全文获取类型
收费全文 | 3074篇 |
免费 | 403篇 |
国内免费 | 727篇 |
专业分类
化学 | 3429篇 |
晶体学 | 29篇 |
力学 | 77篇 |
综合类 | 68篇 |
数学 | 84篇 |
物理学 | 517篇 |
出版年
2024年 | 2篇 |
2023年 | 48篇 |
2022年 | 76篇 |
2021年 | 143篇 |
2020年 | 182篇 |
2019年 | 118篇 |
2018年 | 96篇 |
2017年 | 90篇 |
2016年 | 162篇 |
2015年 | 130篇 |
2014年 | 166篇 |
2013年 | 333篇 |
2012年 | 233篇 |
2011年 | 234篇 |
2010年 | 178篇 |
2009年 | 154篇 |
2008年 | 179篇 |
2007年 | 178篇 |
2006年 | 219篇 |
2005年 | 194篇 |
2004年 | 155篇 |
2003年 | 156篇 |
2002年 | 98篇 |
2001年 | 75篇 |
2000年 | 71篇 |
1999年 | 63篇 |
1998年 | 53篇 |
1997年 | 61篇 |
1996年 | 59篇 |
1995年 | 67篇 |
1994年 | 47篇 |
1993年 | 40篇 |
1992年 | 25篇 |
1991年 | 22篇 |
1990年 | 13篇 |
1989年 | 28篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有4204条查询结果,搜索用时 20 毫秒
1.
Dr. Zhenbo Mo Dr. Takanori Shima Prof. Dr. Zhaomin Hou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8713-8722
Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based acriPNP-pincer ligands {[(acriPNP)Ti]2(μ2-η1:η2-N2)(μ2-H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry. 相似文献
2.
Dr. Wenyan Hao Yuchen Sha Dr. Yi Deng Yi Luo Li Zeng Shan Tang Dr. Yue Weng Prof. Dr. Chien-Wei Chiang Prof. Dr. Aiwen Lei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):4931-4934
An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved. 相似文献
3.
Dr. Todor Baramov Bianca Schmid Ho Ryu Jinhoon Jeong Dr. Karlijn Keijzer Dr. Leonard von Eckardstein Prof. Dr. Mu-Hyun Baik Prof. Dr. Roderich D. Süssmuth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(28):6955-6962
The E. coli siderophore enterobactin, the strongest FeIII chelator known to date, forms hexacoordinate complexes with SiIV, GeIV, and TiIV. Synthetic protocols have been developed to prepare non-symmetric enterobactin analogues with varying denticities. Various benzoic acid residues were coupled to the macrocyclic lactone to afford a diverse library of ligands. These enterobactin analogues were bound to SiIV, GeIV, and TiIV, and the complexes were investigated through experimental and computational techniques. The binding behavior of the synthesized chelators enabled assessment of the contribution of each of the phenolic hydroxy groups in enterobactin to metal-ion complexation. It was found that at least four O-donors are needed for enterobactin derivatives to act as metal binders. Density functional theory calculations indicate that the strong binding behavior of enterobactin can be ascribed to a diminished translational entropy penalty, a common feature of the chelate effect, coupled with the structural arrangement of the three catechol moieties, which allows the triseryl base to be installed without distorting the preferred local metal-binding geometry of the catecholate ligands. 相似文献
4.
Mohammad Nasir Uddin Zainul Abedin Siddique Nobuyuki Mase Monir Uzzaman Wahhida Shumi 《应用有机金属化学》2019,33(6)
A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH2) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties. 相似文献
5.
Recent research has focused on increasing the evidentiary value of latent fingerprints through chemical analysis. Although researchers have optimized the use of organic and metal matrices for matrix‐assisted laser desorption/ionization‐mass spectrometry imaging (MALDI‐MSI) of latent fingerprints, the use of development powders as matrices has not been fully investigated. Carbon forensic powder (CFP), a common nonporous development technique, was shown to be an efficient one‐step matrix; however, a high‐resolution mass spectrometer was required in the low mass range due to carbon clusters. Titanium oxide (TiO2) is another commonly used development powder, especially for dark nonporous surfaces. Here, forensic TiO2 powder is utilized as a single‐step development and matrix technique for chemical imaging of latent fingerprints without the requirement of a high‐resolution mass spectrometer. All studied compounds were successfully detected when TiO2 was used as the matrix in positive mode, although, generally, the overall ion signals were lower than the previously studied CFP. TiO2 provided quality mass spectrometry (MS) images of endogenous and exogenous latent fingerprint compounds. The subsequent addition of traditional matrices on top of the TiO2 powder was ineffective for universal detection of latent fingerprint compounds. Forensic TiO2 development powder works as an efficient single‐step development and matrix technique for MALDI‐MSI analysis of latent fingerprints in positive mode and does not require a high‐resolution mass spectrometer for analysis. 相似文献
6.
