全文获取类型
收费全文 | 5804篇 |
免费 | 125篇 |
国内免费 | 19篇 |
专业分类
化学 | 3697篇 |
晶体学 | 77篇 |
力学 | 232篇 |
数学 | 511篇 |
物理学 | 1431篇 |
出版年
2021年 | 34篇 |
2020年 | 43篇 |
2019年 | 46篇 |
2018年 | 47篇 |
2017年 | 27篇 |
2016年 | 89篇 |
2015年 | 99篇 |
2014年 | 77篇 |
2013年 | 276篇 |
2012年 | 225篇 |
2011年 | 258篇 |
2010年 | 149篇 |
2009年 | 125篇 |
2008年 | 221篇 |
2007年 | 234篇 |
2006年 | 251篇 |
2005年 | 224篇 |
2004年 | 190篇 |
2003年 | 171篇 |
2002年 | 190篇 |
2001年 | 132篇 |
2000年 | 124篇 |
1999年 | 90篇 |
1998年 | 85篇 |
1997年 | 125篇 |
1996年 | 124篇 |
1995年 | 95篇 |
1994年 | 112篇 |
1993年 | 133篇 |
1992年 | 119篇 |
1991年 | 72篇 |
1990年 | 66篇 |
1989年 | 98篇 |
1988年 | 85篇 |
1987年 | 79篇 |
1986年 | 78篇 |
1985年 | 93篇 |
1984年 | 102篇 |
1983年 | 78篇 |
1982年 | 78篇 |
1981年 | 79篇 |
1980年 | 70篇 |
1979年 | 72篇 |
1978年 | 69篇 |
1977年 | 69篇 |
1976年 | 57篇 |
1975年 | 79篇 |
1974年 | 72篇 |
1973年 | 59篇 |
1972年 | 31篇 |
排序方式: 共有5948条查询结果,搜索用时 171 毫秒
971.
Bondarenko L Hentschel S Greiving H Grunenberg J Hopf H Dix I Jones PG Ernst L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(14):3950-3963
A selection of pseudo-geminally substituted [2.2]paracyclophanes, the alkynes 6, 7, 10, 11 a, and 11 b and the alkenes 8 and 9 were prepared for the study of intraannular reactions between functional groups in direct juxtaposition. Whereas 9 and 10 provide the corresponding cyclobutane and cyclobutene derivatives on irradiation (12 and 13, respectively), the bis-alkynes 7 and 11 b do not lead to a cyclobutadiene intermediate. In the latter case the "half-closed" butadiene derivative 17 was isolated. A Paterno-Büchi reaction took place on irradiation of 8 and 6, although the oxetene intermediate 21 produced in the second example did not survive the reaction conditions (ring-opening to 22). Bromine addition to 9, 10, and 7 occurred with high stereoselectivity (formation of the dibromides 27, 30, and 33, respectively), and is rationalized by postulating the formation of the cationic intermediates 26, 29, and 32, respectively. To study the interaction of a carbocation with a facing triple bond, the alcohol 34 was prepared from 6. On acid treatment ring closure to the triply-bridged phane 38 took place, accompanied by the hydration of the triple bond to the ketoalcohol 37. In an interesting intraannular [2+3]cycloaddition reaction the bis-acetylene 11 a, on treatment with n-butyl lithium, provided the cyclopentadiene derivative 42. That the two triple bonds of a pseudo-geminal diacetylene can engage in a cyclization reaction leading to the cyclopentadienone complex 44 was also shown by treating 11 b with iron pentacarbonyl. 相似文献
972.
Martin AN Farquar GR Jones AD Frank M 《Rapid communications in mass spectrometry : RCM》2007,21(22):3561-3568
Single over-the-counter medication tablets were analyzed in real time using Single Particle Aerosol Mass Spectrometry (SPAMS). Dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles dislodged from a single tablet without destroying the shape or markings of each tablet. The solid tablet was placed in a modified-top glass vial and shaken to dislodge and introduce micrometer-sized particles into the SPAMS system. Unique spectra from these particles were obtained in less than 1 s for single tablets of aspirin, ibuprofen, pseudoephedrine, phenylephrine, loratadine, or diphenhydramine. The signals obtained allowed the non-destructive identification of an individual tablet in seconds. SPAMS presents an ideal system for high-throughput analysis of solid drugs. 相似文献
973.
