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991.
Zheng Zhou James McNeely Joshua Greenough Zheng Wei Haixiang Han Mathieu Rouzires Andrey Yu. Rogachev Rodolphe Clrac Marina A. Petrukhina 《Chemical science》2022,13(13):3864
The synthesis of a novel family of homoleptic COT-based heterotrimetallic self-assemblies bearing the formula [LnKCa(COT)3(THF)3] (Ln(iii) = Gd, Tb, Dy, Ho, Er, Tm, and Yb) is reported followed by their X-ray crystallographic and magnetic characterization. All crystals conform to the monoclinic P21/c space group with a slight compression of the unit cell from 3396.4(2) Å3 to 3373.2(4) Å3 along the series. All complexes exhibit a triple-decker structure having the Ln(iii) and K(i) ions sandwiched by three COT2− ligands with an end-bound {Ca2+(THF)3} moiety to form a non-linear (153.5°) arrangement of three different metals. The COT2− ligands act in a η8-mode with respect to all metal centers. A detailed structural comparison of this unique set of heterotrimetallic complexes has revealed consistent trends along the series. From Gd to Yb, the Ln to ring-centroid distance decreases from 1.961(3) Å to 1.827(2) Å. In contrast, the separation of K(i) and Ca(ii) ions from the COT-centroid (2.443(3) and 1.914(3) Å, respectively) is not affected by the change of Ln(iii) ions. The magnetic property investigation of the [LnKCa(COT)3(THF)3] series (Ln(iii) = Gd, Tb, Dy, Ho, Er, and Tm) reveals that the Dy, Er, and Tm complexes display slow relaxation of their magnetization, in other words, single-molecule magnet (SMM) properties. This behaviour is dominated by thermally activated (Orbach-like) and quantum tunneling processes for [DyKCa(COT)3(THF)3] in contrast to [ErKCa(COT)3(THF)3], in which the thermally activated and Raman processes appear to be relevant. Details of the electronic structures and magnetic properties of these complexes are further clarified with the help of DFT and ab initio theoretical calculations.A new class of heterotrimetallic COT-based self-assemblies accommodates metals from groups I–III in three different oxidation states and enables tuning of electronic and magnetic properties. 相似文献
992.
Jie Luo Quan-Quan Zhou Michael Montag Yehoshoa Ben-David David Milstein 《Chemical science》2022,13(13):3894
The highly desirable synthesis of the widely-used primary amides directly from alcohols and ammonia via acceptorless dehydrogenative coupling represents a clean, atom-economical, sustainable process. Nevertheless, such a reaction has not been previously reported, and the existing catalytic systems instead generate other N-containing products, e.g., amines, imines and nitriles. Herein, we demonstrate an efficient and selective ruthenium-catalyzed synthesis of primary amides from alcohols and ammonia gas, accompanied by H2 liberation. Various aliphatic and aromatic primary amides were synthesized in high yields, with no observable N-containing byproducts. The selectivity of this system toward primary amide formation is rationalized through density functional theory (DFT) calculations, which show that dehydrogenation of the hemiaminal intermediate into primary amide is energetically favored over its dehydration into imine.An efficient and selective synthesis of primary amides from alcohols and ammonia, with H2 evolution, has been achieved by an unprecedented acceptorless dehydrogenative process catalyzed by a pyridine-based PNN–ruthenium pincer complex. 相似文献
993.
As a serious worldwide problem, suicide often causes huge and irreversible losses to families and society. Therefore, it is necessary to detect and help individuals with suicidal ideation in time. In recent years, the prosperous development of social media has provided new perspectives on suicide detection, but related research still faces some difficulties, such as data imbalance and expression implicitness. In this paper, we propose a Deep Hierarchical Ensemble model for Suicide Detection (DHE-SD) based on a hierarchical ensemble strategy, and construct a dataset based on Sina Weibo, which contains more than 550 thousand posts from 4521 users. To verify the effectiveness of the model, we also conduct experiments on a public Weibo dataset containing 7329 users’ posts. The proposed model achieves the best performance on both the constructed dataset and the public dataset. In addition, in order to make the model applicable to a wider population, we use the proposed sentence-level mask mechanism to delete user posts with strong suicidal ideation. Experiments show that the proposed model can still effectively identify social media users with suicidal ideation even when the performance of the baseline models decrease significantly. 相似文献
994.