Reactive oxygen species (ROS) are hypothesized to play a role in the sonoporation mechanisms. Nevertheless, the acoustical phenomenon behind the ROS production as well as the exact mechanisms of ROS action involved in the increased cell membrane permeability are still not fully understood. Therefore, we investigated the key processes occurring at the molecular level in and around microbubbles subjected to ultrasound using computational chemistry methods. To confirm the molecular simulation predictions, we measured the ROS production by exposing SonoVue® microbubbles (MBs) to ultrasound using biological assays. To investigate the role of ROS in cell membrane permeabilization, cells were subjected to ultrasound in presence of MBs and plasmid encoding reporter gene, and the transfection level was assessed using flow cytometry. The molecular simulations showed that under sonoporation conditions, ROS can form inside the MBs. These radicals could easily diffuse through the MB shell toward the surrounding aqueous phase and participate in the permeabilization of nearby cell membranes. Experimental data confirmed that MBs favor spontaneous formation of a host of free radicals where HO was the main ROS species after US exposure. The presence of ROS scavengers/inhibitors during the sonoporation process decreased both the production of ROS and the subsequent transfection level without significant loss of cell viability. In conclusion, the exposure of MBs to ultrasound might be the origin of chemical effects, which play a role in the cell membrane permeabilization and in the in vitro gene delivery when generated in its proximity. 相似文献
7.
A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate 下载免费PDF全文
David Van Craen Prof. Dr. Markus Albrecht Prof. Dr. Gerhard Raabe Fangfang Pan Prof. Dr. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3255-3258
Dimeric hierarchically‐assembled titanium(IV) helicates are in solvent‐dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene‐substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels–Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity. 相似文献
8.
Specific Design of Titanium(IV) Phenolato Chelates Yields Stable and Accessible,Effective and Selective Anticancer Agents 下载免费PDF全文
Sigalit Meker Dr. Ori Braitbard Dr. Matthew D. Hall Prof. Jacob Hochman Prof. Edit Y. Tshuva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9986-9995
Octahedral titanium(IV) complexes of phenolato hexadentate ligands were developed and showed very high stability for days in water solutions. In vitro cytotoxicity studies showed that, whereas tetrakis(phenolato) systems are generally of low activity presumably due to inaccessibility, smaller bis(phenolato)bis(alkoxo) complexes feature high anticancer activity and accessibility even without formulations, also toward a cisplatin‐resistant cell line. An all‐aliphatic control complex was unstable and inactive. A leading phenolato complex also revealed: 1) high durability in fully aqueous solutions; accordingly, negligible loss of activity after preincubation for three days in medium or in serum; 2) maximal cellular accumulation and induction of apoptosis following 24–48 h of administration; 3) reduced impact on noncancerous fibroblast cells; 4) in vivo efficacy toward lymphoma cells in murine model; 5) high activity in NCI‐60 panel, with average GI50 of 4.6±2 μm . This newly developed family of TiIV complexes is thus of great potential for anticancer therapy. 相似文献
9.
A series of carbon-coated, nitrogen-doped titanium dioxide photocatalysts was produced and characterized. N-doped TiO2 powder samples were prepared using a sol-gel method and subsequently used for making doped-TiO2 thin films on glass substrates. Carbon layers were coated on the films by a thermal decomposition method using catechol. Diffuse reflectance spectra and Mott-Schottky analyses of the samples proved that nitrogen doping and carbon coating can slightly lower the band gap of TiO2, broaden its absorption to visible light and enhance its n-type character. According to photocatalytic tests against model contaminants, carbon-coated nitrogen-doped TiO2 films have better performance than simple TiO2 on the degradation of Rhodamine B dye molecules, but are poorly effective for degrading 4-chlorophenol molecules. Several possible explanations are proposed for this result, supported by scavenging experiments. This reveals the importance of a broad substrate scope when assessing new photocatalytic materials for water treatment, something which is often overlooked in many literature studies. 相似文献
10.
《Arabian Journal of Chemistry》2020,13(11):8424-8457
Nowadays, increasing extortions regarding environmental problems and energy scarcity have stuck the development and endurance of human society. The issue of inorganic and organic pollutants that exist in water from agricultural, domestic, and industrial activities has directed the development of advanced technologies to address the challenges of water scarcity efficiently. To solve this major issue, various scientists and researchers are looking for novel and effective technologies that can efficiently remove pollutants from wastewater. Nanoscale metal oxide materials have been proposed due to their distinctive size, physical and chemical properties along with promising applications. Cupric Oxide (CuO) is one of the most commonly used benchmark photocatalysts in photodegradation owing to the fact that they are cost-effective, non-toxic, and more efficient in absorption across a significant fraction of solar spectrum. In this review, we have summarized synthetic strategies of CuO fabrication, modification methods with applications for water treatment purposes. Moreover, an elaborative discussion on feasible strategies includes; binary and ternary heterojunction formation, Z-scheme based photocatalytic system, incorporation of rare earth/transition metal ions as dopants, and carbonaceous materials serving as a support system. The mechanistic insight inferring photo-induced charge separation and transfer, the functional reactive radical species involved in a photocatalytic reaction, have been successfully featured and examined. Finally, a conclusive remark regarding current studies and unresolved challenges related to CuO are put forth for future perspectives. 相似文献