全文获取类型
收费全文 | 86856篇 |
免费 | 13695篇 |
国内免费 | 5488篇 |
专业分类
化学 | 82266篇 |
晶体学 | 1253篇 |
力学 | 3040篇 |
综合类 | 197篇 |
数学 | 8482篇 |
物理学 | 10801篇 |
出版年
2024年 | 41篇 |
2023年 | 332篇 |
2022年 | 817篇 |
2021年 | 1079篇 |
2020年 | 1585篇 |
2019年 | 3256篇 |
2018年 | 2989篇 |
2017年 | 3649篇 |
2016年 | 4005篇 |
2015年 | 6161篇 |
2014年 | 6147篇 |
2013年 | 8619篇 |
2012年 | 6858篇 |
2011年 | 6800篇 |
2010年 | 5584篇 |
2009年 | 5743篇 |
2008年 | 5905篇 |
2007年 | 5247篇 |
2006年 | 4840篇 |
2005年 | 4576篇 |
2004年 | 4101篇 |
2003年 | 3477篇 |
2002年 | 3935篇 |
2001年 | 2296篇 |
2000年 | 2031篇 |
1999年 | 1134篇 |
1998年 | 507篇 |
1997年 | 452篇 |
1996年 | 506篇 |
1995年 | 473篇 |
1994年 | 448篇 |
1993年 | 309篇 |
1992年 | 324篇 |
1991年 | 197篇 |
1990年 | 154篇 |
1989年 | 149篇 |
1988年 | 158篇 |
1987年 | 125篇 |
1986年 | 93篇 |
1985年 | 81篇 |
1984年 | 81篇 |
1983年 | 30篇 |
1982年 | 76篇 |
1981年 | 102篇 |
1980年 | 114篇 |
1979年 | 118篇 |
1978年 | 94篇 |
1977年 | 70篇 |
1976年 | 64篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
22.
A (di)graph is supereulerian if it contains a spanning eulerian sub(di)graph. This property is a relaxation of hamiltonicity. Inspired by this analogy with hamiltonian cycles and by similar results in supereulerian graph theory, we analyze a number of sufficient Ore type conditions for a digraph to be supereulerian. Furthermore, we study the following conjecture due to Thomassé and the first author: if the arc‐connectivity of a digraph is not smaller than its independence number, then the digraph is supereulerian. As a support for this conjecture we prove it for digraphs that are semicomplete multipartite or quasitransitive and verify the analogous statement for undirected graphs. 相似文献
23.
Field-effect transistors (FETs) are one of the most widely-used electronic sensors for continuous monitoring and detection of contaminants such as pharmaceuticals and endocrine-disrupting compounds at low concentrations. FETs have been successfully utilized for the rapid analysis of these environmental pollutants due to their advantageous material properties like the disposability, rapid responses and simplicity. This paper presented an up-to-date overview of applied strategies with different bio-based materials in order to enhance the analytical performances of the designed sensors. Comparison and discussion were made between characteristics of recently engineered FET bio-sensors used for the detection of famous and selected pharmaceutical compounds in the literature. The recent progress in environmental research applications, comments on interesting trends, current challenge for future research in endocrine-disrupting chemicals’ (EDCs) detection using FETs biosensors were highlighted. 相似文献
24.
A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection 下载免费PDF全文
Mir Ali Farajzadeh Mohammad Reza Afshar Mogaddam Ali Akbar Alizadeh Nabil 《Biomedical chromatography : BMC》2015,29(12):1921-1931
In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
25.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones 下载免费PDF全文
Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
26.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification 下载免费PDF全文
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献
27.
Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals 下载免费PDF全文
Dr. Yuya Domoto Dr. Eric Busseron Prof. Dr. Mounir Maaloum Dr. Emilie Moulin Prof. Dr. Nicolas Giuseppone 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1938-1948
We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by 1H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases. 相似文献
28.
Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures 下载免费PDF全文
Partha Malakar Prof. Dr. Edamana Prasad 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5093-5100
Self‐assembly of AB2 and AB3 type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model. 相似文献
29.
Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2 下载免费PDF全文
Stefan Kissling Peter T. Altenbuchner Dr. Maximilian W. Lehenmeier Dr. Eberhardt Herdtweck Dr. Peter Deglmann Dr. Uwe B. Seemann Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8148-8157
The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO2 revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO2 co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion. 相似文献
30.
In this paper, we study the local linear convergence properties of a versatile class of Primal–Dual splitting methods for minimizing composite non-smooth convex optimization problems. Under the assumption that the non-smooth components of the problem are partly smooth relative to smooth manifolds, we present a unified local convergence analysis framework for these methods. More precisely, in our framework, we first show that (i) the sequences generated by Primal–Dual splitting methods identify a pair of primal and dual smooth manifolds in a finite number of iterations, and then (ii) enter a local linear convergence regime, which is characterized based on the structure of the underlying active smooth manifolds. We also show how our results for Primal–Dual splitting can be specialized to cover existing ones on Forward–Backward splitting and Douglas–Rachford splitting/ADMM (alternating direction methods of multipliers). Moreover, based on these obtained local convergence analysis result, several practical acceleration techniques are discussed. To exemplify the usefulness of the obtained result, we consider several concrete numerical experiments arising from fields including signal/image processing, inverse problems and machine learning. The demonstration not only verifies the local linear convergence behaviour of Primal–Dual splitting methods, but also the insights on how to accelerate them in practice. 相似文献