Jianxin Zhai Baowen Zhou Haihong Wu Shuaiqiang Jia Mengen Chu Shitao Han Wei Xia Mingyuan He Buxing Han 《Chemical science》2022,13(16):4616
Design of active catalysts for chemical utilization of methane under mild conditions is of great importance, but remains a challenging task. Here, we prepared a Ag/AgCl with SiO2 coating (Ag/AgCl@SiO2) photocatalyst for methane oxidation to carbon monoxide. High carbon monoxide production (2.3 μmol h−1) and high selectivity (73%) were achieved. SiO2 plays a key role in the superior performance by increasing the lifetime of the photogenerated charge carriers. Based on a set of semi in situ infrared spectroscopy, electron paramagnetic resonance, and electronic property characterization studies, it is revealed that CH4 is effectively and selectively oxidized to CO by the in situ formation of singlet 1O2via the key intermediate of COOH*. Further study showed that the Ag/AgCl@SiO2 catalyst could also drive valuable conversion using real sunlight under ambient conditions. As far we know, this is the first work on the application of SiO2 modified Ag/AgCl in the methane oxidation reaction.The Ag/AgCl@SiO2 catalyst exhibits excellent photocatalytic activity in selective aerobic oxidation of methane to carbon monoxide with high selectivity, and extended real light simulation feasibility shows potential in practical application. 相似文献
995.
Randomize-then-optimize (RTO) is widely used for sampling from posterior distribu-tions in Bayesian inverse problems.However,RTO can be computationally intensive for complexity problems due to repetitive evaluations of the expensive forward model and its gradient.In this work,we present a novel goal-oriented deep neural networks (DNN) sur-rogate approach to substantially reduce the computation burden of RTO.In particular,we propose to drawn the training points for the DNN-surrogate from a local approximated posterior distribution-yielding a flexible and efficient sampling algorithm that converges to the direct RTO approach.We present a Bayesian inverse problem governed by elliptic PDEs to demonstrate the computational accuracy and efficiency of our DNN-RTO ap-proach,which shows that DNN-RTO can significantly outperform the traditional RTO. 相似文献
996.
997.
Liu-Qiao Zhang Yang Gao Zhi-Hao Huang Wei Zhang Nian-Chen Zhou Zheng-Biao Zhang Xiu-Lin Zhu 《高分子科学》2021,39(1):60-69
The controlled and efficient synthesis of polymers with tailored topologies is challenging but important for exploring structure/property research. Herein, we proposed a concept of macro-latent monomer to achieve the controlled growth of polymer topologies.The macro-latent monomer was installed by a dynamic furan/maleimide covalent bond at the chain terminal. One-shot reversible additionfragmentation chain transfer(RAFT) polymerization of styrene and the macro-latent monomer created controlled growth of polymer topologies.Low temperature such as 40 ℃ could not activate the macro-latent monomer and thus the polymerization created the homo-polystyrene. By contrast, high temperature of ~110 ℃ activated the macro-latent monomer, and a maleimide-terminated macro-monomer was released via the retro-Diels Alder reaction. This macro-monomer immediately joined the cross polymerization with styrene and thus produced the side chains. By delicately manipulating the polymerization temperature, the predetermined placement of the macro-latent monomer-derived polymeric sidechains created controllably growing topologies, including star-, π-shaped, and density-variable grafting copolymers. This work paved a new way for creating on-demand topologies and would greatly enrich the topology synthesis. 相似文献
998.
Isonitrile group has been identified in many natural products.Due to the broad reactivity of N≡C triple bond,these natural products have valuable pharmaceutical potentials.This review summarizes the current biosynthetic pathways and the corresponding enzymes that are responsible for isonitrile-containing natural product generation.Based on the strategies utilized,two fundamentally distinctive approaches are discussed.In addition,recent progress in elucidating isonitrile group formation mechanisms is also presented. 相似文献
999.
二维纳米材料是一类具有类似二维平面形态,且厚度在纳米级甚至数个原子层的材料,其种类繁多并且具有很多与体相材料不同的物化性质,在众多领域受到了广泛关注。二维纳米材料在催化降解、吸脱附、过滤、传感检测等领域具有可观的应用潜力,还可用于环境污染的防治。通过形貌、元素、基团、缺陷的修饰、改性和材料合成等策略可以调控二维纳米材料的性质,从而研发新的材料体系或者改善二维纳米材料的性能。本文首先归纳了二维纳米材料的种类,并重点阐述了各种改性策略的作用及研究现状,以及改性的二维纳米材料在治理水体污染、大气污染和污染物检测等方面的应用,为二维纳米材料在环境治理领域的发展现状作了系统介绍和展望。 相似文献
1000.
新型药物辅料2-羟丙基-β-环糊精的色谱分离纯化 总被引:1,自引:2,他引:1
利用薄层色谱方法对碱浓度为1.5%、β-环糊精∶环氧丙烷(摩尔比)=1∶21的条件下生成的2-羟丙基-β-环糊精进行了定性分析,并通过对展开剂的选择和优化,得到了3种能有效分离不同取代度2-羟丙基-β-环糊精的展开剂体系,分别为正丙醇-水-浓氨水(6∶3∶1,V/V),异丙醇-水-浓氨水(6∶4∶0.5,V/V)和乙醇-水-浓氨水(6∶3∶0.8,V/V)。通过以乙醇体系为洗脱剂的硅胶柱色谱对其进行分离纯化,得到了两种不同取代的2-羟丙基-β-环糊精。经过ESI-MS谱图分析,确定分离后产品分别为单取代和双取代2-羟丙基-β-环糊精。 相似文献