全文获取类型
收费全文 | 1386篇 |
免费 | 53篇 |
国内免费 | 14篇 |
专业分类
化学 | 954篇 |
晶体学 | 11篇 |
力学 | 41篇 |
数学 | 262篇 |
物理学 | 185篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 45篇 |
2021年 | 55篇 |
2020年 | 26篇 |
2019年 | 29篇 |
2018年 | 29篇 |
2017年 | 20篇 |
2016年 | 58篇 |
2015年 | 46篇 |
2014年 | 56篇 |
2013年 | 89篇 |
2012年 | 93篇 |
2011年 | 113篇 |
2010年 | 41篇 |
2009年 | 52篇 |
2008年 | 81篇 |
2007年 | 91篇 |
2006年 | 76篇 |
2005年 | 59篇 |
2004年 | 53篇 |
2003年 | 59篇 |
2002年 | 32篇 |
2001年 | 25篇 |
2000年 | 17篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 13篇 |
1993年 | 8篇 |
1992年 | 9篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 6篇 |
1975年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有1453条查询结果,搜索用时 0 毫秒
41.
Three types of cross-linked porous organic polymers (either oxygen-, nitrogen-, or sulfur-doped) were carbonized under a chlorine atmosphere to obtain chars in the form of microporous heteroatom-doped carbons. The studied organic polymers constitute thermosetting resins obtained via sol-gel polycondensation of resorcinol and five-membered heterocyclic aldehydes (either furan, pyrrole, or thiophene). Carbonization under highly oxidative chlorine (concentrated and diluted Cl2 atmosphere) was compared with pyrolysis under an inert helium atmosphere. All pyrolyzed samples were additionally annealed under NH3. The influence of pyrolysis and additional annealing conditions on the carbon materials’ porosity and chemical composition was elucidated. 相似文献
42.
This review focuses on the natural sources and pharmacological activity of tormentic acid (TA; 2α,3β,19α-trihydroxyurs-2-en-28-oic acid). The current knowledge of its occurrence in various plant species and families is summarized. Biological activity (e.g., anti-inflammatory, antidiabetic, antihyperlipidemic, hepatoprotective, cardioprotective, neuroprotective, anti-cancer, anti-osteoarthritic, antinociceptive, antioxidative, anti-melanogenic, cytotoxic, antimicrobial, and antiparasitic) confirmed in in vitro and in vivo studies is compiled and described. Biochemical mechanisms affected by TA are indicated. Moreover, issues related to the biotechnological methods of production, effective eluents, and TA derivatives are presented. 相似文献
43.
Paulina Grocholska Andrzej Konieczny Zuzanna Ka
mierczak Krystyna Dbrowska Karolina Panek-Laszczyska Marlena Kak Wojciech Witkiewicz Zbigniew Szewczuk Remigiusz Bchor 《Molecules (Basel, Switzerland)》2021,26(23)
Early detection of any preeclampsia biomarkers may lower the risk of mortality, both for a mother and a child. Our study focuses on techniques for preeclampsia biomarker identification by comparing the results of a method using liquid chromatography mass spectrometry in multiple reaction monitoring mode (LC-MS/MS) with those by the enzyme-linked immunosorbent assay (ELISA) test, as well as by comparing the obtained results with clinical data. In the proposed LC-MS/MS method a tryptic digest peptide charge derivatization strategy was used as a tool for sensitive detection of podocin, i.e., a previously discovered preeclampsia biomarker present in urine samples from pregnant women. Urine samples from pregnant women with diagnosed preeclampsia were collected at different stages of pregnancy and from healthy subjects, and then were analyzed by ELISA test and the proposed method with LC-MS/MS. Charge derivatization of the ε amino group of C-terminal lysine residues in tryptic digests by 2,4,6-triphenylpyrylium salt was performed to increase the ionization efficiency in the LC-MS/MS mode. Podocin was identified at the early stage of pregnancy, while its detection using an ELISA test was not possible. The protocol for urine sample preparation was optimized. Our results show that the proposed method by LC-MS/MS in combination with peptide charge derivatization, provides an ultrasensitive tool for diagnosis of preeclampsia, and provides earlier detection than a clinical diagnosis or ELISA test. The proposed solution may revolutionize medical diagnostics. 相似文献
44.
Lewiński J Marciniak W Lipkowski J Justyniak I 《Journal of the American Chemical Society》2003,125(42):12698-12699
Studies on the reaction of zinc alkyls with O2 are reported which demonstrate that the selective oxygenation of organozinc compound is viable. The reaction of [EtZn(azol)]n (azol = deprotonated 1-aziridineethanol) with an excess of dry O2 in toluene affords the zinc ethylperoxide [EtOOZn(azol)]2[EtZn(azol)]2, while the analogous reaction between Me2Zn and O2 results in the isolation of the Me6Zn7(OMe)8 cluster in high yield. 相似文献
45.
