全文获取类型
收费全文 | 65749篇 |
免费 | 14675篇 |
国内免费 | 5837篇 |
专业分类
化学 | 62027篇 |
晶体学 | 801篇 |
力学 | 2665篇 |
综合类 | 334篇 |
数学 | 5876篇 |
物理学 | 14558篇 |
出版年
2024年 | 70篇 |
2023年 | 633篇 |
2022年 | 1177篇 |
2021年 | 1268篇 |
2020年 | 2386篇 |
2019年 | 3638篇 |
2018年 | 1998篇 |
2017年 | 1712篇 |
2016年 | 4703篇 |
2015年 | 4867篇 |
2014年 | 5193篇 |
2013年 | 6210篇 |
2012年 | 5859篇 |
2011年 | 5213篇 |
2010年 | 4887篇 |
2009年 | 4686篇 |
2008年 | 4410篇 |
2007年 | 3588篇 |
2006年 | 3280篇 |
2005年 | 3128篇 |
2004年 | 2574篇 |
2003年 | 2219篇 |
2002年 | 2929篇 |
2001年 | 2158篇 |
2000年 | 1884篇 |
1999年 | 1045篇 |
1998年 | 592篇 |
1997年 | 502篇 |
1996年 | 491篇 |
1995年 | 418篇 |
1994年 | 360篇 |
1993年 | 274篇 |
1992年 | 280篇 |
1991年 | 277篇 |
1990年 | 223篇 |
1989年 | 178篇 |
1988年 | 123篇 |
1987年 | 97篇 |
1986年 | 117篇 |
1985年 | 85篇 |
1984年 | 76篇 |
1983年 | 62篇 |
1982年 | 44篇 |
1981年 | 45篇 |
1980年 | 34篇 |
1979年 | 25篇 |
1978年 | 26篇 |
1977年 | 27篇 |
1976年 | 25篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 181 毫秒
991.
Ya‐Ping Du Ya‐Wen Zhang Prof. Dr. Zheng‐Guang Yan Dr. Ling‐Dong Sun Prof. Dr. Song Gao Prof. Dr. Chun‐Hua Yan Prof. Dr. 《化学:亚洲杂志》2007,2(8):965-974
We report the synthesis of single‐crystalline and near‐monodispersed NaMF3 (M=Mn, Co, Ni, Mg), LiMAlF6 (M=Ca, Sr), and NaMgF3:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF3 (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF3 nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF3 square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF3:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF3 may be a good candidate host material for red upconversion luminescence. 相似文献
992.
In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10?7 to 5 × 10?3 M with R2 = 0.9989 and 5 × 10?6to 5 × 10?3 M with R2 = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10?4M, and the ratio between the two optical isomers was 99.3:0.7. 相似文献
993.
Synthesis and characterization of new soluble poly(aryl ether nitrile)s containing phthalazinone moiety 总被引:1,自引:0,他引:1
Ming Jing Wang Cheng Liu Li Ming Dong Xi Gao Jian 《中国化学快报》2007,18(5):595-597
A series of novel poly(aryl ether nitrile)s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers (I) with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly(aryl ether nitrile)s including solubility and crystallinity were also studied. 相似文献
994.
995.
The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy. 相似文献
996.
Jean‐Louis Schmitt Adrian‐Mihail Stadler Nathalie Kyritsakas Jean‐Marie Lehn 《Helvetica chimica acta》2003,86(5):1598-1624
Control over the folding of molecular strands may be achieved by appropriate choice of the constituting subunits, in particular for chains of specific heterocycles such as sequences of directly connected pyridine (py) and pyrimidine (pym) rings, which are known to fold into extended helical structures. Since the hydrazone (hyz) group represents an isomorphic analogue of a py site, the condensation of hydrazine and carboxaldehyde derivatives of pym offers a very efficient approach to strands incorporating hyz instead of py units and constituted by sequences of alternating hyz and pym groups. A series of such strands of different lengths, up to ten hyz units, i.e., 1 – 7 , were synthesized. Their spectral properties indicate that they fold indeed into helical shapes. Extensive characterization was performed in solution by 1HNMR spectroscopy and in the solid state by determination of the crystal structures of eight such strands. They all display the expected helical geometry with up to 3 1/3 turns and direct stacking contacts. The efficiency and flexibility of the synthetic approach as well as its wide potential for generation of diversity through lateral decoration make the (hyz? pym) subunit a particularly attractive helicity codon. 相似文献
997.
Qing‐Xiang Liu Feng‐Bo Xu Qing‐Shan Li Xian‐Shun Zeng Xue‐Bing Leng Zheng‐Zhi Zhang 《中国化学》2002,20(9):878-883
Dinuclear silver (I) six‐membered ring complex [Ag2 (bta)2 ‐(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement. 相似文献
998.
配合物Cu(phen)2 (dca)2的合成及晶体结构 总被引:7,自引:0,他引:7
合成了配合物Cu(phen)2 (dca)2(phen=C12H8N2为1,10-邻菲啰啉,dca-为二氰基氨基阴离子),用IR对其结构进行了初步表征,并测定了配合物的晶体结构.该晶体属单斜晶系,空间群为P21/c;晶胞参数a=0.8869(2)nm,b=1.4691(2)nm,c=1.9298(2)nm,β=100.90(1)°;V=2.4691(8)nm3,Z=4,F(000)=1132.00,Dc=1.496g/cm3,R=0.051,RW=0.068.中心铜(Ⅱ)离子分别与两个phen中的四个N原子和两个dca-的两个N原子配位,形成六配位的变形八面体结构. 相似文献
999.
An oligosaccharide homologue named SnS-2 was isolated from the root of Scrophularia ningpoensis Hemsl.SnS-2 was purified by means of gel-permeation chromatography and ion-exchange chromatography. Its physicochemical properties, including carbohydrate content and molecular weight were determined. The structure of SnS-2 was elucidated by chemical methods along with ^1H and ^13C NMR spectroscopy, including two-dimensional DQCOSY and H-detected ^1H, ^13C HMQC experiments. These results show that SnS-2 possesses a backbone consisting of terminal α-Galp-(1→, α-Galp-(1→6), α-Glcp-(1→6) and nonreducing end β-Fruf-(2→. The bioactive assay showed that it could inhibit the growth of Lewis pulmonary carcinoma implanted in mice. 相似文献
1000.
A method was developed for the determination of rare earth impurities in high purity Gd(2)O(3) by inductively coupled plasma mass spectrometry (ICP-MS). The matrix suppression effect of Gd(2)O(3) on signals of rare earth impurities was compensated for by Re internal standardization. The spectra overlap interferences from GdH, GdO, GdOH(n) (n=1-3) on Tb, Tm, Yb and Lu were eliminated by 2-thylhexylhydrogen-2-ethylhexy phosphonate (EHEHP) extraction chromatographic separation. The detection limits for REEs were 0.005-0.017 ng ml(-1) in solution and 0.002-0.05 mug g(-1) in solid. Recoveries of spiked sample for REEs were from 88 to 121% with the precision of 1.0-7.5% RSD. Determination of trace REEs in two Gd(2)O(3) samples were performed. The method can be applied to analysis of 99.99-99.9999% high purity Gd(2)O(3). 相似文献