全文获取类型
收费全文 | 23401篇 |
免费 | 4255篇 |
国内免费 | 3819篇 |
专业分类
化学 | 10722篇 |
晶体学 | 445篇 |
力学 | 1091篇 |
综合类 | 339篇 |
数学 | 2026篇 |
物理学 | 6325篇 |
无线电 | 10527篇 |
出版年
2024年 | 96篇 |
2023年 | 461篇 |
2022年 | 798篇 |
2021年 | 838篇 |
2020年 | 883篇 |
2019年 | 802篇 |
2018年 | 765篇 |
2017年 | 831篇 |
2016年 | 906篇 |
2015年 | 1289篇 |
2014年 | 1495篇 |
2013年 | 1851篇 |
2012年 | 2075篇 |
2011年 | 2136篇 |
2010年 | 1929篇 |
2009年 | 1855篇 |
2008年 | 1902篇 |
2007年 | 1817篇 |
2006年 | 1623篇 |
2005年 | 1366篇 |
2004年 | 1026篇 |
2003年 | 777篇 |
2002年 | 760篇 |
2001年 | 620篇 |
2000年 | 611篇 |
1999年 | 371篇 |
1998年 | 197篇 |
1997年 | 175篇 |
1996年 | 148篇 |
1995年 | 128篇 |
1994年 | 114篇 |
1993年 | 127篇 |
1992年 | 82篇 |
1991年 | 68篇 |
1990年 | 62篇 |
1989年 | 48篇 |
1988年 | 61篇 |
1987年 | 32篇 |
1986年 | 38篇 |
1985年 | 26篇 |
1984年 | 30篇 |
1983年 | 25篇 |
1982年 | 22篇 |
1981年 | 19篇 |
1980年 | 20篇 |
1979年 | 19篇 |
1978年 | 23篇 |
1977年 | 9篇 |
1974年 | 9篇 |
1971年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
181.
EPR study showed that the semi-quinone radical anion of chloranil (TCQ) was formed in a charge-transfer process between ground state chloranil as acceptor and each one of the following ground state donors,i.e.,N,N'-diethyl aniline (DEA),phenothiazine (PTZ),carbazole (CBZ),pyrene (PY),ferrocene (FRO),triphenylphosphine (TPP),triethylamine (TEA),anthracene (AN) and N,N-diethyl-3-aminophenyl ester of palmitic acid (DPP).Our results indicate that there is a tunneling effect for the ground-state charge-transfer process between chloranil and the donor. 相似文献
182.
Bo Jiang Hui Song Yunqing Kang Shengyao Wang Qi Wang Xin Zhou Kenya Kani Yanna Guo Jinhua Ye Hexing Li Yoshio Sakka Joel Henzie Yamauchi Yusuke 《Chemical science》2020,11(3):791
Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO2 into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis. 相似文献
183.
Yaohao Li Xiaoyang Guan Patrick K. Chaffey Yuan Ruan Bo Ma Shiying Shang Michael E. Himmel Gregg T. Beckham Hai Long Zhongping Tan 《Chemical science》2020,11(34):9262
Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies. In this study, we examine the impact of O-glycosylation on the binding selectivity of a model Family 1 carbohydrate-binding module (CBM), which has been shown to be one of the primary sub-domains responsible for non-productive lignin binding in multi-modular cellulases. Specifically, we examine the relationship between glycan structure and the binding specificity of the CBM to cellulose and lignin substrates. We find that the glycosylation pattern of the CBM exhibits a strong influence on the binding affinity and the selectivity between both cellulose and lignin. In addition, the large set of binding data collected allows us to examine the relationship between binding affinity and the correlation in motion between pairs of glycosylation sites. Our results suggest that glycoforms displaying highly correlated motion in their glycosylation sites tend to bind cellulose with high affinity and lignin with low affinity. Taken together, this work helps lay the groundwork for future exploitation of glycoengineering as a tool to improve the performance of industrial enzymes.Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies.The cell walls of terrestrial plants primarily comprise the polysaccharides cellulose, hemicellulose, and pectin, as well as the heterogeneous aromatic polymer, lignin. In nature, carbohydrates derived from plant polysaccharides provide a massive carbon and energy source for biomass-degrading fungi, bacteria, and archaea, which together are the primary organisms that recycle plant matter and are a critical component of the global carbon cycle. Across the various environments in which these microbes break down lignocellulose, a few known enzymatic and chemical systems have evolved to deconstruct polysaccharides to soluble sugars.1–6 These natural systems are, in several cases, being evaluated for industrial use to produce sugars for further conversion into renewable biofuels and chemicals.From an industrial perspective, overcoming biomass recalcitrance to cost-effectively produce soluble intermediates, including sugars for further upgrading remains the main challenge in biomass conversion. Lignin, the evolution of which in planta provided a significant advantage for terrestrial plants to mitigate microbial attack, is now widely recognized as a primary cause of biomass recalcitrance.7 Chemical and/or biological processing scenarios of lignocellulose have been evaluated8 and several approaches have been scaled to industrial biorefineries to date. Many biomass conversion technologies overcome recalcitrance by partially or wholly removing lignin from biomass using thermochemical pretreatment or fractionation. This approach enables easier polysaccharide access for carbohydrate-active enzymes and/or microbes. There are however, several biomass deconstruction approaches that employ enzymes or microbes with whole, unpretreated biomass.9,10 In most realistic biomass conversion scenarios wherein enzymes or microbes are used to depolymerize polysaccharides, native or residual lignin remains.11,12 It is important to note that lignin can bind and