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81.
The allylidene complex (CO)5W=CH---C(Ph)=C(Ph)H (4) reacts with cyclopentadiene by stereospecific transfer of the carbene ligand to one of the two double bonds of cyclopentadiene to give a cis-divinylcyclopropane complex 5. The divinylcyclopropane ligand coordinates to the metal via the unsubstituted double bond. Addition of bromide to solutions of 5 gives rise to the formation of [(CO)5WBr]− and a bicyclo[3.2.1]octadiene (6), the Cope rearrangement product of the free divinylcyclopropane. Thermolysis of 5 affords 6 and its (CO)5W complex. The reaction of 4 with furan (8a), 2-methylfuran (8b) and 3-methylfuran (8c) affords the (CO)5W(bicyclo[3.2.1]oxahepta- diene) complexes (9a–c), The formation of 9a–c which is chemo-, regio- and stereospecific is explained by a tandem cyclopropanation/Cope rearrangement sequence. The bicyclic ligands 10a–c are liberated from the metal either by thermolysis of solutions of 9a–c or by addition of bromide. 相似文献
82.
Genistein and orobol 8-C-beta-D-glucopyranosides (1 and 3) were firstly synthesized in overall yields of 39% and 41% from 2,4-di-O-benzylphloroacetophenone (4), as follows: (1) the formation of the chalcone (6, 7) by aldol condensation of the benzyl-protected C-glycosylphloroacetophenone (5), a key intermediate of the total synthesis of 1 and 3 and synthesized by a C-glycosylation method involving the O-->C glycoside rearrangement of 4 in 96% yield; (2) the formation of isoflavones (10, 11 and 12, 13) by the formation of acetals by oxidative rearrangement of the protected chalcones (8 and 9) using Tl(NO3)3, followed by acid-catalyzed cyclization; (3) a final debenzylation by hydrogenolysis. 相似文献
83.
We examined the expression of recombination-activating genes (RAG-1 and RAG-2) and activation-induced cytidine deaminase (AID) by mature human blood B cells stimulated with anti-CD40 in the presence of IL-4 or IL-13. IL-4 was an effective cofactor for RAG-1 and RAG-2 expression, whereas IL-13 was not. In addition, IL-4-dependent RAG expression combined with AID and IgE expression allowed predominant expression of newly rearranged lambda light chains on IgE+ cells generated from kappa+ cells. Although the magnitudes of IL-4- and IL-13-dependent AID and IgE expression were related to expression levels of binding subunits of the IL-4 and IL-13 receptors, IL-13 was ineffective for light chain replacement in the induced IgE+ cells due to the failure in RAG expression. Our studies using mature blood B cells indicate that IL-4-responsive cells, unlike IL-13-responsive cells, undergo lambda gene rearrangement leading to replacement in parallel with RAG expression and suggest that this replacement may contribute to the regulation of affinity maturation of IgE antibodies. 相似文献
84.
Lespinasse J Réthoré MO North MO Bovier-Lapierre M Lundsteen C Fert-Ferrer S Bugge M Kirchoff M 《Annales de génétique》2004,47(3):315-324
Balanced complex chromosomal rearrangements (BCCR) encompass a heterogeneous group of rare chromosomal aberrations. In this paper, we report three cases of BCCRs. In two the probands were referred for either genetic counseling or prenatal management. One case was ascertained after chromosome analysis performed because of psychiatric manifestations; this was an isolated finding. We also outline the molecular cytogenetic techniques, which were essential in confirming and precisely delineating the BCCRs identified in these patients. In addition the various aspects of genetic counseling for this type of chromosomal rearrangement, highlighting the details particular to each individual case are discussed. We discuss the classification for this type of chromosomal mutation. 相似文献
85.
Jonathan F. Hull 《Inorganica chimica acta》2010,363(6):1243-6654
Ru(DMSO)4Cl2 is catalytically active for converting aldehydes to primary amides via oxime intermediates. This catalyst is readily available, and requires no additional ligands, a great simplification compared to previous work. A Ru(II)/(IV) mechanism is proposed. 相似文献
86.
