全文获取类型
收费全文 | 1784篇 |
免费 | 186篇 |
国内免费 | 225篇 |
专业分类
化学 | 1432篇 |
晶体学 | 11篇 |
力学 | 56篇 |
综合类 | 32篇 |
数学 | 227篇 |
物理学 | 437篇 |
出版年
2023年 | 18篇 |
2022年 | 29篇 |
2021年 | 41篇 |
2020年 | 71篇 |
2019年 | 40篇 |
2018年 | 58篇 |
2017年 | 48篇 |
2016年 | 60篇 |
2015年 | 54篇 |
2014年 | 68篇 |
2013年 | 130篇 |
2012年 | 101篇 |
2011年 | 108篇 |
2010年 | 85篇 |
2009年 | 70篇 |
2008年 | 92篇 |
2007年 | 113篇 |
2006年 | 99篇 |
2005年 | 104篇 |
2004年 | 104篇 |
2003年 | 85篇 |
2002年 | 70篇 |
2001年 | 53篇 |
2000年 | 67篇 |
1999年 | 39篇 |
1998年 | 41篇 |
1997年 | 36篇 |
1996年 | 33篇 |
1995年 | 21篇 |
1994年 | 21篇 |
1993年 | 20篇 |
1992年 | 31篇 |
1991年 | 23篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 10篇 |
1986年 | 19篇 |
1985年 | 9篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 14篇 |
1981年 | 10篇 |
1980年 | 13篇 |
1979年 | 5篇 |
1978年 | 10篇 |
1977年 | 7篇 |
1976年 | 17篇 |
1973年 | 4篇 |
1972年 | 2篇 |
排序方式: 共有2195条查询结果,搜索用时 656 毫秒
1.
建立了水产品中11种海洋生物毒素的高效液相色谱-四极杆/静电场轨道阱高分辨质谱(HPLC-Q-Orbitrap HRMS)检测方法。该方法采用分级提取原理,结合分散固相萃取技术(dSPE)和载体辅助液液萃取技术(SLLE),建立了对亲水性及亲脂性海洋生物毒素的"一站式"提取净化体系。在优化条件下,11种毒素在一定质量浓度范围内具有良好的线性关系,相关系数(r)均大于0.99。该方法对11种毒素的检出限为1~10μg/kg,定量下限为2~20μg/kg,加标回收率为55.6%~122%,相对标准偏差为5.4%~16%。方法快速高效,可操作性强,解决了不同理化性质的海洋生物毒素的通用性检测问题,可满足水产品中海洋生物毒素的快速筛查要求。 相似文献
2.
Prof. Sławomir J. Grabowski 《Chemphyschem》2019,20(4):565-574
ωB97XD/aug-cc-pVTZ calculations were performed for complexes of dihydrogen, cyclopropane, cyclobutane and cyclopentane, with simple proton donating species such as hydrogen fluoride, hydrogen chloride, water, hydrogen cyanide and acetylene. Numerous dependencies between geometrical, energetic and topological parameters of complexes considered were found, since various theoretical approaches were applied: Quantum Theory of ‘Atoms in Molecules’ (QTAIM), Natural Bond Orbital (NBO) method and energy decomposition analysis (EDA). It was confirmed that complexes of dihydrogen and cyclopropane are linked through the A−H…σ interactions that may be classified as hydrogen bonds. In the case of complexes of cyclobutane such hydrogen bonds are rather weak. Other type and also weak A−H…C hydrogen bonds are formed for complexes with cyclopentane. 相似文献
3.
气敏传感器具有气体识别、探测和监测等功能, 广泛应用于工业生产等领域, 但在泄漏预警时缺乏迅速识别和定位等功能. 本文基于传感器制备工艺偏差分析, 通过对传感器气敏机制的研究, 提出一种基于Ni-SnO2纳米颗粒的气敏传感器物理不可克隆函数(Gas Sensor-Physical Unclonable Function, GS-PUF)设计方案. 该方案利用掺杂Ni元素的方法, 结合静电喷雾沉积技术制备Ni-SnO2气敏传感器, 以获取更加稳定可靠的物理特征值, 然后采集气敏传感器对不同浓度下气体的响应数据, 最后利用随机阻值多位平衡算法比较不同组气敏传感器响应电信号值, 实现PUF数据输出. 制备每组样本可产生128位二进制数据的多组PUF样本, 进行对比实验. 结果表明, 所设计的GS-PUF具有气体泄漏源头识别定位的功能, 且随机性提升至99%, 唯一性达49.80%. 相似文献
4.
色彩是民族服饰的核心要素,也是民族文化元素的重要组成部分,构建一套兼具科学性与实用性的色彩体系极具挑战性。在传统色彩地理学方法基础上,通过提取主题色和改进的关联规则挖掘方法,获取色彩数据、寻找色彩规则,并对其进行自然色彩体系(NCS)编谱分析,构建了一套苗族服饰色彩体系(Miao’s costume color system,MCCS)。该体系有助于进一步挖掘苗族服饰的配色规律,实现对苗族服饰色彩的数字化保护,为民族服饰色彩传承机理的探索与研究提供新的思路。 相似文献
5.
Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer 下载免费PDF全文
Jeffrey P. Calame 《Journal of Polymer Science.Polymer Physics》2015,53(10):740-759
Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759 相似文献
6.
Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines 下载免费PDF全文
Wataru Makiguchi Shinzo Kobayashi Keisuke Furukawa Hiroki Iida Yoshio Furusho Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):990-999
An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999 相似文献
7.
以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外分光光度计研究了其热分解现象和热分解动力学,采用表面张力仪对其表面活性进行了测定.结果表明,所合成的引发剂AIBL具有预想的结构和较高的纯度,其热分解反应属于一级反应,热分解活化能为134.80 k J/mol,70℃下水中的半衰期约为4 h;AIBL在水溶液中具有表面活性,其临界胶束浓度为0.13 g/L,对应的表面张力为33.57 m N/m.以丙烯酰胺为单体、AIBL为引发剂制备了水溶性端基疏水聚合物SPAM.采用溴化法研究其转化率,应用乌氏黏度法、零切黏度法以及荧光探针对其缔合作用进行了研究.结果表明,AIBL具有良好的引发丙烯酰胺聚合的能力;相对于不带疏水长链的引发剂所合成的聚合物PAM,SPAM具有明显的疏水缔合效应,这说明AIBL成功地将疏水长链引入到聚合物的端基中,从而形成端基疏水聚合物. 相似文献
8.
Yuqing Yang Ehsan Raee Prof. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(10):e202104332
A unique trend in the binding affinity between cationic metal−organic cages (MOCs) and external counteranions in aqueous media was observed. Similar to many macroions, two MOCs, sharing similar structures but carrying different number of charges, self-assembled into hollow spherical single-layered blackberry-type structures through counterion-mediated attraction. Dynamic and static light scattering and isothermal titration calorimetry measurements confirm the stronger interactions among less charged MOCs and counteranions than that of highly charged MOCs, leading to larger assembly sizes. DOSY NMR measurements suggest the significance of thick hydration shells of highly charged MOCs, inhibiting the MOC-counterion binding and weakening the interaction between them. This study demonstrates that the greater role played by hydration shell on ion-pair formation comparing with charge density of MOCs. 相似文献
9.
Kamila B. Muchowska Dominic J. Pascoe Stefan Borsley Ivan V. Smolyar Ioulia K. Mati Catherine Adam Gary S. Nichol Kenneth B. Ling Scott L. Cockroft 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14710-14716
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
10.
This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems. 相似文献