A rabbit antibody immunoaffinity (IA) column procedure was evaluated as a cleanup method for the determination of atrazine in soil, sediment, and food. Four IA columns were prepared by immobilizing a polyclonal rabbit anti-atrazine antibody solution to HiTrap Sepharose columns. Atrazine was bound to the IA columns when the loading solvents were either 100% water, 2% acetonitrile in water, or 10% methanol in phosphate buffered saline (PBS). Quantitative removal of atrazine from the IA columns was achieved with elution solvents of either 70% ethanol in water, 70% methanol in water, or 100% methanol. One control column was prepared using nonspecific rabbit IgG antibody. This control column did not retain any applied atrazine indicating atrazine did not bind indiscriminately to protein or the Sepharose support. The four IA columns showed reproducible coupling efficiency for the immobilization of the atrazine antibody and consistent binding and releasing of atrazine. The coupling efficiency (4.25 mg of antibody in 1 mL of resin bed) for the four IA columns ranged from 93 to 97% with an average of 96 ± 2% (2.1%). Recoveries of the 500, 50, and 5 ng mL−1 atrazine standard solutions from the four IA columns were 107 ± 7% (6.5%), 122 ± 14% (12%), and 114 ± 9% (8.0%) respectively, based on enzyme-linked immunosorbent assay (ELISA) data. The maximum loading was approximately 700 ng of atrazine for each IA column (∼0.16 μg of atrazine per mg of antibody). The IA columns could withstand 100% methanol as the elution solvent and could be reused more than 50 times with no change in performance. The IA columns were challenged with soil, sediment, and duplicate-diet food samples and effectively removed interferences from these various matrices for subsequent gas chromatography/mass spectrometry (GC/MS) or ELISA analysis. The log-transformed ELISA and GC/MS data were significantly correlated for soil, sediment and food samples although the ELISA values were slightly higher than those obtained by GC/MS. The IA column cleanup procedure coupled with ELISA analysis could be used as an alternative effective analytical method for the determination of atrazine in complex sample media such as soil, sediment, and food samples. 相似文献
974.
The Mizoroki-Heck reaction is a palladium-catalyzed reaction of both practical importance and scientific significance. Two challenges currently faced by practitioners of the Heck and other palladium-catalyzed coupling reactions are (i) minimizing the costs associated with this reaction by developing high TON catalysts or facilitating catalyst recovery and (ii) elucidating the nature of the active species when using various different precatalysts. These two challenges, one practical and one fundamental, served as our motivation in our studies of immobilized molecular palladium(II) complexes as precatalysts in Mizoroki-Heck reactions. This Forum Article describes our investigations in this area, highlighting our approach to the elucidation of the active catalyst by combining kinetic and poisoning studies of several different related precatalysts, our development of new, selective catalyst poisons, and our quest for stable, recyclable supported Heck, Suzuki, and Sonogashira coupling catalysts. Under high-temperature conditions (120 degrees C), all precatalysts studied are conclusively shown to decompose, liberating soluble, active palladium(0) species that are the true catalysts. Techniques for the elucidation of the nature of the truly active Pd species are enumerated. 相似文献
975.
Possible modes of deactivation of Jacobsen's Co-salen catalyst during the hydrolytic kinetic resolution (HKR) of epichlorohydrin were explored by UV-vis spectroscopy, X-ray absorption spectroscopy, and electrospray ionization mass spectrometry, combined with recycling studies. Although an active Co(III)-salen catalyst deactivated substantially after multiple cycles without regeneration, the catalyst maintained its +3 oxidation state throughout the runs. Thus, deactivation of Co-salen during HKR was not the result of Co reduction. The mass spectrum of a deactivated material showed that catalyst dimerization does not account for the loss of activity. Results from various catalyst pretreatment tests, as well as from catalysts containing various counterions (acetate, tosylate, chloride, iodide) indicated that the rate of addition of the Co-salen counterions to epoxide forming Co-OH during the reaction correlated with deactivation. The extent of counterion addition to epoxide was influenced by the exposure time and the nucleophilicity of the counterion. An oligo(cyclooctene)-supported Co-OAc salen catalyst, which was 25 times more active than the standard Co-salen catalyst, was recycled multiple times with negligible deactivation. 相似文献
976.
Shaw R Laye RH Jones LF Low DM Talbot-Eeckelaers C Wei Q Milios CJ Teat S Helliwell M Raftery J Evangelisti M Affronte M Collison D Brechin EK McInnes EJ 《Inorganic chemistry》2007,46(12):4968-4978
We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe)18Cl6] (M=FeIII, CrIII) and [V14(L)6O6(OMe)18Cl6-xOx] (L=anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe14(C2H2N3)6O6(OMe)18Cl6], [Cr14(bta)6O6(OMe)18Cl6] (btaH=benzotriazole), [V14O6(Me2bta)6(OMe)18Cl6-xOx] [Me2btaH=5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-Cl}2+ and {VIV=O}2+] and for the distorted [FeIII14O9(OH)(OMe)8(bta)7(MeOH)5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S相似文献
977.
