全文获取类型
收费全文 | 692篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 509篇 |
晶体学 | 5篇 |
力学 | 23篇 |
数学 | 58篇 |
物理学 | 123篇 |
出版年
2023年 | 5篇 |
2022年 | 14篇 |
2021年 | 13篇 |
2020年 | 14篇 |
2019年 | 26篇 |
2018年 | 9篇 |
2017年 | 20篇 |
2016年 | 24篇 |
2015年 | 17篇 |
2014年 | 26篇 |
2013年 | 45篇 |
2012年 | 39篇 |
2011年 | 39篇 |
2010年 | 21篇 |
2009年 | 22篇 |
2008年 | 36篇 |
2007年 | 37篇 |
2006年 | 34篇 |
2005年 | 39篇 |
2004年 | 20篇 |
2003年 | 17篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 9篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1988年 | 5篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1968年 | 2篇 |
1967年 | 2篇 |
1964年 | 2篇 |
1962年 | 2篇 |
1957年 | 2篇 |
1934年 | 3篇 |
排序方式: 共有718条查询结果,搜索用时 15 毫秒
51.
J.S. Yadav B.V. Subba Reddy V. Sunitha K. Srinivasa Reddy K.V.S. Ramakrishna 《Tetrahedron letters》2004,45(42):7947-7950
Aryl amines react with endocyclic ene-carbamates such as tert-butyl 2,3-dihydro-1H-1-pyrrolecarboxylate and tert-butyl 1,2,3,4-tetrahydro-1-pyridinecarboxylate, on the surface of montmorillonite KSF clay under mild conditions to afford the corresponding 3-aminopropylhexahydropyrrolo[3,2-c]quinoline or 4-aminobutyloctahydrobenzo[h][1,6]naphthyridine derivatives in excellent yields with moderate diastereoselectivity. 相似文献
52.
53.
Nirogi R Bhyrapuneni G Kandikere V Mudigonda K Ajjala D Suraneni R Mukkanti K 《Biomedical chromatography : BMC》2008,22(12):1424-1433
A sensitive and selective high-performance liquid chromatography-positive ion electrospray tandem mass spectrometry method was developed and validated for the quantification of amisulpride in 100 microL of human plasma. Following liquid-liquid extraction, the analytes were separated using an isocratic mobile phase on a reverse-phase column and analyzed by MS/MS in the multiple reaction monitoring mode using the respective (M + H)(+) ions, m/z 370-242 for amisulpride and m/z 341-112 for the internal standard. The assay exhibited a linear dynamic range with a lower range of 0.1-100 ng/mL and a higher range of 1-500 ng/mL of amisulpride in human plasma. The lower limit of quantification was 0.1 ng/mL with a relative standard deviation of less than 10%. Acceptable precision and accuracy were obtained for both linearity ranges. A run time of 2.0 min for each sample made it possible to analyze more than 275 human plasma samples per day. The validated method has been successfully used to analyze plasma samples for application in pharmacokinetic studies. 相似文献
54.
A highly sensitive and selective spectrofluorimetric method for the determination of 0.05-2.00 mug germanium is described. Germanium is treated with chromotropic acid at pH 2.5 and the resultant anionic complex is extracted as an ion pair with rhodamine into toluene. Addition of butanol to the organic extract releases the fluorescent dye and facilitates its measurement at 570 nm after exciting at 540 nm. The method provides a detection limit of 0.003 mug ml(-1) and is virtually free from interference from extraneous ions. The relative standard deviaiton is 2.9% for ten determinations of 1.0 mug germanium. The method has been applied to the determination of germanium in various ores, minerals and rock samples. 相似文献
55.
The formation of a pink-coloured product when rhodamine 6G is treated with tetraiodomercurate(II) is used to determine mercury (5–25 μg) in a final volume of 25 ml. The reaction occurs immediately over the pH range 1–7 and, when the system is stabilized with gelatin, the absorbance remains unchanged at 575 nm for at least 24 h. The few interfering ions can be masked by the addition of appropriate reagent solutions. The method is simple and reliable and provides a molar absorptivity of 7.0·104 l mole-1 cm-1. 相似文献
56.
Topological Polymer Chemistry Enters Surface Science: Linear versus Cyclic Polymer Brushes 下载免费PDF全文
Giulia Morgese Lucca Trachsel Dr. Matteo Romio Mohammad Divandari Dr. Shivaprakash N. Ramakrishna Dr. Edmondo M. Benetti 《Angewandte Chemie (International ed. in English)》2016,55(50):15583-15588
The cyclic polymer topology strongly alters the interfacial, physico‐chemical properties of polymer brushes, when compared to the linear counterparts. In this study, we especially concentrated on poly‐2‐ethyl‐2‐oxazoline (PEOXA) cyclic and linear grafts assembled on titanium oxide surfaces by the “grafting‐to” technique. The smaller hydrodynamic radius of ring PEOXAs favors the formation of denser brushes with respect to linear analogs. Denser and more compact cyclic brushes generate a steric barrier that surpasses the typical entropic shield by a linear brush. This phenomenon, translates into an improved resistance towards biological contamination from different protein mixtures. Moreover, the enhancement of steric stabilization coupled to the intrinsic absence of chain ends by cyclic brushes, produce surfaces displaying a super‐lubricating character when they are sheared against each other. All these topological effects pave the way for the application of cyclic brushes for surface functionalization, enabling the modulation of physico‐chemical properties that could be just marginally tuned by applying linear grafts. 相似文献
57.
