全文获取类型
收费全文 | 86711篇 |
免费 | 6741篇 |
国内免费 | 11514篇 |
专业分类
化学 | 70871篇 |
晶体学 | 1965篇 |
力学 | 1314篇 |
综合类 | 961篇 |
数学 | 9284篇 |
物理学 | 20571篇 |
出版年
2023年 | 996篇 |
2022年 | 1113篇 |
2021年 | 2284篇 |
2020年 | 2179篇 |
2019年 | 3179篇 |
2018年 | 2038篇 |
2017年 | 3125篇 |
2016年 | 2747篇 |
2015年 | 2616篇 |
2014年 | 3473篇 |
2013年 | 6559篇 |
2012年 | 4750篇 |
2011年 | 5262篇 |
2010年 | 4364篇 |
2009年 | 5310篇 |
2008年 | 5637篇 |
2007年 | 5916篇 |
2006年 | 5099篇 |
2005年 | 4170篇 |
2004年 | 4031篇 |
2003年 | 3492篇 |
2002年 | 5551篇 |
2001年 | 2386篇 |
2000年 | 2025篇 |
1999年 | 1571篇 |
1998年 | 1392篇 |
1997年 | 1305篇 |
1996年 | 1238篇 |
1995年 | 1250篇 |
1994年 | 1075篇 |
1993年 | 1011篇 |
1992年 | 931篇 |
1991年 | 656篇 |
1990年 | 478篇 |
1989年 | 427篇 |
1988年 | 425篇 |
1987年 | 301篇 |
1986年 | 307篇 |
1985年 | 413篇 |
1984年 | 300篇 |
1983年 | 179篇 |
1982年 | 360篇 |
1981年 | 533篇 |
1980年 | 479篇 |
1979年 | 523篇 |
1978年 | 405篇 |
1977年 | 306篇 |
1976年 | 269篇 |
1974年 | 93篇 |
1973年 | 171篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
71.
Joachim Loup Uttam Dhawa Fabio Pesciaioli Joanna Wencel‐Delord Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2019,58(37):12803-12818
Molecular syntheses largely rely on time‐ and labour‐intensive prefunctionalization strategies. In contrast, C?H activation represents an increasingly powerful approach that avoids lengthy syntheses of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, and crop protection, among others. The enantioselective functionalization of omnipresent C?H bonds has emerged as a transformative tool for the step‐ and atom‐economical generation of chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium and rhodium catalysts. Indeed, despite significant achievements, the use of inexpensive and sustainable 3d metals in asymmetric C?H activations is still clearly in its infancy. Herein, we discuss the remarkable recent progress in enantioselective transformations via organometallic C?H activation by 3d base metals up to April 2019. 相似文献
72.
An efficient and practical route to β‐keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM‐41‐supported Schiff base‐pyridine bidentate copper (II) complex [MCM‐41‐Sb,Py‐Cu (OAc)2] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β‐keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)2. MCM‐41‐Sb,Py‐Cu (OAc)2 is also easy to recover and is recyclable up to eight times with almost consistent activity. 相似文献
73.
We present novel inorganic–organic hybrid catalyst to accomplish domino multi‐component reaction (MCR) for synthesis of 3‐amino‐2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐carbonitrile/carboxylate derivatives. This methodology offers remarkable development by easy production of H3PMo12O40/Hyd‐SBA‐15 in regard to solving the problem of using harsh catalysts, also it demonstrates to be impressive and environmentally friendly in term of low reaction times and high yields. 相似文献
74.
