全文获取类型
收费全文 | 345篇 |
免费 | 10篇 |
专业分类
化学 | 244篇 |
晶体学 | 1篇 |
力学 | 22篇 |
数学 | 38篇 |
物理学 | 50篇 |
出版年
2023年 | 3篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2017年 | 5篇 |
2016年 | 8篇 |
2015年 | 18篇 |
2014年 | 7篇 |
2013年 | 12篇 |
2012年 | 13篇 |
2011年 | 16篇 |
2010年 | 10篇 |
2009年 | 13篇 |
2008年 | 15篇 |
2007年 | 17篇 |
2006年 | 11篇 |
2005年 | 11篇 |
2004年 | 11篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2000年 | 4篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 16篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1979年 | 3篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1972年 | 4篇 |
1970年 | 2篇 |
1968年 | 2篇 |
1942年 | 2篇 |
1938年 | 2篇 |
1937年 | 5篇 |
1932年 | 2篇 |
1885年 | 4篇 |
1865年 | 3篇 |
排序方式: 共有355条查询结果,搜索用时 15 毫秒
1.
2.
Jean‐Louis Schmitt Adrian‐Mihail Stadler Nathalie Kyritsakas Jean‐Marie Lehn 《Helvetica chimica acta》2003,86(5):1598-1624
Control over the folding of molecular strands may be achieved by appropriate choice of the constituting subunits, in particular for chains of specific heterocycles such as sequences of directly connected pyridine (py) and pyrimidine (pym) rings, which are known to fold into extended helical structures. Since the hydrazone (hyz) group represents an isomorphic analogue of a py site, the condensation of hydrazine and carboxaldehyde derivatives of pym offers a very efficient approach to strands incorporating hyz instead of py units and constituted by sequences of alternating hyz and pym groups. A series of such strands of different lengths, up to ten hyz units, i.e., 1 – 7 , were synthesized. Their spectral properties indicate that they fold indeed into helical shapes. Extensive characterization was performed in solution by 1HNMR spectroscopy and in the solid state by determination of the crystal structures of eight such strands. They all display the expected helical geometry with up to 3 1/3 turns and direct stacking contacts. The efficiency and flexibility of the synthetic approach as well as its wide potential for generation of diversity through lateral decoration make the (hyz? pym) subunit a particularly attractive helicity codon. 相似文献
3.
4.
5.
6.
Solvolysis of 4-Alkydenbicyclo[3.2.0]hept-2-en-6-oles. Synthesis of 1-Vinylfulvenes and 8,8-Diphenylheptafulvene Four 4-alkylidenebicyclo[3.2.0]hept-2-en-6-ones 2–5 , obtained via ketene cycloaddition to fulvenes, were reduced to separated mixtures of the ‘endo’ -alcohols ‘endo’- 6 to ‘endo’- 9 (68–73%) and ‘exo’- 6 to ‘exo’- 9 (3–20%). Treatment of some of these alcohols with (CF3SO2)2O in CH2Cl2/pyridine caused a spontaneous solvolysis to yield unsaturated 7-membered rings as pyridinium triflates 10–12 or 1-vinylfulvenes 13 and 14 , a new class of reactive tetraenes: Both ‘endo’- 9 and ‘exo’- 9 , having two methyl groups at C(7), were converted into the vinylfulvene 13 (≈ 80%). The alcohols with two H-atoms at C(7) exhibited a stereochemically controlled reaction selectivity, inasmuch as ‘endo’- 6 to ‘endo’- 8 afforded only the corresponding 7-membered-ring pyridinium salts 10–12 (66–79%), while ‘exo’- 6 produced only the vinylfulvene 14 (77%). A stereoelectronic control argument explains the C(1), C(5)-bond cleavage with ‘endo’- B and ‘endo’– 6 -‘endo’- 8 , as well as the C(1), C(7)-bond cleavage with ‘exo’- B , ‘exo’- 6 , and with both ‘endo’- and ‘exo’- 9 . Thermolysis (120°) of the pyridinium triflates 10 and 11 yielded the 3-isopropenyl-cycloheptatrienes 18 and 19 , respectively (≈90%); similar conditions (145°) applied to the triflate 12 produced the doubly cyclized fluorene derivative 21 (60%). When the iodide 22 derived from the triflate 12 with Nal was heated in refluxing toluene, 8,8-diphenylheptafulvene ( 23 , 86%) was obtained. 相似文献
7.
A new methodology based on pressurized liquid extraction (PLE) followed by LC-MS is presented for the simultaneous and unequivocal determination of alkylphenol ethoxylates (APEOs) and their degradation products, alkylphenols (APs) and alkylphenoxy carboxylates (APECs), in sediment samples. The protocol, applicable to a full range of APEO oligomers and degradation products, permits the sensitive and selective determination of APEOs (nEO = 1-15), APECs (nEO = 0-1) and APs at low ppb levels (LODs = 1-5 microg/kg) in sediment samples. Optimization of the operational parameters of PLE clearly demonstrates that significant thermal losses of APs occur during extraction at elevated temperatures. The loss of octylphenol (OP) at 100 degrees C was 61.2% and of nonylphenol (NP) 40.0%, whereas other compounds were completely recovered. Thus, to avoid losses due to the volatility of alkylphenols, a low extraction temperature should be applied. The conditions that gave the best results for all target compounds were as follows: extraction solvent mixture, methanol-acetone (1:1, v/v); temperature, 50 degrees C; pressure, 1500 p.s.i.; two static cycles. Using PLE and a subsequent clean-up with solid-phase extraction (SPE), the simultaneous extraction of APEOs, APs and APECs from sediment samples was achieved yielding recoveries >70% and producing low MS background noise. The developed methodology was applied on a routine basis to the analysis of alkylphenolic compounds in sediment samples. APEOs and their persistent degradation products were detected in significant concentrations in sediments from Portuguese rivers, especially at sites situated in the proximity of industrial plants (mainly the textile industry). The total concentration of alkylphenolic compounds (APEOs+APs+APECs) ranged from 155 to 2400 microg/kg. Of all the alkylphenolic compounds, NP comprised 40 to 50% with concentrations up to 1172 microg/kg. 相似文献
8.
9.
Mohammad Vatankhah‐Varnoosfaderani Amin GhavamiNejad Saud Hashmi Florian J. Stadler 《Macromolecular rapid communications》2015,36(5):447-452
Copolymers of N‐isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self‐healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV–vis and 1H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self‐healing properties are tested rheologically. The produced reversible organogel can self‐encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual‐targeted and controlled drug delivery and release—by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.