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371.
Xie J Okano A Pierce JG James RC Stamm S Crane CM Boger DL 《Journal of the American Chemical Society》2012,134(2):1284-1297
The total synthesis of [Ψ[C(═S)NH]Tpg(4)]vancomycin aglycon (8) and its unique AgOAc-promoted single-step conversion to [Ψ[C(═NH)NH]Tpg(4)]vancomycin aglycon (7), conducted on a fully deprotected substrate, are disclosed. The synthetic approach not only permits access to 7, but it also allows late-stage access to related residue 4 derivatives, alternative access to [Ψ[CH(2)NH]Tpg(4)]vancomycin aglycon (6) from a common late-stage intermediate, and provides authentic residue 4 thioamide and amidine derivatives of the vancomycin aglycon that will facilitate ongoing efforts on their semisynthetic preparation. In addition to early stage residue 4 thioamide introduction, allowing differentiation of one of seven amide bonds central to the vancomycin core structure, the approach relied on two aromatic nucleophilic substitution reactions for formation of the 16-membered diaryl ethers in the CD/DE ring systems, an effective macrolactamization for closure of the 12-membered biaryl AB ring system, and the defined order of CD, AB, and DE ring closures. This order of ring closures follows their increasing ease of thermal atropisomer equilibration, permitting the recycling of any newly generated unnatural atropisomer under progressively milder thermal conditions where the atropoisomer stereochemistry already set is not impacted. Full details of the evaluation of 7 and 8 along with several related key synthetic compounds containing the core residue 4 amidine and thioamide modifications are reported. The binding affinity of compounds containing the residue 4 amidine with the model D-Ala-D-Ala ligand 2 was found to be only 2-3 times less than the vancomycin aglycon (5), and this binding affinity is maintained with the model d-Ala-d-Lac ligand 4, representing a nearly 600-fold increase in affinity relative to the vancomycin aglycon. Importantly, the amidines display effective dual, balanced binding affinity for both ligands (K(a)2/4 = 0.9-1.05), and they exhibit potent antimicrobial activity against VanA resistant bacteria ( E. faecalis , VanA VRE) at a level accurately reflecting these binding characteristics (MIC = 0.3-0.6 μg/mL), charting a rational approach forward in the development of antibiotics for the treatment of vancomycin-resistant bacterial infections. In sharp contrast, 8 and related residue 4 thioamides failed to bind either 2 or 4 to any appreciable extent, do not exhibit antimicrobial activity, and serve to further underscore the remarkable behavior of the residue 4 amidines. 相似文献
372.
Blumenkrantz G Li X Han ET Newitt DC Crane JC Link TM Majumdar S 《Magnetic resonance imaging》2006,24(8):1001-1007
PURPOSE: Recent studies have proposed that magnetic resonance (MR) T1rho relaxation time is associated with loss of macromolecules. The depletion of macromolecules in the matrix of the intervertebral disc may be an initiating factor in degenerative disc disease. The purpose of this study was to test the feasibility of quantifying T1rho relaxation time in phantoms and intervertebral discs of healthy volunteers using in vivo MR imaging at 3 T. MATERIALS AND METHODS: A multislice T1rho spiral sequence was used to quantify T1rho relaxation time in phantoms with different agarose concentrations and in the intervertebral discs of 11 healthy volunteers (mean age=31.3 years; age range=23-60 years; gender: 5 females, 6 males). RESULTS: The phantom studies demonstrated the feasibility of using spiral imaging at 3 T. The in vivo results indicate that the median T1rho value of the nucleus (116.6+/-21.4 ms) is significantly greater (P<0.05) than that of the annulus (84.1+/-11.7 ms). The correlations between the age of the volunteers and T1rho relaxation time in the nucleus (r2=-0.82; P=0.0001) and the annulus (r2=-0.37; P=0.04) were significant. A trend of decreasing T1rho values from L3-4 to L4-5 to L5-S1 was evident. CONCLUSION: The results of this study suggest that in vivo T1rho quantification is feasible and may potentially be a clinical tool in identifying early degenerative changes in the intervertebral disc. 相似文献
373.
Blanco-Rodríguez AM Busby M Gradinaru C Crane BR Di Bilio AJ Matousek P Towrie M Leigh BS Richards JH Vlcek A Gray HB 《Journal of the American Chemical Society》2006,128(13):4365-4370
The triplet metal-to-ligand charge transfer ((3)MLCT) dynamics of two structurally characterized Re(I)(CO)(3)(phen)(HisX)-modified (phen = 1,10-phenanthroline; X = 83, 109) Pseudomonas aeruginosa azurins have been investigated by picosecond time-resolved infrared (TRIR) spectroscopy in aqueous (D(2)O) solution. The (3)MLCT relaxation dynamics exhibited by the two Re(I)-azurins are very different from those of the sensitizer [Re(I)(CO)(3)(phen)(im)](+) (im = imidazole). Whereas the Re(I)(CO)(3) intramolecular vibrational relaxation in Re(I)(CO)(3)(phen)(HisX)Az (4 ps) is similar to that of [Re(I)(CO)(3)(phen)(im)](+) (2 ps), the medium relaxation is much slower ( approximately 250 vs 9.5 ps); the 250-ps relaxation is attributable to reorientation of D(2)O molecules as well as structural reorganization of the rhenium chromophore and nearby polar amino acids in each of the modified proteins. 相似文献
374.
375.
1869年,门捷列夫在第一张元素周期表中的锆元素后留出原子量为180的元素位置,预测铪与锆同族。1913年,原子序数和莫斯莱定律的提出揭示了铪元素在周期表中位置排列的实质,为铪元素的发现提供理论基础。20世纪20年代,玻尔理论的发展证实铪与锆同族,指导科学家从锆矿石中寻找铪元素。1923年,赫维西和科斯特借助X射线光谱技术发现铪元素,彰显了X射线光谱技术的独特价值。20世纪30年代以后,同位素理论和质谱技术促成了铪同位素的发现,使人们对铪元素有了新的认识。总之,铪元素及其同位素的发现是技术进步和思想发展的共同结晶。 相似文献