献
25.
C. E. Nwankire V. J. Law A. Nindrayog B. Twomey K. Niemi V. Milosavljević W. G. Graham D. P. Dowling 《Plasma Chemistry and Plasma Processing》2010,30(5):537-552
Plasma diagnostics of atmospheric plasmas is a key tool in helping to understand processing performance issues. This paper
presents an electrical, optical and thermographic imaging study of the PlasmaStream atmospheric plasma jet system. The system
was found to exhibit three operating modes; one constricted/localized plasma and two extended volume plasmas. At low power
and helium flows the plasma is localized at the electrodes and has the electrical properties of a corona/filamentary discharge
with electrical chaotic temporal structure. With increasing discharge power and helium flow the plasma expands into the volume
of the tube, becoming regular and homogeneous in appearance. Emission spectra show evidence of atomic oxygen, nitric oxide
and the hydroxyl radical production. Plasma activated gas temperature deduced from the rotational temperature of nitrogen
molecules was found to be of order of 400 K: whereas thermographic imaging of the quartz tube yielded surface temperatures
between 319 and 347 K. 相似文献
26.
We present a new graded-index photonic crystal (GRIN PhC) structure which can be made by laser interference lithography (LIL). It can be applied as miniaturized focusing lens. Numerical simulations are carried out on the structures with different widths, lengths, and modulations. In the qualitative analysis of the focal length, focusing of a GRIN PhC was proved to originate from both the graded sizes of the rods and multimode interference. Multimode interference dominates the focusing effect when a GRIN PhC has a small length or a small difference in the rod sizes. Intensity distributions in different cases were given to support the conclusion. 相似文献
27.
We point out the need for Behavioral Operational Research (BOR) in advancing the practice of OR. So far, in OR behavioral phenomena have been acknowledged only in behavioral decision theory but behavioral issues are always present when supporting human problem solving by modeling. Behavioral effects can relate to the group interaction and communication when facilitating with OR models as well as to the possibility of procedural mistakes and cognitive biases. As an illustrative example we use well known system dynamics studies related to the understanding of accumulation. We show that one gets completely opposite results depending on the way the phenomenon is described and how the questions are phrased and graphs used. The results suggest that OR processes are highly sensitive to various behavioral effects. As a result, we need to pay attention to the way we communicate about models as they are being increasingly used in addressing important problems like climate change. 相似文献
28.
We investigate the influence of a temperature-dependent shear viscosity over entropy density ratio η/s on the transverse momentum spectra and elliptic flow of hadrons in ultrarelativistic heavy-ion collisions. We find that the elliptic flow in √S(NN)=200 GeV Au+Au collisions at RHIC is dominated by the viscosity in the hadronic phase and in the phase transition region, but largely insensitive to the viscosity of the quark-gluon plasma (QGP). At the highest LHC energy, the elliptic flow becomes sensitive to the QGP viscosity and insensitive to the hadronic viscosity. 相似文献
29.
We analyze a field experiment where ambient air is injected into the soil during the summer and extracted again during the winter. A multiphase model accounting for the conductive transport as well as the convective transport with the moving liquid and gas phases is used along with a more simplified single-phase model where the convective transport is due to the gas alone. The latter model also accounts for subzero wintertime temperatures. The multiphase model captures well both the seasonal variations and the actual test sequence, the main calibration being in the adjustment of medium permeabilities based on the observed pressure responses. The effect of the injection pump on the temperature and humidity of the injection air needs to be known accurately. Taking into account the humidity of the injection air explicitly instead of using humidity-corrected enthalpy values also has an effect. The effect of various humidity and specific enthalpy assumptions is of the order of 1–1.5°C, while ignoring the wintertime subzero temperatures has an effect of 1–2°C. These differences are of the same order of magnitude as the heterogeneity-introduced differences in field data. Using the simplified single-phase model typically appears to cause a difference of 1–2°C, but can yield an even higher deviation of the order of 3–4°C. 相似文献
30.
The C(21)-C(40) fragment of fibrinogen receptor inhibitor tetrafibricin was prepared in 12 steps from propane diol (longest linear sequence). In this approach, 6 C-C bonds are formed via asymmetric iridium catalyzed transfer hydrogenative carbonyl allylation and 2 C═C bonds are formed via Grubbs olefin cross-metathesis. 相似文献