全文获取类型
收费全文 | 204篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 125篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 14篇 |
物理学 | 66篇 |
出版年
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2016年 | 1篇 |
2015年 | 1篇 |
2014年 | 2篇 |
2013年 | 3篇 |
2012年 | 5篇 |
2011年 | 7篇 |
2010年 | 3篇 |
2009年 | 6篇 |
2008年 | 10篇 |
2007年 | 16篇 |
2006年 | 10篇 |
2005年 | 6篇 |
2004年 | 6篇 |
2003年 | 11篇 |
2002年 | 10篇 |
2001年 | 11篇 |
2000年 | 2篇 |
1999年 | 7篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1972年 | 4篇 |
1968年 | 4篇 |
1967年 | 4篇 |
1966年 | 2篇 |
1965年 | 1篇 |
1874年 | 1篇 |
排序方式: 共有210条查询结果,搜索用时 0 毫秒
11.
Natalie R. Altvater Rick W. Dorn Melissa C. Cendejas William P. McDermott Brijith Thomas Aaron J. Rossini Ive Hermans 《Angewandte Chemie (International ed. in English)》2020,59(16):6546-6550
Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B2(OH)xO(3?x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using 11B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO3 units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle. 相似文献
12.
Jaska CA Dorn H Lough AJ Manners I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):271-281
Reaction of [Pt(PEt(3))(3)] with the primary and secondary phosphine-borane adducts PhRPH x BH(3) (R=H, Ph) resulted in oxidative addition of a P-H bond at the Pt(0) center to afford the complexes trans-[PtH(PPhR x BH(3))(PEt(3))(2)] (1: R=H; 2: R=Ph). The products 1 and 2 were characterized by (1)H, (11)B, (13)C, (31)P, and (195)Pt NMR spectroscopy, and the molecular structures were verified by X-ray crystallography. In both cases, a trans arrangement of the hydride ligand with respect to the phosphidoborane ligand was observed. When 2 was treated with PhPH(2) x BH(3), a novel phosphidoborane ligand-exchange reaction occurred which yielded 1 and Ph(2)PH x BH(3). Treatment of 2 with one equivalent of depe (depe=1,2-bis(diethylphosphino)ethane) resulted in the formation of the complex cis-[PtH(PPh(2) x BH(3))(depe)] (3), in which the hydride ligand and the phosphidoborane ligand are in a cis arrangement. Treatment of 3 with PhPH(2) x BH(3) was found to result in an exchange of the phosphidoborane ligands to give the complex cis-[PtH(PPhH x BH(3))(depe)] (4) and Ph(2)PH x BH(3). Complex 4 was found to undergo further reaction in the presence of PhPH(2) x BH(3) to give meso-cis-[Pt(PPhH x BH(3))(2)(depe)] (5) and rac-cis-[Pt(PPhH x BH(3))(2)(depe)] (6). 相似文献
13.
As a follow-up to earlier investigations into the high-pressure polymerization of ethylene with symmetrically substituted bifunctional peroxides, the suitability of 2,5-dimethylhexane-2-t-butylperoxy-5-perpivalate, a peroxide with different substituents on both O—O groups, has been tested. The polymerization tests were carried out in continuous operation in a stirred autoclave at 1700 bar, 240–285°C, a residence time of 60 s, and an initiator concentration of 3–25 mol ppm in the feed. Conversions of up to 30% were achieved. The specific initiator consumption was 0.2–1 g initiator per kg polyethylene. The density of the polymers obtained was 0.915–0.925 g/mL, their average molecular weight was 40 × 103 to 60 × 103, and their melt flow index was 0.001–100 g/10 min. On the basis of the molecular weight distribution, polydispersities of 4–7 were obtained. 相似文献
14.
M. Kroon E. Andreasson E. Persson Jutemar V. Petersson L. Persson M. Dorn P.A.T. Olsson 《Experimental Mechanics》2018,58(1):75-86
Injection-moulding is one of the most common manufacturing processes used for polymers. In many applications, the mechanical properties of the product is of great importance. Injection-moulding of thin-walled polymer products tends to leave the polymer structure in a state where the mechanical properties are anisotropic, due to alignment of polymer chains along the melt flow direction. The anisotropic elastic-viscoplastic properties of low-density polyethylene, that has undergone an injection-moulding process, are therefore examined in the present work. Test specimens were punched out from injection-moulded plates and tested in uniaxial tension. Three in-plane material directions were investigated. Because of the small thickness of the plates, only the in-plane properties could be determined. Tensile tests with both monotonic and cyclic loading were performed, and the local strains on the surface of the test specimens were measured using image analysis. True stress vs. true strain diagrams were constructed, and the material response was evaluated using an elastic-viscoplasticity law. The components of the anisotropic compliance matrix were determined together with the direction-specific plastic hardening parameters. 相似文献
15.
Georgios Velkos Denis S. Krylov Kyle Kirkpatrick Lukas Spree Vasilii Dubrovin Bernd Büchner Stanislav M. Avdoshenko Valeriy Bezmelnitsyn Sean Davis Paul Faust James Duchamp Harry C. Dorn Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2019,58(18):5891-5896
The azafullerene Tb2@C79N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb?Tb bond. Relaxation of magnetization in Tb2@C79N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τQTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped. 相似文献
16.
