全文获取类型
收费全文 | 5911篇 |
免费 | 826篇 |
国内免费 | 592篇 |
专业分类
化学 | 3277篇 |
晶体学 | 38篇 |
力学 | 162篇 |
综合类 | 81篇 |
数学 | 2703篇 |
物理学 | 1068篇 |
出版年
2024年 | 5篇 |
2023年 | 37篇 |
2022年 | 106篇 |
2021年 | 169篇 |
2020年 | 179篇 |
2019年 | 203篇 |
2018年 | 150篇 |
2017年 | 246篇 |
2016年 | 282篇 |
2015年 | 240篇 |
2014年 | 368篇 |
2013年 | 578篇 |
2012年 | 414篇 |
2011年 | 407篇 |
2010年 | 377篇 |
2009年 | 404篇 |
2008年 | 444篇 |
2007年 | 454篇 |
2006年 | 329篇 |
2005年 | 303篇 |
2004年 | 210篇 |
2003年 | 196篇 |
2002年 | 166篇 |
2001年 | 173篇 |
2000年 | 109篇 |
1999年 | 100篇 |
1998年 | 70篇 |
1997年 | 68篇 |
1996年 | 63篇 |
1995年 | 80篇 |
1994年 | 64篇 |
1993年 | 64篇 |
1992年 | 64篇 |
1991年 | 45篇 |
1990年 | 17篇 |
1989年 | 23篇 |
1988年 | 22篇 |
1987年 | 13篇 |
1986年 | 15篇 |
1985年 | 15篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 17篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1973年 | 6篇 |
1972年 | 2篇 |
1971年 | 1篇 |
排序方式: 共有7329条查询结果,搜索用时 15 毫秒
31.
M. Sc. Mukesh Kumar Singh Prof. Gopalan Rajaraman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):980-983
This theoretical study suggests that CH???π stacking interactions between monomeric units can be used to design novel single‐chain magnets (SCMs), as the sign of coupling is predictable and such chains inherently yield negative axial anisotropy, a condition often difficult to achieve in conventional SCMs. 相似文献
32.
Pyrrolo‐dC Metal‐Mediated Base Pairs in the Reverse Watson–Crick Double Helix: Enhanced Stability of Parallel DNA and Impact of 6‐Pyridinyl Residues on Fluorescence and Silver‐Ion Binding 下载免费PDF全文
Haozhe Yang Hui Mei Prof. Dr. Frank Seela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):10207-10219
Reverse Watson–Crick DNA with parallel‐strand orientation (ps DNA) has been constructed. Pyrrolo‐dC (PyrdC) nucleosides with phenyl and pyridinyl residues linked to the 6 position of the pyrrolo[2,3‐d]pyrimidine base have been incorporated in 12‐ and 25‐mer oligonucleotide duplexes and utilized as silver‐ion binding sites. Thermal‐stability studies on the parallel DNA strands demonstrated extremely strong silver‐ion binding and strongly enhanced duplex stability. Stoichiometric UV and fluorescence titration experiments verified that a single 2pyPyrdC–2pyPyrdC pair captures two silver ions in ps DNA. A structure for the PyrdC silver‐ion base pair that aligns 7‐deazapurine bases head‐to‐tail instead of head‐to‐head, as suggested for canonical DNA, is proposed. The silver DNA double helix represents the first example of a ps DNA structure built up of bidentate and tridentate reverse Watson–Crick base pairs stabilized by a dinuclear silver‐mediated PyrdC pair. 相似文献
33.
34.
Using controlled radical polymerization to confirm the lower critical solution temperature of an N‐(alkoxyalkyl) acrylamide polymer in aqueous solution 下载免费PDF全文
Xeniya Savelyeva Lucia Li Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2015,53(1):59-67
N‐(3‐Methoxypropyl) acrylamide (MPAM) was polymerized by controlled radical polymerization (CRP) methods such as nitroxide‐mediated polymerization (NMP) and reversible addition–fragmentation chain‐transfer polymerization (RAFT). CRP was expected to yield well‐defined polymers with sharp lower critical solution temperature (LCST) transitions. NMP with the BlocBuilder (2‐([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropanoic acid) and SG1 ([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino] oxidanyl) initiating system revealed low yields and lack of control (high dispersity, ? ~ 1.5–1.6, and inhibition of chain growth). However, RAFT was far more effective, with linear number average molecular weight, , versus conversion, X, plots, low ? ~ 1.2–1.4 and the ability to form block copolymers using N,N‐diethylacrylamide (DEAAM) as the second monomer. Poly(MPAM) (with = 13.7–25.3 kg mol?1) thermoresponsive behavior in aqueous media revealed cloud point temperatures (CPT)s between 73 and 92 °C depending on solution concentration (ranging from 1 to 3 wt %). The and the molecular weight distribution were the key factors determining the CPT and the sharpness of the response, respectively. Poly(MPAM)‐b‐poly(DEAAM) block copolymer ( = 22.3 kg mol?1, ? = 1.41, molar composition FDEAAM = 0.38) revealed dual LCSTs with both segments revealing distinctive CPTs (at 75 and 37 °C for poly(MPAM) and poly(DEAAM) blocks, respectively) by both UV–Vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 59–67 相似文献
35.
Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products 下载免费PDF全文
Dr. Ahmed M. Debela Dr. Mayreli Ortiz Dr. Valerio Beni Prof. Serge Thorimbert Dr. Denis Lesage Prof. Richard B. Cole Prof. Ciara K. O'Sullivan Prof. Bernold Hasenknopf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17721-17727
The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11O39{Sn(CH2)2CO}]8? and [P2W17O61{Sn(CH2)2CO}]6? have been used to link to a 5′‐NH2 terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis. 相似文献
36.
基于全球稀土资源的供需形势和中国稀土资源减少的趋势,运用系统动力学的模型来预测未来17年我国稀土资源储备量。选取了2000~2013的生产和消费数据,通过定量模拟计算中国稀土供需差波动系数,设计了稀土资源供需差波动范围分别为0%,20%的两个方案,模拟计算了两个方案的年储备量、累计储备量和储备量绝对值。方案一范围是(-0%,+0%),仿真预测出稀土未来17年累积储备量为720551 t,即战略储备规模达到720551 t,该方案下不论供需差发生如何波动,国家都会进行储备或释放调节;方案二范围是(-20%,+20%),预测出未来17年战略储备规模为461331 t,国家只需在这个范围外进行收储释放调节,从而调节市场供求,降低价格波动幅度。本文从不同供需差的波动系数来模拟计算储备量,目的是为国家相关部门在进行稀土储备决策时提供参考,可以根据我国经济景气状况和供需形势,以及稀土产业发展状况,进行不同规模的稀土储备。 相似文献
37.
Hyperbranched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits 下载免费PDF全文
Dr. Sai Bi Min Chen Xiaoqiang Jia Ying Dong Prof. Dr. Zonghua Wang 《Angewandte Chemie (International ed. in English)》2015,54(28):8144-8148
A hyper‐branched hybridization chain reaction (HB‐HCR) is presented herein, which consists of only six species that can metastably coexist until the introduction of an initiator DNA to trigger a cascade of hybridization events, leading to the self‐sustained assembly of hyper‐branched and nicked double‐stranded DNA structures. The system can readily achieve ultrasensitive detection of target DNA. Moreover, the HB‐HCR principle is successfully applied to construct three‐input concatenated logic circuits with excellent specificity and extended to design a security‐mimicking keypad lock system. Significantly, the HB‐HCR‐based keypad lock can alarm immediately if the “password” is incorrect. Overall, the proposed HB‐HCR with high amplification efficiency is simple, homogeneous, fast, robust, and low‐cost, and holds great promise in the development of biosensing, in the programmable assembly of DNA architectures, and in molecular logic operations. 相似文献
38.
Chain‐Growth Click Polymerization of AB2 Monomers for the Formation of Hyperbranched Polymers with Low Polydispersities in a One‐Pot Process 下载免费PDF全文
Yi Shi Robert W. Graff Xiaosong Cao Xiaofeng Wang Haifeng Gao 《Angewandte Chemie (International ed. in English)》2015,54(26):7631-7635
Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB2 monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed CuI, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83. 相似文献
39.
Colette J. Whitfield Andrew T. Turley Dr. Eimer M. Tuite Prof. Bernard A. Connolly Dr. Andrew R. Pike 《Angewandte Chemie (International ed. in English)》2015,54(31):8971-8974
A polymerase chain reaction (PCR) derived method for preparing long DNA, consisting of multiple repeat units of one to ten base pairs, is described. Two seeding oligodeoxynucleotides, so‐called oligoseeds, which encode the repeat unit and produce a duplex with 5′‐overhangs, are extended using a thermostable archaeal DNA polymerase. Multiple rounds of heat–cool extension cycles, akin to PCR, rapidly elongate the oligoseed. Twenty cycles produced long DNA with uniformly repeating sequences to over 20 kilobases (kb) in length. The polynucleotides prepared include [A]n/[T]n, [AG]n/[TC]n, [A2G]n/[T2C]n, [A3G]n/[T3C]n, [A4G]n/[T4C]n, [A9G]n/[T9C]n, [GATC]n/[CTAG]n, and [ACTGATCAGC]n/[TGACTAGTCG]n, indicating that the method is extremely flexible with regard to the repeat length and base sequence of the initial oligoseeds. DNA of this length (20 kb≈7 μm) with strictly defined base reiterations should find use in nanomaterial applications. 相似文献
40.
An Efficient Labelling Approach to Harness Backbone and Side‐Chain Protons in 1H‐Detected Solid‐State NMR Spectroscopy 下载免费PDF全文
Deni Mance Dr. Tessa Sinnige Mohammed Kaplan Siddarth Narasimhan Mark Daniëls Dr. Klaartje Houben Prof. Marc Baldus Dr. Markus Weingarth 《Angewandte Chemie (International ed. in English)》2015,54(52):15799-15803
1H‐detection can greatly improve spectral sensitivity in biological solid‐state NMR (ssNMR), thus allowing the study of larger and more complex proteins. However, the general requirement to perdeuterate proteins critically curtails the potential of 1H‐detection by the loss of aliphatic side‐chain protons, which are important probes for protein structure and function. Introduced herein is a labelling scheme for 1H‐detected ssNMR, and it gives high quality spectra for both side‐chain and backbone protons, and allows quantitative assignments and aids in probing interresidual contacts. Excellent 1H resolution in membrane proteins is obtained, the topology and dynamics of an ion channel were studied. This labelling scheme will open new avenues for the study of challenging proteins by ssNMR. 相似文献