全文获取类型
收费全文 | 8903篇 |
免费 | 414篇 |
国内免费 | 61篇 |
专业分类
化学 | 6008篇 |
晶体学 | 92篇 |
力学 | 288篇 |
数学 | 809篇 |
物理学 | 2181篇 |
出版年
2023年 | 46篇 |
2022年 | 39篇 |
2021年 | 197篇 |
2020年 | 179篇 |
2019年 | 173篇 |
2018年 | 172篇 |
2017年 | 145篇 |
2016年 | 296篇 |
2015年 | 274篇 |
2014年 | 353篇 |
2013年 | 599篇 |
2012年 | 744篇 |
2011年 | 830篇 |
2010年 | 472篇 |
2009年 | 387篇 |
2008年 | 618篇 |
2007年 | 583篇 |
2006年 | 513篇 |
2005年 | 474篇 |
2004年 | 409篇 |
2003年 | 315篇 |
2002年 | 283篇 |
2001年 | 193篇 |
2000年 | 141篇 |
1999年 | 93篇 |
1998年 | 49篇 |
1997年 | 61篇 |
1996年 | 78篇 |
1995年 | 75篇 |
1994年 | 75篇 |
1993年 | 56篇 |
1992年 | 58篇 |
1991年 | 46篇 |
1990年 | 48篇 |
1989年 | 34篇 |
1988年 | 25篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 26篇 |
1984年 | 18篇 |
1983年 | 17篇 |
1982年 | 18篇 |
1981年 | 16篇 |
1980年 | 10篇 |
1979年 | 13篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 10篇 |
1972年 | 9篇 |
排序方式: 共有9378条查询结果,搜索用时 15 毫秒
71.
We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C–H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation. 相似文献
72.
Studying protein ubiquitination is difficult due to the complexity of the E1–E2–E3 ubiquitination cascade. Here we report the discovery that C-terminal ubiquitin thioesters can undergo direct transthiolation with the catalytic cysteine of the model HECT E3 ubiquitin ligase Rsp5 to form a catalytically active Rsp5∼ubiquitin thioester (Rsp5∼Ub). The resulting Rsp5∼Ub undergoes efficient autoubiquitination, ubiquitinates protein substrates, and synthesizes polyubiquitin chains with native Ub isopeptide linkage specificity. Since the developed chemical system bypasses the need for ATP, E1 and E2 enzymes while maintaining the native HECT E3 mechanism, we named it “Bypassing System” (ByS). Importantly, ByS provides direct evidence that E2 enzymes are dispensable for K63 specific isopeptide bond formation between ubiquitin molecules by Rsp5 in vitro. Additionally, six other E3 enzymes including Nedd4-1, Nedd4-2, Itch, and Wwp1 HECT ligases, along with Parkin and HHARI RBR ligases processed Ub thioesters under ByS reaction conditions. These findings provide general mechanistic insights on protein ubiquitination, and offer new strategies for assay development to discover pharmacological modulators of E3 enzymes. 相似文献
73.
Calix[4]arene-based cation receptor 1 has been synthesised by following a multi-step synthetic procedure. The fluorescence properties of 1 upon the addition of various metal ions were investigated by fluorescence spectroscopy. As a result, it was revealed that 1 displayed dramatic quenching effect upon the exposure to Cs+. In contrast, no significant quenching effects were observed upon the addition of other metal ions such as Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ag+, Zn2+ and Ni2+. Compound 1 was also found by Job plot to form a 1:1 complex with Cs+. In addition, we also prepared 1-embedded electrospun nanofibrous film (NF-1) as an adsorbent for Cs+. NF-1 is proved to adsorb Cs+ effectively from an aqueous solution, indicating that it would be usefully utilised as an adsorbent to remove Cs+. 相似文献
74.
The use of liquid crystals (LCs) as anisotropic solvents is desired for various potential applications and usually for other organic and inorganic compounds. In this work, solvent polarity parameters are obtained using a spectroscopic method for four LCs with a range of high and low dielectric anisotropy (?ε). Solvatochromic polarity parameters for these LCs were defined via Kamlet–Abboud–Taft polarity functions characterizing different temperatures and phases, isotropic and anisotropic, and using the Reichardt’s dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio) phenolate standard probe. The investigated polarity parameters reveal the effects of LC media on the photo-physical behaviour of solute molecules in isotropic and anisotropic media. Subsequently, a new LC polarity parameter (Zo) is introduced as an overall matrix anisotropy polarity parameter to characterize variation between isotropic and anisotropic phases. The values of Zo are sorted from higher to lower dielectric anisotropies (?ε). 相似文献
75.