The interaction of EDTA with barium sulfate 总被引:1,自引:0,他引:1
Jones F Jones P Ogden MI Richmond WR Rohl AL Saunders M 《Journal of colloid and interface science》2007,316(2):553-561
Ethylenediaminetetraacetic acid (EDTA) is a known complexing agent that interacts with a host of cations. In this paper, various techniques are used to elucidate the mechanism of interaction between EDTA and barium sulfate surfaces. It is shown that complexation with metal ions is not sufficient to explain the inhibition of barite crystallization but that other processes such as chemisorption must also occur. EDTA is shown to always adsorb as the mono-protonated species - suggesting that the molecule is able to lose a proton when it adsorbs at lower pH. Molecular modelling shows that the interaction of the surface barium ions with the carboxylate group is an important one. Finally, in situ turbidity measurements provide information about the mechanism of nucleation/growth modification. It is found that the EDTA molecule inhibits barium sulfate nucleation and that this could be its primary means of inhibiting precipitation of barium sulfate. 相似文献
978.
Novak M Brinster AM Dickhoff JN Erb JM Jones MP Leopold SH Vollman AT Wang YT Glover SA 《The Journal of organic chemistry》2007,72(26):9954-9962
Quinol esters 2b, 2c, and 3b and sulfonamide 4c were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester 2b predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester 2c decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, 8, apparently by an SN1 mechanism. This is also a minor decomposition pathway for 2b, but the mechanism in that case is not likely to be SN1. Decomposition of 2c in the presence of N3- leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, 14, produced by N3--induced hydrolysis of 8, followed by a series of oxidations and nucleophilic additions by N3-. No products suggestive of N3--trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester 3b reacts with N3- to generate the two adducts 2-azido-4-isopropylphenol, 5b, and 3-azido-4-isopropylphenol, 11b. Although 5b is the expected product of N3- trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N3- with 3b. No oxenium ion is involved. The sulfonamide 4c predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, 17, and 2-azido-4-tert-butylphenol, 5c, in the presence of N3-. These products may indicate that 4c generates the oxenium ion 1c, but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that 1c has been produced. If 1c has been generated, the N3--trapping data indicate that it is a very short-lived and reactive species in H2O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of 1c is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of 1a-c are in the picosecond range. 相似文献
979.
Benkoski JJ Jones RL Douglas JF Karim A 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3530-3537
We present a novel platform, dubbed fossilized liquid assembly, for the creation of 2-D assemblies from nanoscale building blocks. The system consists of an oil/water interface in which the oil phase can be flash-cured upon UV exposure. The photopolymerizable material, 1,12-dodecanediol dimethacrylate, solidifies in as little as 1 s when exposed to UV light. The rapid cross-linking allows one to obtain a "snapshot" of the assembly process for particles that segregate to the oil/water interface. Among the particles investigated were nonpolar 0.39 microm poly(methyl methacrylate) latex spheres, nonpolar 10 microm polystyrene latex spheres, highly polarizable 5 nm Au nanocrystals, dipolar 10 nm CdTe quantum dots, and magnetic 25 nm magnetite nanoparticles. The aggregates formed by this process were typically either globular or fractal in appearance. By comparing with simulation, we can perform quantitative image analysis on the resulting micrographs to define a rigorous set of standards for distinguishing among the main classes of aggregation: flocculation, equilibrium phase separation, and true self-assembly. 相似文献
980.
Fabrication and thermal analysis of submicron silver tubes prepared from electrospun fiber templates
Submicron silver tubes have been synthesized by a polymer-based template approach. Two different approaches to metallization, electroless deposition and exchange plating, were evaluated within the template approach. Silver films with average thickness approximately 50-100 nm were deposited on polycarbonate fibers approximately 400 nm in diameter by each technique, resulting in tubes with a diameter between 450 and 500 nm after thermal degradation of core fibers. These nanomaterials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and scanning thermal microscopy. The thermal conductivity of the silver submicron tubes was found to differ depending on the method of preparation, with tubes from electroless plating possessing relative thermal conductivity values that were 1 order of magnitude higher than that from exchange plating, 3000 W/m x K and 660 W/m x K, respectively. Interestingly, these results indicate that silver submicron tubes possess higher thermal conductivity than the bulk metal. This observation is discussed in the context of the continuous conduction path of the tubes and their high surface area-to-volume ratio. 相似文献