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151.
Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions
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Dr. Wing Y. Man Dr. David Ellis Dr. Georgina M. Rosair Prof. Alan J. Welch 《Angewandte Chemie (International ed. in English)》2016,55(14):4596-4599
Two‐electron reduction of 1,1′‐bis(o‐carborane) followed by reaction with [Ru(η‐mes)Cl2]2 affords [8‐(1′‐1′,2′‐closo‐C2B10H11)‐4‐(η‐mes)‐4,1,8‐closo‐RuC2B10H11]. Subsequent two‐electron reduction of this species and treatment with [Ru(η‐arene)Cl2]2 results in the 14‐vertex/12‐vertex species [1‐(η‐mes)‐9‐(1′‐1′,2′‐closo‐C2B10H11)‐13‐(η‐arene)‐1,13,2,9‐closo‐Ru2C2B10H11] by direct electrophilic insertion, promoted by the carborane substituent in the 13‐vertex/12‐vertex precursor. When arene=mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in a process that makes the metal–ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of a series of previously reported 14‐vertex dicobaltacarboranes. 相似文献
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Delafuente DA Kosturko GW Graham PM Harman WH Myers WH Surendranath Y Klet RC Welch KD Trindle CO Sabat M Harman WD 《Journal of the American Chemical Society》2007,129(2):406-416
A series of pyridine complexes are prepared of the general form TpW(NO)(PMe3)(pyr) where pyr is either pyridine or a substituted pyridine. Depending on substitution pattern, the pyridine can be either N- or eta2-coordinated, and the role of the pyridine substituents and metal oxidation state in determining this equilibrium is explored. For eta2-pyridine complexes, the substituent pattern and solubility characteristics also determine the ratio of coordination diastereomers. Rates of both intra- and interfacial linkage isomerizations are explored along with the pyridine rotational barrier. This study is supported by DFT calculations and X-ray data and includes characterization of both eta2-pyridine and eta2-pyridinium complexes. 相似文献
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Standard reference materials for foods and dietary supplements 总被引:1,自引:0,他引:1
Sharpless KE Thomas JB Christopher SJ Greenberg RR Sander LC Schantz MM Welch MJ Wise SA 《Analytical and bioanalytical chemistry》2007,389(1):171-178
Well-characterized certified reference materials are needed by laboratories in the food testing, dietary supplement, and nutrition
communities to facilitate compliance with labeling laws and improve the accuracy of information provided on product labels,
so that consumers can make good choices. As a result of the enactment of the Nutrition Labeling and Education Act of 1990
and the Infant Formula Act of 1980, the National Institute of Standards and Technology (NIST) worked to develop a series of
food-matrix standard reference materials (SRMs) characterized for nutrient concentrations. These include SRM 1544 Fatty Acids
and Cholesterol in a Frozen Diet Composite, SRM 1546 Meat Homogenate, SRM 1548a Typical Diet, SRM 1566b Oyster Tissue, SRM
1846 Infant Formula, SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue, SRM 2383 Baby Food Composite,
SRM 2384 Baking Chocolate, SRM 2385 Slurried Spinach, and SRM 2387 Peanut Butter. With the enactment of the Dietary Supplement
Health and Education Act of 1994, NIST has been working to develop suites of dietary supplement SRMs characterized for active
and marker compounds and for toxic elements and pesticides, where appropriate. An updated SRM 1588b Organics in Cod Liver
Oil, a suite of ephedra-containing materials (SRMs 3240–3245), a carrot extract in oil (SRM 3276), and a suite of ginkgo-containing
materials (SRMs 3246–3248) are available. Several other materials are currently in preparation. Dietary supplements are sometimes
provided in forms that are food-like; for these, values may also be assigned for nutrients, for example SRM 3244 Ephedra-Containing
Protein Powder. Both the food-matrix and dietary supplement reference materials are intended primarily for validation of analytical
methods. They may also be used as “primary control materials” in assignment of values to in-house (secondary) control materials
to confirm accuracy and to establish measurement traceability to NIST. 相似文献
160.
Haskins RW Maier RS Ebeling RM Marsh CP Majure DL Bednar AJ Welch CR Barker BC Wu DT 《The Journal of chemical physics》2007,127(7):074708
We performed tight-binding molecular dynamics on single-walled carbon nanotubes with and without a variety of defects to study their effect on the nanotube modulus and failure through bond rupture. For a pristine (5,5) nanotube, Young's modulus was calculated to be approximately 1.1 TPa, and brittle rupture occurred at a strain of 17% under quasistatic loading. The predicted modulus is consistent with values from experimentally derived thermal vibration and pull test measurements. The defects studied consist of moving or removing one or two carbon atoms, and correspond to a 1.4% defect density. The occurrence of a Stone-Wales defect does not significantly affect Young's modulus, but failure occurs at 15% strain. The occurrence of a pair of separated vacancy defects lowers Young's modulus by approximately 160 GPa and the critical or rupture strain to 13%. These defects apparently act independently, since one of these defects alone was independently determined to lower Young's modulus by approximately 90 GPa, also with a critical strain of 13%. When the pair of vacancy defects adjacent, however, Young's modulus is lowered by only approximately 100 GPa, but with a lower critical strain of 11%. In all cases, there is noticeable strain softening, for instance, leading to an approximately 250 GPa drop in the apparent secant modulus at 10% strain. When a chiral (10,5) nanotube with a vacancy defect was subjected to tensile strain, failure occurred through a continuous spiral-tearing mechanism that maintained a high level of stress (2.5 GPa) even as the nanotube unraveled. Since the statistical likelihood of defects occurring near each other increases with nanotube length, these studies may have important implications for interpreting the experimental distribution of moduli and critical strains. 相似文献