Prof. Dr. Steven Stevenson Amanda J. Rothgeb Katelyn R. Tepper Prof. Dr. James Duchamp Prof. Dr. Harry C. Dorn Xian B. Powers Mrittika Roy Prof. Dr. Marilyn M. Olmstead Prof. Dr. Alan L. Balch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12545-12551
Purified samples of Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78 have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho2O3 or Tb4O7. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C2(22010)-C78 cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho3N or Tb3N unit is planar. Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78 use the same cage previously found for Gd3N@C2(22010)-C78 rather than the IPR-obeying cage found in Sc3N@D3h-C78. 相似文献
17.
Gorga MP Neely ST Dorn PA Dierking D Cyr E 《The Journal of the Acoustical Society of America》2002,112(6):2910-2920
Measurements of DPOAE level in the presence of a suppressor were used to describe a pattern that is qualitatively similar to population studies in the auditory nerve and to behavioral studies of upward spread of masking. DPOAEs were measured in the presence of a suppressor (f3) fixed at either 2.1 or 4.2 kHz, and set to each of seven levels (L3) from 20 to 80 dB SPL. In the presence of a fixed f3 and L3 combination, f2 was varied from about 1 oct below to at least 1/2 oct above f3, while L2 was set to each of 6 values (20-70 dB SPL). L1 was set according to the equation L1 = 0.4L2 + 39 [Janssen et al., J. Acoust. Soc. Am. 103, 3418-3430 (1998)]. At each L2, L1 combination, DPOAE level was measured in a control condition in which no suppressor was presented. Data were converted into decrements (the amount of suppression, in dB) by subtracting the DPOAE level in the presence of each suppressor from the DPOAE level in the corresponding control condition. Plots of DPOAE decrements as a function of f2 showed maximum suppression when f2 approximately = f3. As L3 increased, the suppressive effect spread more towards higher f2 frequencies, with less spread towards lower frequencies relative to f3. DPOAE decrement versus L3 functions had steeper slopes when f2 > f3, compared to the slopes when f2 < f3. These data are consistent with other findings that have shown that response growth for a characteristic place (CP) or frequency (CF) depends on the relation between CP or CF and driver frequency, with steeper slopes when driver frequency is less than CF and shallower slopes when driver frequency is greater than CF. For a fixed amount of suppression (3 dB), L3 and L2 varied nearly linearly for conditions in which f3 approximately = f2, but grew more rapidly for conditions in which f3 < f2, reflecting the basal spread of excitation to the suppressor. The present data are similar in form to the results observed in population studies from the auditory nerve of lower animals and in behavioral masking studies in humans. 相似文献
18.
19.
Evidence of the compressive growth of basilar-membrane displacement can be seen in distortion-product otoacoustic emission (DPOAE) levels measured as a function of stimulus level. When the levels of the two stimulus tones (f1 and f2) are related by the formula L1 = 39 dB + 0.4 x L2 [Kummer et al., J. Acoust. Soc. Am. 103, 3431-3444 (1998)] the shape of the function relating DPOAE level to L2 is similar (up to an L2 of 70 dB SPL) to the classic Fletcher and Munson [J. Acoust. Soc. Am. 9, 1-10 (1933)] loudness function when plotted on a logarithmic scale. Explicit estimates of compression have been derived based on recent DPOAE measurements from the laboratory. If DPOAE growth rate is defined as the slope of the DPOAE I/O function (in dB/dB), then a cogent definition of compression is the reciprocal of the growth rate. In humans with normal hearing, compression varies from about 1 at threshold to about 4 at 70 dB SPL. With hearing loss, compression is still about 1 at threshold, but grows more slowly above threshold. Median DPOAE I/O data from ears with normal hearing, mild loss, and moderate loss are each well fit by log functions. When the I/O function is logarithmic, then the corresponding compression is a linear function of stimulus level. Evidence of cochlear compression also exists in DPOAE suppression tuning curves, which indicate the level of a third stimulus tone (f3) that reduces DPOAE level by 3 dB. All three stimulus tones generate compressive growth within the cochlea; however, only the relative compression (RC) of the primary and suppressor responses is observable in DPOAE suppression data. An RC value of 1 indicates that the cochlear responses to the primary and suppressor components grow at the same rate. In normal ears, RC rises to 4, when f3 is an octave below f2. The similarities between DPOAE and loudness compression estimates suggest the possibility of predicting loudness growth from DPOAEs; however, intersubject variability makes such predictions difficult at this time. 相似文献
20.
Moshammer R Ullrich J Feuerstein B Fischer D Dorn A Schröter CD Crespo Lopez-Urrutia JR Hoehr C Rottke H Trump C Wittmann M Korn G Sandner W 《Physical review letters》2003,91(11):113002
Electron emission for single ionization of Ne by 25 fs, 1.0 PW/cm(2) laser pulses at 800 nm has been investigated in a kinematically complete experiment using a "reaction microscope." Mapping the complete final state momentum space with high resolution, a distinct local minimum is observed at P(e parallel )=0, where P(e parallel ) is the electron momentum parallel to the laser polarization. Whereas tunneling theory predicts a maximum at zero momentum, our findings are in good agreement with recent semiclassical predictions which were interpreted to be due to "recollision." 相似文献