全文获取类型
收费全文 | 150468篇 |
免费 | 28329篇 |
国内免费 | 15722篇 |
专业分类
化学 | 118645篇 |
晶体学 | 1643篇 |
力学 | 7754篇 |
综合类 | 867篇 |
数学 | 16765篇 |
物理学 | 48845篇 |
出版年
2024年 | 404篇 |
2023年 | 2355篇 |
2022年 | 4239篇 |
2021年 | 4472篇 |
2020年 | 5668篇 |
2019年 | 6604篇 |
2018年 | 5086篇 |
2017年 | 4436篇 |
2016年 | 8673篇 |
2015年 | 8715篇 |
2014年 | 9955篇 |
2013年 | 12459篇 |
2012年 | 13306篇 |
2011年 | 12919篇 |
2010年 | 10178篇 |
2009年 | 9873篇 |
2008年 | 9872篇 |
2007年 | 8601篇 |
2006年 | 7823篇 |
2005年 | 6877篇 |
2004年 | 5587篇 |
2003年 | 4606篇 |
2002年 | 5183篇 |
2001年 | 4012篇 |
2000年 | 3637篇 |
1999年 | 2803篇 |
1998年 | 2113篇 |
1997年 | 1865篇 |
1996年 | 1891篇 |
1995年 | 1671篇 |
1994年 | 1468篇 |
1993年 | 1196篇 |
1992年 | 1080篇 |
1991年 | 938篇 |
1990年 | 777篇 |
1989年 | 614篇 |
1988年 | 474篇 |
1987年 | 416篇 |
1986年 | 391篇 |
1985年 | 312篇 |
1984年 | 221篇 |
1983年 | 188篇 |
1982年 | 139篇 |
1981年 | 100篇 |
1980年 | 69篇 |
1979年 | 35篇 |
1978年 | 28篇 |
1976年 | 23篇 |
1975年 | 23篇 |
1957年 | 31篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
62.
在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。 相似文献
63.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
64.
65.
Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Bin Liu Hongyun Fang Prof. Xiaofang Li Wenting Cai Lipiao Bao Marc Rudolf Fabian Plass Prof. Louzhen Fan Prof. Xing Lu Prof. Dirk M. Guldi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):746-752
Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc3N@C80 to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc3N@C80 and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics. 相似文献
66.
67.
68.
Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Deia Abd El‐Hady Hassan M. Albishri Rajesh Rengarajan 《Biomedical chromatography : BMC》2015,29(6):925-934
In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r2) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
69.
针对星模拟器与星敏感器观星的色温不匹配对星敏感器光信号定标精度产生的影响,设计了一种基于LED的多色温多星等单星模拟器,采用该系统模拟特定色温的星光用于星敏感器光信号定标,大幅降低了色温非匹配带来的定标误差。从理论上分析了色温非匹配影响星敏感器光信号的定标精度的机理;根据设计指标确定了星模拟器的设计方案,主要解决了光源的选型、多色温多星等单星模拟器驱动和控制系统、色温星等匹配算法、多色温多星等单星模拟器软件设计四项关键技术问题;对多色温多星等单星模拟器进行了标定和性能测试:0等星4000K和3等星7000 K星光的光谱匹配误差分别为4.87%和7.83%,星等等级分别为0.03和2.93;光源稳定后,多色温多星等单星模拟器的平行光管出口Φ100 mm口径内的照度非均匀度为6.5%,均满足设计指标。 相似文献
70.
Nonlinear Dynamics - In this paper, the current-controlled DC–DC buck converter from a new perspective are studied through the switching theory of flow, and the analytical conditions of the... 相似文献