全文获取类型
收费全文 | 87503篇 |
免费 | 5343篇 |
国内免费 | 12304篇 |
专业分类
化学 | 69282篇 |
晶体学 | 1163篇 |
力学 | 2330篇 |
综合类 | 849篇 |
数学 | 12673篇 |
物理学 | 18853篇 |
出版年
2023年 | 650篇 |
2022年 | 1170篇 |
2021年 | 1760篇 |
2020年 | 2369篇 |
2019年 | 2289篇 |
2018年 | 1962篇 |
2017年 | 2798篇 |
2016年 | 3006篇 |
2015年 | 2525篇 |
2014年 | 3463篇 |
2013年 | 6834篇 |
2012年 | 6504篇 |
2011年 | 5153篇 |
2010年 | 4362篇 |
2009年 | 5914篇 |
2008年 | 6117篇 |
2007年 | 6329篇 |
2006年 | 5749篇 |
2005年 | 4855篇 |
2004年 | 4490篇 |
2003年 | 3621篇 |
2002年 | 3100篇 |
2001年 | 2547篇 |
2000年 | 2198篇 |
1999年 | 2114篇 |
1998年 | 1798篇 |
1997年 | 1449篇 |
1996年 | 1178篇 |
1995年 | 1339篇 |
1994年 | 1189篇 |
1993年 | 991篇 |
1992年 | 945篇 |
1991年 | 632篇 |
1990年 | 531篇 |
1989年 | 499篇 |
1988年 | 375篇 |
1987年 | 287篇 |
1986年 | 269篇 |
1985年 | 211篇 |
1984年 | 228篇 |
1983年 | 125篇 |
1982年 | 199篇 |
1981年 | 164篇 |
1980年 | 182篇 |
1979年 | 166篇 |
1978年 | 144篇 |
1977年 | 88篇 |
1976年 | 74篇 |
1974年 | 41篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
71.
The persistent, bioaccumulative, and toxic properties of certain per- and polyfluoroalkyl substances (PFAS) raise concerns for environmental and human health. This has led to the gradual phase-out from production and commerce of some legacy PFAS. Fluoroalkylether compounds (ether-PFAS) are among the fluorinated alternative chemicals that are beginning to be reported in impacted and background environments. Extensive monitoring activities were conducted since 2015–2019 to bridge knowledge gaps on the environmental fate and effects of ether-PFAS including F-53B (6:2 chlorinated polyfluoroalkyl ether sulfonate [6:2 Cl-PFAES] and 8:2 Cl-PFAES), Gen-X (hexafluoropropylene oxide dimer acid [HFPO-DA]), and ADONA (dodecafluoro-3H-4,8-dioxanonanoate). In recent years, advances in nontarget screening using high-resolution mass spectrometry have revealed the identities of other infrequently monitored ether-PFAS. In this critical review, we provide an up-to-date inventory of the structures of ether-PFAS discovered in the recent literature. Their environmental occurrence, fate, and effects are discussed on a comparative perspective with some legacy PFAS such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Information on the methods employed for the quantitative and semi-quantitative analysis of ether-PFAS is also provided, including sample preparation and mass spectrometry analysis, analytical performance, and limitations. In particular, the compiled database of MS/MS fragment ions (n = 111) can be useful in spectrum interpretation of novel ether-PFAS. The concluding remarks open on possible research avenues and the challenges that remain to be addressed. 相似文献
72.
Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K3[Fe(CN)6] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni2.6Cu0.4 MOFs material shows the highest specific capacitance (1282 F g?1 at 1 A g?1 in mixed 2 M KOH and 0.1 M K3[Fe(CN)6]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production. 相似文献
73.
Li Song Jiaxiang Lin Yang He Jingqing Li Jing Sheng Shichun Jiang Dinghai Huang 《Journal of Polymer Science.Polymer Physics》2019,57(3):142-151
Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151 相似文献
74.
By 5-h reaction of cis-[RuIICl2(DMSO)4] (M2) with K10[α2-P2W17O61] (M3) in ice-cooled, HCl-acidic aqueous solution, a water-soluble 1:2-type diamagnetic ruthenium(II) complex of formula K18[RuII(DMSO)2(P2W17O61)2]·35H2O (M1) was unexpectedly obtained as an analytically pure, homogeneous tan-colored solid, in which two DMSO ligands are coordinated to the ruthenium(II) atom. The cytotoxic potential of the complex was tested on C33A, DLD-1, and HepG-2 cancer cells and human normal embryonic lung fibroblasts cell MRC-5; the viability of the treated cells was evaluated by MTT assay. The mode of cell death was assessed by morphological study of DNA damage and apoptosis assays. Compound M1 induced cell death in a dose-dependent manner, and the mode of cell death was essentially apoptosis though necrosis was also noticed. Cell cycle analysis by flow cytometry indicated that M1 caused cell cycle arrest and accumulated cells in S phase. 相似文献
75.
Bahareh Heidari Majid M. Heravi Mohammad Reza Nabid Roya Sedghi Seyyed Emad Hooshmand 《应用有机金属化学》2019,33(1)
A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions. 相似文献
76.
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
77.
This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but ) nonlinearities. 相似文献
78.
Ke Xu Evan T. Vickers Longshi Rao Dr. Sarah A. Lindley A'Lester C. Allen Prof. Binbin Luo Prof. Xueming Li Prof. Jin Zhong Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):5014-5021
CH3NH3PbBr3 perovskite quantum dots (PQDs) are synthesized by using four different linear alkyl phosphonic acids (PAs) in conjunction with (3-aminopropyl)triethoxysilane (APTES) as capping ligands. The resultant PQDs are characterized by means of XRD, TEM, Raman spectroscopy, FTIR spectroscopy, UV/Vis, photoluminescence (PL), time-resolved PL, and X-ray photoelectron spectroscopy (XPS). PA chain length is shown to control the PQD size (ca. 2.9–4.2 nm) and excitonic absorption band positions (λ=488–525 nm), with shorter chain lengths corresponding to smaller sizes and bluer absorptions. All samples show a high PL quantum yield (ca. 46–83 %) and high PL stability; this is indicative of a low density of band gap trap states and effective surface passivation. Stability is higher for smaller PQDs; this is attributed to better passivation due to better solubility and less steric hindrance of the shorter PA ligands. Based on the FTIR, Raman, and XPS results, it is proposed that Pb2+ and CH3NH3+ surface defects are passivated by R−PO32− or R−PO2(OH)−, whereas Br− surface defects are passivated by R−NH3+ moieties. This study establishes the combination of PA and APTES ligands as a highly effective dual passivation system for the synergistic passivation of multiple surface defects of PQDs through primarily ionic bonding. 相似文献
79.
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
80.
Ethan M. Cunningham Alexander S. Gentleman Peter W. Beardsmore 《Molecular physics》2019,117(21):2990-3000
ABSTRACTWe present the results of a combined experimental and computational study of the structures of gas-phase M+(N2O)n (M?=?Li, Al) complexes. Infrared spectra were recorded in the region of the N2O asymmetric (N?=?N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M+(N2O)n (M?=?Cu, Ag, Au and M?=?Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li+ complexes, there is, however, evidence for the presence of bound N2 moieties, indicating the presence of inserted, OLi+N2(N2O)n–type structures. The weak N2 band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al+(N2O)n complexes whose infrared spectra can be understood on the basis of molecularly-bound N2O ligands. The differences in M+(N2O)n structures observed for these closed–shell, ns2, metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. 相似文献