Deliang Kong Lihua Guo Meng Tian Shumiao Zhang Zhenzhen Tian Huayun Yang Ye Tian Zhe Liu 《应用有机金属化学》2019,33(1)
Fifteen organometallic Ir(III) half‐sandwich complexes ( 1A – 5C ) having the general formula [(η5‐Cpx)Ir(N^N)Cl]PF6 (Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph) or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph); N^N = diamine) have been synthesized and characterized. The molecular structure of 1A was determined using single‐crystal X‐ray diffraction analysis. The hydrolysis of 1A – 5C was monitored using UV–visible spectra. Complexes 3A – 3C showed catalytic activity for the oxidation of NADH to NAD+, where 3C showed the highest turnover number of 29.9 within 450 min. Cytotoxicity examination by MTT assay was carried out against two human cancer cell lines (HeLa and A549) after 24 or 48 h drug treatment. The complexes showed high potency, where the most potent complex ( 3C ; IC50 = 3.4 μM) was six times more active than cisplatin against A549 cells after 24 h drug exposure. Cytotoxic potency towards A549 cells increased with phenyl substitution on Cp ring: Cpxbiph > Cpxph > Cp*. In addition, the biological studies showed that 3C caused cell apoptosis and cell cycle arrest at G1 phase in A549 cancer cells. Moreover, 3C increased the level of reactive oxygen species markedly after 24 h, which may provide an important basis for killing cancer cells. Confocal laser scanning microscopy was used to track 3C in A549 cells. The cellular localization experiment showed that 3C targeted lysosomes and caused lysosomal damage. 相似文献
75.
CoFe2O4@SiO2‐CPTES‐Guanidine‐Cu(II) magnetic nanoparticles were synthesized and used as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of polyhydroquinolines and 2,3‐dihydroquinazoline‐4(1H)‐ones and for the oxidation of sulfides. The structure of this nanocatalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X‐ray diffraction and inductively coupled plasma optical emission spectrometry. Simple preparation, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst are some of the advantages of this protocol. 相似文献
76.
The radius of spatial analyticity for solutions of the KdV equation is studied. It is shown that the analyticity radius does not decay faster than as time t goes to infinity. This improves the works of Selberg and da Silva (2017) [30] and Tesfahun (2017) [34]. Our strategy mainly relies on a higher order almost conservation law in Gevrey spaces, which is inspired by the I-method. 相似文献
77.
Maurice Dörr Sebastian Lips Prof. Dr. Carlos Alberto Martínez-Huitle Dr. Dieter Schollmeyer Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7835-7838
We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways. 相似文献
78.
Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO2, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO2, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO2 under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO2]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO2), 365.8 K (TCCA-DMF)/NaNO2, and 358 K (TCCA-DMA)/NaNO2. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction. 相似文献
79.
Daniel Grinberg Sabrina Siddique Minh‐Quyen Le Richard Liang Jean‐Fabien Capsal Pierre‐Jean Cottinet 《Journal of Polymer Science.Polymer Physics》2019,57(2):109-115
Additive manufacturing (AM), otherwise known as three‐dimensional (3D) printing, is driving major innovations in many areas, such as engineering, manufacturing, art, education, and medicine. Although a considerable amount of progress has been made in this field, additional research work is required to overcome various remaining challenges. Recently, one of the actively researched areas lies in the AM of smart materials and structures. Electroactive materials incorporated in 3D printing have given birth to 4D printing, where 3D printed structures can perform as actuating and/or sensing systems, making it possible to deliver electrical signals under external mechanical stimuli and vice versa. In this paper, we present a lightweight, low cost piezoelectric material based on the dispersion of inorganic ferroelectric submicron particles in a polymer matrix. We report on how the proposed material is compatible with the AM process. Finally, we discuss its potential applications for healthcare, especially in smart implants prostheses. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 109–115 相似文献
80.
A cheap synthesis of the so‐called ‘decalin‐1,8‐diones’ started with the conjugate (1,4‐) addition of cyclohex‐2‐en‐1‐one derivatives to the γ‐position of the dilithium derivative (buta‐1,3‐diene‐1,1‐bis(olate)) of crotonic acid. Hydrogenation of these ‘1,4‐γ’ adducts and final cyclization afforded the enol tautomers of decalin‐1,8‐diones. Nucleophilic substitutions at these 3‐oxoenols by NH3 or primary amines created only monoamino products (namely, 3‐oxoenamines) whose reactions with OPCl3 yielded dihydro(1,3,2)oxazaphosphinin‐2‐one derivatives. The two regioisomers of a trimethyl‐3‐oxoenamine served as models for the constitutional assignments of the two rapidly interconverting (hence, individually NMR‐invisible), tautomeric trimethyl‐3‐oxoenols. Such methyl substitutions served to break the ‘pretended’ symmetry of ‘decalin‐1,8‐dione’. Hydrazine and 3‐oxoenols furnished oxygen‐free indazole derivatives whose N?H bonds exchanged with t1/2=ca. 0.00035 s at ca. ?58(9) °C. 相似文献