sequester carbohydrate-active enzymes, which in turn can affect conversion performance.13Therefore, efforts aimed at improving cellulose binding selectivity relative to lignin have emerged as major thrusts in cellulase studies.14–25 Multiple reports in the past a few years have made exciting new contributions to our collective understanding of how fungal glycoside hydrolases, which are among the most well-characterized cellulolytic enzymes given their importance to cellulosic biofuels production, bind to lignin from various pretreatments.15,17 Taken together, these studies have demonstrated that the Family 1 carbohydrate-binding modules (CBMs) often found in fungal cellulases are the most relevant sub-domains for non-productive binding to lignin,15,17,20,26 likely due to the hydrophobic face of these CBMs that is known to be also responsible for cellulose binding (Fig. 1).27Open in a separate windowFig. 1Model of glycosylated CBM binding the surface of a cellulose crystal. Glycans are shown in green with oxygen atoms in red, tyrosines known to be critical to binding shown in purple, and disulfide bonds Cys8–Cys25 and Cys19–Cys35 in yellow.Furthermore, several studies have been published recently using protein engineering of Family 1 CBMs to improve CBM binding selectivity to cellulose with respect to lignin. Of particular note, Strobel et al. screened a large library of point mutations in both the Family 1 CBM and the linker connecting the catalytic domain (CD) and CBM.21,22 These studies demonstrated that several mutations in the CBM and one in the linker led to improved cellulose binding selectivity compared to lignin. The emerging picture is that the CBM-cellulose interaction, which occurs mainly as a result of stacking between the flat, hydrophobic CBM face (which is decorated with aromatic residues) and the hydrophobic crystal face of cellulose I, is also likely the main driving force in the CBM-lignin interaction given the strong potential for aromatic–aromatic and hydrophobic interactions.Alongside amino acid changes, modification of O-glycosylation has recently emerged as a potential tool in engineering fungal CBMs, which Harrison et al. demonstrated to be O-glycosylated.28–31 In particular, we have revealed that the O-mannosylation of a Family 1 CBM of Trichoderma reesei cellobiohydrolase I (TrCel7A) can lead to significant enhancements in the binding affinity towards bacterial microcrystalline cellulose (BMCC).30,32,33 This observation, together with the fact that glycans have the potential to form both hydrophilic and hydrophobic interactions with other molecules, led us to hypothesize that glycosylation may have a unique role in the binding selectivity of Family 1 CBMs to cellulose relative to lignin and as such, glycoengineering may be exploited to improve the industrial performance of these enzymes. To test this hypothesis, in the present study, we systematically probed the effects of glycosylation on CBM binding affinity for a variety of lignocellulose-derived cellulose and lignin substrates and investigated routes to computationally predict the binding properties of different glycosylated CBMs. 相似文献
184.
基于Lagrange原理和假设模态法建立了旋转输液管的动力学模型.通过降阶升维的方法求解系统的特征值问题,并分析了旋转输液管自由振动特性.得到了不同端部集中质量和转速下,系统特征值随流速升高的演变轨迹.揭示了临界流速随系统参数的变化规律.研究发现,内部流体的流动对旋转输液管动力学特性存在显著影响.在某些参数组合下,系统低阶模态能够形成不同形式的内共振关系.预示了旋转输液管模型蕴含丰富的动力学现象. 相似文献
185.
Fuzzy Optimization and Decision Making - In this paper, an uncertain nonlinear switched system is a nonlinear switched system disturbed by subjective uncertainties, which can be illustrated by... 相似文献
186.
In this paper, a tumor immune model with time delay is studied. First, the stability of nonnegative equilibria is analyzed. Then the time delay τ is selected as a bifurcation parameter and the existence of Hopf bifurcation is proved. Finally, by using the canonical method and the central manifold theory, the criteria for judging the direction and stability of Hopf bifurcation are given. 相似文献
187.
188.
A series ofc-axis oriented YBa2Cu3O
x
-films with different oxygen content were prepared by laser deposition. The oxygen contentx was determined by X-ray diffraction and by resonant Rutherford-back-scattering (RRBS) measurements. Thec-axis length in these films of YBa2Cu3O
x
is about 0.5% larger compared to bulk values. We describe transport measurements in magnetic fields up to 7 Tesla between room temperature andT
c
in samples with an oxygen content between the orthorhombic-to-tetragonal transition (x6.4) and full oxygenation (x7). The ratio /R
H
was investigated with respect to the two-dimensional Luttinger liquid theory and the model of the two-dimensional ionic metal. We report on deviations from the expected quadratic temperature behaviour of /R
H
, especially in films with high oxygen content. 相似文献
189.
190.
在现代化国防和航空航天领域,目标表面涂覆具有热防护、电磁屏蔽、降低红外辐射等性能的材料,可有效保护目标,但其处于目标的表面,长期受到周围环境影响,易出现气泡、划痕、脱落等不同类型的损伤,造成涂层性能大幅度降低,无法有效保护目标。因此,需要定期对目标涂层进行检测和维护。通过研究涂层损伤与温度和发射率之间的关系,结合热辐射定律、比色测温技术、发射率测量方法,搭建一套红外热像仪的检测装置,提出一种基于涂层温度和发射率场的涂层损伤检测方法。将研制的检测装置应用于以铝为基底的氧化铝涂层,通过分析氧化铝的温度和发射率准确识别涂层内部和外部损伤,验证了基于温度和发射率场的涂层损伤检测方法的理论模型,以及检测装置的可行性与适用性。 相似文献