In this study, the gene encoding an α-amylase from a psychrophilic Arthrobacter agilis PAMC 27388 strain was cloned into a pET-28a(+) vector and heterologously expressed in Escherichia coli BL21(DE3). The recombinant α-amylase with a molecular mass of about 80 kDa was purified by using Ni2+-NTA affinity chromatography. This recombinant α-amylase exhibited optimal activity at pH 3.0 and 30 °C and was highly stable at varying temperatures (30–60 °C) and within the pH range of 4.0–8.0. Furthermore, α-amylase activity was enhanced in the presence of FeCl3 (1 mM) and β-mercaptoethanol (5 mM), while CoCl2 (1 mM), ammonium persulfate (5 mM), SDS (10 %), Triton X-100 (10 %), and urea (1 %) inhibited the enzymatic activity. Importantly, the presence of Ca2+ ions and phenylmethylsulfonyl fluoride (PMSF) did not affect enzymatic activity. Thin layer chromatography (TLC) analysis showed that recombinant A. agilis α-amylase hydrolyzed starch, maltotetraose, and maltotriose, producing maltose as the major end product. These results make recombinant A. agilis α-amylase an attractive potential candidate for industrial applications in the textile, paper, detergent, and pharmaceutical industries. 相似文献
76.
Research in the environmentally friendly energy field has grown rapidly due to severe problems such as global warming and climate change. Sodium-ion technology is one of the most promising alternatives to lithium-ion batteries. Use of ionic liquids containing thiocyanate anion has been considered because of their low cost, low viscosity, and nonhazardous nature. In this work, polyethylene oxide (PEO)–sodium perchlorate (NaClO4) samples containing different amounts of 1-butyl-3-methylimidazolium thiocyanate ionic liquid were prepared by a solution casting method. Addition of the ionic liquid to the PEO–NaClO4 electrolyte further increased the ionic conductivity. The electrolyte containing 30 wt% ionic liquid exhibited the maximum ionic conductivity of ~5.0 × 10?4 S/cm at room temperature. Fourier-transform infrared (FT-IR) spectroscopy revealed the interaction between the polymer chain and salt ion complexes for various sodium salt contents. Differential scanning calorimetry (DSC) demonstrated that the crystallinity was reduced by addition of 1-butyl-3-methylimidazolium thiocyanate ionic liquid. 相似文献
77.
Kabindra Kafle Yong Bum Park Christopher M. Lee Joshua J. Stapleton Sarah N. Kiemle Daniel J. Cosgrove Seong H. Kim 《Cellulose (London, England)》2017,24(8):3145-3154
The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm?1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (νC=O, 1745 cm?1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm?1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development. 相似文献
78.
Jinhae?Park Wei?WangEmail author Pingwen?Zhang Zhifei?Zhang 《Calculus of Variations and Partial Differential Equations》2017,56(2):41
In this paper, we investigate the structure and stability of the isotropic-nematic interface in 1-D. In the absence of the anisotropic energy, the uniaxial solution is the only global minimizer. In the presence of the anisotropic energy, the uniaxial solution with the homeotropic anchoring is stable for \(L_2<0\) and unstable for \(L_2>0\). We also present many interesting open questions, some of which are related to De Giorgi conjecture. 相似文献
79.
Naeem Khan Nargis Jamila Yun MiDang Cheong Mi Lee Yu Min Park Ga Hyun Lee 《Analytical letters》2017,50(15):2426-2446
This study reports the concentrations of eight trace essential (Zn, Mn, Cu, Ni, Cr, Co, V, and Se) and four toxic elements (Pb, As, Cd, and Hg) in commonly consumed stone fruits from South Korea. The samples were digested by microwave-induced combustion and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The concentrations of mercury were analyzed by direct mercury analysis (DMA). The analytical techniques were validated by linearity, limits of detection and quantification, precision, recovery, and for accuracy by analyzing a spinach leave-certified reference material; satisfactory results were obtained in all cases. The concentrations of essential trace elements varied considerably among the stone fruits. Generally stone fruits contained comparatively high concentrations of Zn (0.946 to 7.86?µg/g) and Mn (below the limit of detection to 1.66?µg/g), while lower contents of Cu (0.214 to 1.24?µg/g), Cr (0.032 to 0.114?µg/g), Ni (0.006 to 0.091?µg/g), Co (0.004 to 0.016?µg/g), V (below the limit of detection to 0.023?µg/g), and Se (0.0002 to 0.005?µg/g) were obtained. The concentrations (µg/g) of toxic metals were 0.007 (peach) to 0.016 (cherry) for Pb, 0.001 (plum) to 0.007 (cherry) for As, 0.002 (apricot and cherry) to 0.003 (peach) for Cd, and 0.0003 (peach) to 0.0016 (jujube) for Hg. The values for the estimated dietary intakes, target hazard quotients, and hazard indices were lower than the recommended safety limits by World Health Organization. Therefore, the analyzed stone fruits were deemed to be safe for human consumption. 相似文献
80.
Dr. Chiyoung Park Dr. Beom Joo Yang Ki Beom Jeong Dr. Chae Bin Kim Prof. Seunghyun Lee Dr. Bon-Cheol Ku 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(20):5577-5581
The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with CuII ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and CuII. We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non-covalent engineering of MSN surfaces that should be suitable for various applications in materials science. 相似文献