全文获取类型
收费全文 | 1935篇 |
免费 | 172篇 |
国内免费 | 357篇 |
专业分类
化学 | 1401篇 |
晶体学 | 14篇 |
力学 | 33篇 |
综合类 | 15篇 |
数学 | 160篇 |
物理学 | 841篇 |
出版年
2024年 | 2篇 |
2023年 | 29篇 |
2022年 | 28篇 |
2021年 | 40篇 |
2020年 | 62篇 |
2019年 | 47篇 |
2018年 | 42篇 |
2017年 | 70篇 |
2016年 | 70篇 |
2015年 | 56篇 |
2014年 | 100篇 |
2013年 | 160篇 |
2012年 | 124篇 |
2011年 | 158篇 |
2010年 | 115篇 |
2009年 | 135篇 |
2008年 | 145篇 |
2007年 | 160篇 |
2006年 | 124篇 |
2005年 | 96篇 |
2004年 | 71篇 |
2003年 | 74篇 |
2002年 | 59篇 |
2001年 | 39篇 |
2000年 | 64篇 |
1999年 | 52篇 |
1998年 | 49篇 |
1997年 | 55篇 |
1996年 | 42篇 |
1995年 | 25篇 |
1994年 | 32篇 |
1993年 | 39篇 |
1992年 | 28篇 |
1991年 | 18篇 |
1990年 | 7篇 |
1989年 | 12篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有2464条查询结果,搜索用时 265 毫秒
131.
Concentration sensitivity is a key performance indicator for analytical techniques including for capillary electrophoresis-mass spectrometry (CE–MS) with electrospray ionization (ESI). In this study, a flow-through microvial interface was used to couple CE with MS and improve the ESI stability and detection sensitivity. By infusing a peptide mixture through the interface into an MS detector at a typical flow rate for CE-MS analysis, the spatial region near the interface was mapped for MS signal intensity. When the sprayer tip was within a 6 × 6.5 × 5 mm region in front of the MS inlet, the ESI was stable with no significant loss of signal intensity for ions with m/z 239. Finite element simulations showed that the average electric field strength at the emitter tip did not change significantly with minor changes in emitter tip location. Experiments were conducted with four different mass spectrometer platforms coupled to CE via the flow-through microvial interface. Key performance indicators, that is, limit of detection (LOD) and linearity of calibration curves were measured for nine amino acids and five peptides. Inter- and intraday reproducibility were also tested. The results were shown to be suitable for quantification when internal standards were used. 相似文献
132.
采用高温固相法成功制备了Na3Sc2-x-y(PO4)3∶xTm3+,yDy3+荧光粉,利用X射线衍射仪、扫描电子显微镜和荧光光谱仪对荧光粉进行了物相、形貌和发光性能进行了表征。 在Na3Sc2(PO4)3∶0.06Tm3+,yDy3+荧光粉中,物质的量分数6%的Tm3+和6%的Dy3+在360 nm激发下呈现出白光发射,其发射光谱在460~685 nm范围内存在Tm3+位于457 nm的特征发射峰,对应于Tm3+的3H6→1D2跃迁,以及Dy3+位于483、577和672 nm处的3个特征发射峰,分别对应于Dy3+的4F9/2→6H15/2、4F9/2→6H13/2和4F9/2→6H11/2的跃迁。 观测到Na3Sc2(PO4)3∶Tm3+荧光粉的发射光谱与Na3Sc2(PO4)3∶Dy3+的激发光谱有较好的重叠,且Tm3+的荧光寿命随Dy3+浓度的增加逐渐降低,因此在Na3Sc2(PO4)3∶Tm3+,Dy3+荧光粉中存在Tm3+向Dy3+的能量传递。 利用Dexter和Reisfeld近似分析了能量转移机制,发现从Tm3+到Dy3+的能量传递临界距离为1.6 nm,能量传递过程是通过偶极-偶极相互作用进行的。 Na3Sc2(PO4)3∶0.06Tm3+,0.06Dy3+荧光粉具有较好的耐受热猝灭性能,在423、473和523 K时的发射强度分别为298 K时发射强度的97.6%、89.2%和78.6%。 随着Dy3+浓度的增加,Na3Sc2(PO4)3∶0.06Tm3+,yDy3+荧光粉的发光颜色由蓝色转变为白色,再由白色变黄色。 Na3Sc2(PO4)3∶Tm3+,Dy3+荧光粉作为一种可调色或单相白光荧光粉在发光二极管上具有潜在的应用前景。 相似文献
133.
以脯氨酸(Pro)为保护剂,盐酸羟胺为还原剂,通过一步化学还原法制备脯氨酸稳定的铜纳米团簇(Cu NCs)。采用分子荧光仪和紫外可见吸收仪对Cu NCs的光学性质进行分析,通过透射电子显微镜(TEM)、X射线光电子能谱(XPS)和傅里叶变换红外波谱仪(FTIR)对Cu NCs的结构进行表征。TEM图像显示Cu NCs的形貌为球状,平均直径为1.89 nm。Cu NCs溶液在紫外光下呈蓝色,最大激发和发射波长分别为397和458 nm。Cu NCs的荧光可以选择性地被三硝基苯酚(PA)猝灭。该探针对PA的线性响应范围为0.5~15μmol/L和20~70μmol/L,检测限为0.092μmol/L(S/N=3)。可能的检测机理是静态猝灭和内滤效应。此外,该荧光探针已成功应用于实际水样品中PA的测定。 相似文献
134.
