全文获取类型
收费全文 | 415篇 |
免费 | 18篇 |
专业分类
化学 | 332篇 |
晶体学 | 4篇 |
力学 | 1篇 |
数学 | 41篇 |
物理学 | 55篇 |
出版年
2023年 | 6篇 |
2022年 | 18篇 |
2021年 | 23篇 |
2020年 | 7篇 |
2019年 | 11篇 |
2018年 | 14篇 |
2017年 | 9篇 |
2016年 | 19篇 |
2015年 | 15篇 |
2014年 | 25篇 |
2013年 | 22篇 |
2012年 | 35篇 |
2011年 | 55篇 |
2010年 | 23篇 |
2009年 | 15篇 |
2008年 | 20篇 |
2007年 | 22篇 |
2006年 | 17篇 |
2005年 | 12篇 |
2004年 | 15篇 |
2003年 | 16篇 |
2002年 | 10篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1995年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有433条查询结果,搜索用时 15 毫秒
91.
Baranac-Stojanović M Koch A Kleinpeter E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(1):370-376
Based on the nucleus‐independent chemical shift (NICS) concept, isotropic magnetic shielding values have been computed along the three Cartesian axes for ethene, cyclobutadiene, benzene, naphthalene, and benzocyclobutadiene, starting from the molecular/ring center up to 10 Å away. These through‐space NMR spectroscopic shielding (TSNMRS) values, which reflect the anisotropic effects, have been broken down into contributions from localized‐ and canonical molecular orbitals (LMOs and CMOs); these contributions revealed that the proton NMR spectroscopic chemical shifts of nuclei that are spatially close to the C?C double bond or the aromatic ring should not be explained in terms of the conventionally accepted π‐electron shielding/deshielding effects. In fact, these effects followed the predictions only for the antiaromatic cyclobutadiene ring. 相似文献
92.
Marija Matković Krešimir Molčanov Robert Glaser Kata Mlinarić-Majerski 《Tetrahedron》2012,68(42):8795-8804
2-(1-Adamantyl)-β-butyrolactones 3a and 3b were synthesized using very common peptide coupling reagents under mild conditions and their ring-opening reactions were then studied. These novel lactones showed pronounced stability and were resistant to cleavage upon acidic water extraction and column chromatographic purification. The adamantane moiety plays an important function in lowering the lactone reactivity by protecting the electrophilic sites on the four membered ring via steric hindrance. However under certain conditions, both O–C(carbonyl) and O–C(alkyl) bond-cleavage ring-opening reactions were observed. Bond-cleavage at physiological temperature makes these novel lactones especially noteworthy. Novel adamantyl-β-butyrolactones have a potential to act as biomembrane soluble amphiphiles that might exhibit a combination of stability and biological activity with the latter hopefully predominating. 相似文献
93.
Tomislav Bali Marija Paurevi Marta Po
kaj Martina Medvidovi-Kosanovi Dominik Goman Aleksandar Szchenyi Zsolt Preisz Sndor Kunsgi-Mt 《Molecules (Basel, Switzerland)》2022,27(12)
The century-old, well-known odd–even effect phenomenon is still a very attractive and intriguing topic in supramolecular and nano-scale organic chemistry. As a part of our continuous efforts in the study of supramolecular chemistry, we have prepared three novel aromatic alcohols (1,2-bis[2-(hydroxymethyl)phenoxy]butylene (Do4OH), 1,2-bis[2-(hydroxymethyl)phenoxy]pentylene (Do5OH) and 1,2-bis[2-(hydroxymethyl)phenoxy]hexylene (Do6OH)) and determined their crystal and molecular structures by single-crystal X-ray diffraction. In all compounds, two benzyl alcohol groups are linked by an aliphatic chain of different lengths (CH2)n; n = 4, 5 and 6. The major differences in the molecular structures were found in the overall planarity of the molecules and the conformation of the aliphatic chain. Molecules with an even number of CH2 groups tend to be planar with an all-trans conformation of the aliphatic chain, while the odd-numbered molecule is non-planar, with partial gauche conformation. A direct consequence of these structural differences is visible in the melting points—odd-numbered compounds of a particular series display systematically lower melting points. Crystal and molecular structures were additionally studied by the theoretical calculations and the melting points were correlated with packing density and the number of CH2 groups. The results have shown that the generally accepted rule, higher density = higher stability = higher melting point, could not be applied to these compounds. It was found that the denser packaging causes an increase in the percentage of repulsive H‧‧‧H interactions, thereby reducing the stability of the crystal, and consequently, the melting points. Another interesting consequence of different molecular structures is their electrochemical and antioxidative properties—a non-planar structure displays the highest oxidation peak of hydroxyl groups and moderate antioxidant activity. 相似文献
94.