Nirogi RV Kandikere VN Shukla M Mudigonda K Maurya S Boosi R 《Rapid communications in mass spectrometry : RCM》2006,20(11):1695-1700
A simple, sensitive and rapid high-performance liquid chromatography/positive electrospray ionization tandem mass spectrometry method was developed and validated for the assay of clopidogrel in human plasma. Following liquid-liquid extraction, the analytes were separated using an isocratic mobile phase on a reversed-phase column and analyzed by mass spectrometry in the multiple reaction monitoring mode using the respective [M+H](+) ions, m/z 322/212 for clopidogrel and m/z 264/154 for the internal standard. The assay exhibited a linear dynamic range of 5-6000 pg/mL for clopidogrel in human plasma. The lower limit of quantification was 5 pg/mL with a relative standard deviation of less than 8%. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.5 min for each sample made it possible to analyze more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies. 相似文献
58.
Ramakrishna G Jose DA Kumar DK Das A Palit DK Ghosh HN 《The journal of physical chemistry. B》2006,110(20):10197-10203
Femtosecond transient absorption spectroscopy has been employed to understand the excited state dynamics of [Ru(bpy)(2)Sq](+) (I; bpy is 2,2'-bipyridyl, and Sq is the deprotonated species of the semiquinone form of 1,2-dihydroxy benzene) and its derivatives, a widely studied near-infrared (NIR) active electrochromic dye. Apart from the well-defined dpi(Ru) --> pi(bpy)-based metal-to-ligand charge transfer (MLCT) transition bands at approximately 480 nm, this class of molecules generally shows another dpi(Ru) --> pi(Sq)(SOMO)-based intense MLCT band at around 900 nm, which is known to be redox active and bleaches reversibly upon a change in the oxidation state of the coordinated dioxolene moiety. To have better insight into the photoinduced electron transfer dynamics associated with this MLCT transition, detailed investigations have been carried out on exciting this MLCT band at 800 nm. Immediately after photoexcitation, bleach at 900 nm has been observed, whose recovery is found to follow a triexponential function with major contribution from the ultrafast component. This ultrafast component of approximately 220 fs has been ascribed to the S(1) to S(0) internal conversion process. In addition to the bleach, we have detected two transient species absorbing at 730 and 1000 nm with a formation time approximately 220 fs for both species. The excited state lifetimes for these two transient species have been measured to be 1.5 and 11 ps and have been attributed to excited singlet ((1)MLCT) and triplet ((3)MLCT) states, respectively. Transient measurements carried out on the different but analogous derivatives (II and III) have also shown similar recovery dynamics except that the rate for the internal conversion process has increased with the decrease in the S(1) to S(0) energy gap. The observed results are consistent with the energy gap law for nonradiative decay from S(1) to S(0). 相似文献
59.
Kaur S Ma Z Gopal R Singh G Ramakrishna S Matsuura T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(26):13085-13092
Electrospun nanofibrous membranes (ENM) which have a porous structure have a huge potential for various liquid filtration applications. In this paper, we explore the viability of using plasma-induced graft copolymerization to reduce the pore sizes of ENMs. Poly(vinylidene) fluoride (PVDF) was electrospun to produce a nonwoven membrane, comprised of nanofibers with diameters in the range of 200-600 nm. The surface of the ENM was exposed to argon plasma and subsequently graft-copolymerized with methacrylic acid. The effect of plasma exposure time on grafting was studied for both the ENM and a commercial hydrophobic PVDF (HVHP) membrane. The grafting density was quantitatively measured with toluidine blue-O. The degree of grafting increased steeply with an increase in plasma exposure time for the ENM, attaining a maximum of 180 nmol/mg after 120 s of plasma treatment. However, the increase in the grafting density on the surface of the HVHP membrane was not as drastic, reaching a plateau of 65 nmol/mg after 60 s. The liquid entry permeation of water dropped extensively for both membranes, indicating a change in surface properties. Field emission scanning electron microscopy micrographs revealed an alteration in the surface pore structure for both membranes after grafting. Bubble point measurements of the ENM reduced from 3.6 to 0.9 um after grafting. The pore-size distribution obtained using the capillary flow porometer for the grafted ENM revealed that it had a similar profile to that of a commercial hydrophilic commercial PVDF (HVLP) membrane. More significantly, water filtration studies revealed that the grafted ENM had a better flux throughput than the HVLP membrane. This suggests that ENMs can be successfully engineered through surface modification to achieve smaller pores while retaining their high flux performance. 相似文献
60.
Chandrasekhar S Narsihmulu Ch Reddy NR Sultana SS 《Chemical communications (Cambridge, England)》2004,(21):2450-2451
We demonstrate for the first time, L-proline as a chiral catalyst for transfer aldol reaction between aldehydes and diacetone alcohol. 相似文献