通过带有PEG官能团的双丙烯酸酯大分子单体的RAFT环聚合反应合成含有十一元环重复结构的PEG大分子刷.不同PEG长度的连接1,2,3-三氮唑的双丙烯酸酯大分子单体通过点击化学反应合成.PEG侧链的较大位阻效应影响双丙烯酸酯大分子单体的聚合行为,以致于双丙烯酸酯大分子单体优先进行环化聚合反应而不发生交联反应.核磁数据和凝胶渗透色谱证明高效的环化聚合反应,而且没有副反应发生.PEG大分子刷在紫外光激发下有较强的荧光,而荧光则强烈依赖于聚合物刷的浓度,这归因于环聚合物在水中的聚集.PEG大分子刷的荧光能被DNA淬灭. 相似文献
135.
采用高温固相法制备了Ca9Al(PO4)7∶Eu2+蓝色荧光粉,研究了Ca9Al(PO4)7∶Eu2+的发光、浓度猝灭及温度稳定性.Ca9Al(PO4)7∶Eu2+的激发光谱覆盖200~350 nm紫外区;发射光谱为一主峰位于445 nm的宽谱,对应Eu2+的4f6 5d1--→4f特征跃迁.研究发现,随Eu2+掺杂量的增大,Ca9Al(PO4)7∶Eu2+的发射强度呈现先增大、后减小的变化趋势,最大发射强度对应的Eu2+掺杂量为0.01,即存在浓度猝灭效应,对应的机理为电偶极-电偶极相互作用;依据晶格常数,得出临界距离为2.297 nm.在25~300℃范围内改变光谱测量温度,发现温度升高到150℃时,Ca9Al(PO4)7∶Eu2+的发射强度变为25℃时的81.0%,对应的激活能为0.268 eV,说明材料具有较好的温度稳定性. 相似文献
136.
Yujin Lee Hyo Geun Koo Seung Pyo Jang Alan B. Erdmann Samantha S. Vernetti Cheal Kim 《Supramolecular chemistry》2014,26(3-4):245-250
The synthesis, spectroscopic characterisation, conformational switching and fluorescence quenching efficiency of a resorcinarene-based cavitand containing Zn-salen (Zn-Cav) are reported. Synthesis of Zn-Cav was accomplished by the condensation of a quinoxaline derivatised with Zn-salen and a resorcinarene-based cavitand containing three quinoxalines. 1H NMR spectroscopy confirmed that in DMSO, chloroform and acetone Zn-Cav resides in the vase conformation. The molecular geometry of Zn-Cav selectively changes from vase to kite under acidic conditions. Detection by fluorescence quenching of nitro-containing molecules, such as 4-nitrotoluene, 2,4-dinitrotoluene and 2,3-dimethyl-2,3-dinitrobutane was explored by spectrofluorimetry. It was found that the fluorescence of Zn-Cav is efficiently quenched by nitroaromatic compounds. 相似文献
137.
Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency 下载免费PDF全文
Bappaditya Gole Dr. Arun Kumar Bar Prof. Partha Sarathi Mukherjee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2276-2291
Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (KS) as well as collisional constants (KC) has revealed that MOF‐1 and MOF‐2 have higher KS values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level. 相似文献
138.
Rationally Investigating the Influence of T1 Location on Electroluminescence Performance of Aryl Amine Modified Phosphine Oxide Materials 下载免费PDF全文
Chunmiao Han Liping Zhu Jing Li Fangchao Zhao Dr. Hui Xu Prof. Dongge Ma Prof. Pengfei Yan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16350-16359
The correspondence between triplet location effect and host‐localized triplet–triplet annihilation and triplet–polaron quenching effects was performed on the basis of a series of naphthyldiphenylamine (DPNA)‐modified phosphine oxide hosts. The number and ratio of DPNA and diphenylphosphine oxide was adjusted to afford symmetrical and unsymmetrical molecular structures and different electronic environments. As designed, the first triplet (T1) states were successfully localized on the specific DPNA chromophores. Owing to the meso‐ and multi‐insulating linkages, identical optical properties and comparable electrical performance was observed, including the same first singlet (S1) and T1 energy levels to support the similar singlet and triplet energy transfer and the close frontier molecular orbital energy levels. This established the basis of rational investigation on T1 location effect without interference from other optoelectronic factors. 相似文献
139.
140.
在pH 2.1~4.1的Britton-Robinson(BR)缓冲溶液中,头孢噻肟钠(CFTM)与吖黄素(AF)形成1∶1的离子缔合物,导致吖黄素溶液荧光猝灭。当分别于最大激发和最大发射波长(λex/λem=266 nm/506 nm)进行测量时,荧光猝灭值(ΔF)与CFTM浓度在一定范围呈良好的线性关系。该方法灵敏度高,测定CFTM的线性范围和检出限分别为0.07~5.0 mg/L和0.021 mg/L。考察了体系的荧光光谱特征、适宜的反应条件和共存物质的影响,讨论了离子缔合物的组成。基于离子缔合反应,发展了测定CFTM的高灵敏、简便、快速的新方法,将其用于血清和尿液中CFTM的测定,结果满意。 相似文献