Alja Prah Tanja Gavrani Andrej Perdih Marija Sollner Dolenc Janez Mavri 《Molecules (Basel, Switzerland)》2022,27(19)
Monoamine oxidases (MAOs) are an important group of enzymes involved in the degradation of neurotransmitters and their imbalanced mode of action may lead to the development of various neuropsychiatric or neurodegenerative disorders. In this work, we report the results of an in-depth computational study in which we performed a static and a dynamic analysis of a series of substituted β-carboline natural products, found mainly in roasted coffee and tobacco smoke, that bind to the active site of the MAO-A isoform. By applying molecular docking in conjunction with structure-based pharmacophores and molecular dynamics simulations coupled with dynamic pharmacophores, we extensively investigated the geometric aspects of MAO-A binding. To gain insight into the energetics of binding, we used the linear interaction energy (LIE) method and determined the key anchors that allow productive β-carboline binding to MAO-A. The results presented herein could be applied in the rational structure-based design and optimization of β-carbolines towards preclinical candidates that would target the MAO-A enzyme and would be applicable especially in the treatment of mental disorders such as depression. 相似文献
95.
96.
Functionalized 1,2-dithioles have been synthesized by a ring opening-closing process of 5-substituted- and 5-unsubstituted-2-alkylidene-4-oxothiazolidines with Lawesson's reagent. The 13C NMR data confirmed the meso-ionic structure of these aromatic-type 1,2-dithioles. 相似文献
97.
JPC – Journal of Planar Chromatography – Modern TLC - Quantitative determination of the pesticides alachlor, atrazine and α-cypermethrin in aquatic samples is reported. The method... 相似文献
98.
Ana Dunja Mance Marija indler-Kulyk KreImir Jakop
i Antonija Hergold-Brundi Ante Nagl 《Journal of heterocyclic chemistry》1997,34(4):1315-1322
N-Alkenyl-N-(5-substituted-2-furfuryl)-N-p-toluidines 1–10 have been selected to study the intramolecular Diels-Alder reaction of furans. New epoxyisoindolines 11–20 were prepared and fully characterised. 相似文献
99.
Silica Gel as a Promoter of Sequential Aza‐Michael/Michael Reactions of Amines and Propiolic Esters: Solvent‐ and Metal‐Free Synthesis of Polyfunctionalized Conjugated Dienes 下载免费PDF全文
Dr. Jovana Aleksić Dr. Milovan Stojanović Prof. Dr. Marija Baranac‐Stojanović 《化学:亚洲杂志》2018,13(14):1811-1835
We present an efficient, simple, metal‐ and solvent‐free silica‐gel‐promoted synthesis of functionalized conjugated dienes by sequential aza‐Michael/Michael reactions by starting from commercially available primary amines and propiolic esters. The scope and usefulness of the method is demonstrated for 31 examples, including a range of propiolic esters, aliphatic amines, and differently substituted aromatic amines. For aliphatic amines, the products were obtained within 0.5 to 4 h in 52 to 85 % yield, compared with 3.5 to 22 h under classical solution‐phase synthesis, which proceeds with similar or lower yields. The method was found to be particularly useful for weakly nucleophilic aromatic amines, which provided products in 21 to 73 % yield over 2.5 to 9.5 h compared with yields of 0 to 49 % over 1 to 6 d under standard solution‐phase conditions, and for more hydrophobic esters that gave products in yields of 47 to 79 % over 1 to 3 h compared with 0 to 45 % over 4 to 114 h in solvent. 相似文献
100.
DFT (B3LYP/6-31G) and ab initio molecular orbital theory (QCISD/cc-pVDZ) are used to investigate several possible mechanisms involving free radical intermediates as well as their protonated forms for processes related to the coenzyme B(12)-dependent rearrangement catalyzed by ethanolamine ammonia lyase. Two major types of rearrangements are discussed in detail, intramolecular migration and dissociation of the amine/ammonia groups, for both of which several scenarios are considered. According to the calculations, the complete dissociation of the migrating group and its subsequent association constitute an unlikely route for both the protonated and the unprotonated reactant because of the high-energy barriers (more than 23 kcal/mol) involved in these steps. Direct migration of the protonated amine group is far more favorable (10.4 kcal/mol) and therefore presents the most likely candidate for the actual enzymatic reaction. The calculations further imply that the direct loss of an ammonium cation (10.6 kcal/mol) represents a feasible pathway as well. Comparing the rearrangements for the aminoethanol radical and its protonated counterpart, in line with previous findings reported by Golding, Radom, and co-workers, we find that the migration of a protonated group is in general associated with lower energy barriers, suggesting that the actual enzyme substrate quite likely corresponds to (partially) protonated aminoethanol. As the extent of the substrate protonation/deprotonation by the active site of the enzyme may vary, the actual energy barriers are expected to range between the values calculated for the two extreme cases of a substrate, that is, the aminoethanol radical 2 and its fully protonated form 6. 相似文献