Gajewski JJ Bocian W Brichford NL Henderson JL 《The Journal of organic chemistry》2002,67(12):4236-4240
The competitive kinetics of additions of allyl to benzaldehyde-h and -d from allyltributyl tin, from diisopropyltartrylallyl boronate, and from allyl bromide and zinc dust in aqueous tetrahydrofuran have inverse secondary deuterium kinetic isotope effects, SDKIEs. These inverse SDKIEs are in contrast to the normal SDKIEs that were obtained with allyl lithium and allyl Grignard, suggesting rate-determining single-electron transfer in these cases. By various MO calculations the transition state for addition of allyl boronate occurs with substantial B-O bond formation and little C-C bond formation. The magnitudes of the SDKIEs with the other two allylating reagents, when compared with reasonable equilibrium isotope effects for the addition, suggest transition states with substantial C-C bond formation. 相似文献
46.
Marlena Pięta Jacek Kędzia Dorota Kowalczyk Jakub Wojciechowski Wojciech M. Wolf Tomasz Janecki 《Tetrahedron》2019,75(17):2495-2505
An efficient, versatile, enantioselective synthesis of 1,3-disubstituted and 1,3,6-trisubstituted 5-methylidenedihydrouracils applying Horner-Wadsworth Emmons methodology was developed. Starting 1,3-disubstituted 5-diethoxyphosphoryluracils were subjected to reduction of the double bond or addition of various Grignard reagents and obtained Horner-Wadsworth Emmons reagents were used for the olefination of formaldehyde. Enantioselective synthesis of 1,3,6-trisubstituted 5-methylidenedihydrouracils was accomplished by introducing (R,R)- or (S,S)-di(1-phenylethylamino)phosphoryl groups as chiral auxiliary. Additions of Grignard reagents in the presence of these groups were highly and complimentary diastereoselective (de?~?80%). Further separation of the diastereomeric mixtures by column chromatography enabled synthesis of (R)- and (S)-1,3,6-trisubstituted-5-methylidenedihydrouracils with ee?≥?98%. Furthermore, absolute configuration of the adducts and final products was established using single crystal X-ray analysis. Stereochemical course of the addition reactions is also discussed. 相似文献
47.
Gorzkiewicz Krzysztof Mietelski Jerzy Wojciech Kierepko Renata Brudecki Kamil 《Journal of Radioanalytical and Nuclear Chemistry》2019,322(3):1311-1321
Journal of Radioanalytical and Nuclear Chemistry - This paper presents results of the development process of low-background, digital gamma-rays spectrometer equipped with Broad Energy Germanium... 相似文献
48.
Dr. Łukasz Wolański Mateusz Domański Prof. Wojciech Grochala Dr. Paweł Szarek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10290-10293
Theoretical calculations utilizing relativistic ZORA Hamiltonian point to the conceivable existence of an IrNO3 molecule in C3v geometry. This minimum is shown to correspond to genuine nonavalent iridium nitride trioxide, which is a neutral analogue of cationic [IrO4]+ species detected recently. Despite the presence of nitride anion, the molecule is protected by substantial barriers exceeding 200 kJ mol−1 against transformations leading, for example, to global minimum (O=)2Ir−NO, which contains metal at a lower formal oxidation state. 相似文献
49.
Blazewicz J Glover F Kasprzak M Markiewicz WT Oğuz C Rebholz-Schuhmann D Swiercz A 《Computational Biology and Chemistry》2006,30(5):313-320
DNA sequencing by hybridization (SBH) induces errors in the biochemical experiment. Some of them are random and disappear when the experiment is repeated. Others are systematic, involving repetitions in the probes of the target sequence. A good method for solving SBH problems must deal with both types of errors. In this work we propose a new hybrid genetic algorithm for isothermic and standard sequencing that incorporates the concept of structured combinations. The algorithm is then compared with other methods designed for handling errors that arise in standard and isothermic SBH approaches. DNA sequences used for testing are taken from GenBank. The set of instances for testing was divided into two groups. The first group consisted of sequences containing positive and negative errors in the spectrum, at a rate of up to 20%, excluding errors coming from repetitions. The second group consisted of sequences containing repeated oligonucleotides, and containing additional errors up to 5% added into the spectra. Our new method outperforms the best alternative procedures for both data sets. Moreover, the method produces solutions exhibiting extremely high degree of similarity to the target sequences in the cases without repetitions, which is an important outcome for biologists. The spectra prepared from the sequences taken from GenBank are available on our website http://bio.cs.put.poznan.pl/. 相似文献