Modular rearrangements play an important role in protein evolution. Functional modules, often tantamount to structural domains or smaller fragments, are in many cases well conserved but reoccur in a different order and across many protein families. The underlying genetic mechanisms are gene duplication, fusion, and loss of sequence fragments. As a consequence, the sequential order of domains can be inverted, leading to what is known as circularly permutated proteins. Using a recently developed algorithm, we have identified a large number of such rearrangements and analyzed their evolutionary history. We searched for examples which have arisen by one of the three postulated mechanisms: independent fusion/fission, "duplication/deletion," and plasmid-mediated "cut and paste." We conclude that all three mechanisms can be observed, with the independent fusion/fission being the most frequent. This can be partly attributed to highly mobile domains. Duplication/deletion has been found in modular proteins such as peptide synthases. 相似文献
87.
Relationship between growth irradiance and the xanthophyll cycle pool in the diatom Nitzschia palea 总被引:1,自引:0,他引:1
The size and de-epoxidation state of the xanthophyll cycle pool was measured in cultures of Nitzschia palea grown at six fluence rates in continuous light or with a 12 h photoperiod. In both series the size of the pool increased with increasing irradiance. The de-epoxidized form, diatoxanthin, was only present at fluence rates saturating for growth. The portion of diadinoxanthin, which was not readily de-epoxidized in saturating light, was constant and not related to the size of the pool. In the culture grown in a light-dark cycle at 300 μmol photons m-2 s-1 (PAR) increasing de-epoxidation took place in the latter half of the photoperiod, when the rate of photosynthesis was decreasing. A rapid, spectrophotometric method for measuring the extent of de-epoxidation of the xanthophyll cycle pool in a culture of diatoms is described. Upon addition of a small volume of hydrochloric acid to an extract of pigments in 90% acetone, the absorbance at 480 nm is reduced. The size of the reduction is a measure of the state of the xanthophyll cycle pool, since the absorbance of diatoxanthin is reduced by 5%, but the absorbance of diadinoxanthin by 87% due to an epoxide-furanoid rearrangement, which causes the absorption spectrum to be shifted by ca 20 nm towards shorter wavelengths. 相似文献
88.
Y. Hisatomi K. Hanada S. Iida 《TAG. Theoretical and applied genetics. Theoretische und angewandte Genetik》1997,95(7):1049-1056
Transposable elements have often been discovered as new insertion sequences in known genes, and minisatellites are often
employed as molecular markers in diagnostic and mapping studies. We compared the genes for flower pigmentation in a line of
the common morning glory bearing fully colored flowers with those in two anthocyanin
flaked
mutable lines producing variegated flowers and found RFLPs at the region of the ANS gene for anthocyanin biosynthesis. The DNA rearrangements detected by the RFLPs are due to integration of a novel type of
minisatellite, MiniSip1, having a long LTR retrotransposon, RTip1, inserted in the mutable lines. The structural analysis of the rearranged region revealed that the 12.4-kb RTip1 element is flanked by 5-bp target duplications within the MiniSip1 sequence and contains two LTR sequences of about 590 bp, a primer binding site for tRNALys, a typical polypurine tract and another new type of minisatellite, MiniSip2. Since no long open reading frame corresponding to the gag and pol genes was found, RTip1 appears to be a defective Ty3/gypsy-like element. Interestingly, the 269-bp-long MiniSip1 element comprises two alternating motifs of 41 bp and 19 bp, whereas the 962 bp long MiniSip2 element consists of two partially alternating motifs of 86 bp and 90 bp which are partially homologous to each other. Possible
evolutionary processes that may have generated the rearranged structure at the ANS gene region are also discussed.
Received: 25 April 1997 / Accepted: 16 May 1997 相似文献
90.
A series of new 1-aryl-6,7-dihydroxy tetrahydroisoquinolines with several substitution patterns in the 1-aryl group at C-1 were prepared in good yields. The influence of each substituent on the affinity and selectivity for D1 and D2 dopaminergic receptors was studied. Moreover, N-alkyl salts of these tetrahydroisoquinolines were used as starting material to synthesize a series of new 1-aryl-7,8-dihydroxy 3-tetrahydrobenzazepines derivatives with electron-withdrawing substituents at C-2 position by the diastereoselective Stevens rearrangement. The structure-activity relationship of these compounds was explored to evaluate the effect of the functional group at C-2 in benzazepines and the modification in the aryl group at the isoquinoline C-1 position towards the affinity and selectivity for the mentioned receptors. The 1-aryl-6,7-dihydroxy tetrahydroisoquinoline 4c shows significant affinity towards D2 receptor, with Ki value of 31 nM. This significant affinity can be attributed to the presence of a thiomethyl group, and it is the most active 1-aryl-6,7-dihydroxy tetrahydroisoquinoline derivative reported to date. 相似文献