共查询到20条相似文献,搜索用时 15 毫秒
1.
Zhang L Liu HL Yang GH Huang XR Li Y Sun YB Sun CC 《Journal of molecular modeling》2011,17(12):3173-3181
A detailed doublet potential energy surface for the reaction of CH with CH3CCH is investigated at the B3LYP/6-311G(d,p) and G3B3 (single-point) levels. Various possible reaction pathways are probed.
It is shown that the reaction is initiated by the addition of CH to the terminal C atom of CH3CCH, forming CH3CCHCH 1 (1a,1b). Starting from 1 (1a,1b), the most feasible pathway is the ring closure of 1a to CH3–cCCHCH 2 followed by dissociation to P
3
(CH3–cCCCH+H), or a 2,3 H shift in 1a to form CH3CHCCH 3 followed by C–H bond cleavage to form P
5
(CH2CHCCH+H), or a 1,2 H-shift in 1 (1a, 1b) to form CH3CCCH2
4 followed by C–H bond fission to form P
6
(CH2CCCH2+H). Much less competitively, 1 (1a,1b) can undergo 3,4 H shift to form CH2CHCHCH 5. Subsequently, 5 can undergo either C–H bond cleavage to form P
5
(CH2CHCCH+H) or C–C bond cleavage to generate P
7
(C2H2+C2H3). Our calculated results may represent the first mechanistic study of the CH + CH3CCH reaction, and may thus lead to a deeper understanding of the title reaction. 相似文献
2.
Takako Mashiko Kenta Yamada Shuichi Hiraoka Umpei Nagashima 《Molecular simulation》2015,41(10-12):845-849
Molecular dynamics simulations were performed for the hexameric nanocubes of methylated (16) and demethylated (26) gear-shaped amphiphiles in pure methanol to reveal the difference in structural fluctuation between 16 and 26. Within our simulation time of 2.0 ns, the cubic structure of 16 in methanol is maintained, whereas that of 26 is collapsed. We found that the triple π-stacking moieties consisting of the three 3-pyridyl groups in 26 are more fluctuated than those in 16. This suggests that methyl groups serve to reduce structural fluctuation for nanocubes. We also found that the existence of the solvent molecules near the nanocube is an important factor for the collapse of the 26 structure. 相似文献
3.
L. K. Kaczmarek 《Biological cybernetics》1976,22(4):229-234
A simplified model is presented of the dynamics of excitatory and inhibitory neurons in the cerebral cortex. A key feature of the model is that neurons may cease to fire when strongly depolarized (spike inactivation). Computer simulations for different parameters reveal five classes of solutons: a) steady states in which neither excitatory nor inhibitory cells are active, b) steady states in which one or both types of cells fire repetitively, c) states in which one type of cell fluctuates rapidly between bursts of action potentials and inactivity due to strong depolarization, d) rhythmic activity in which both types of cells fire in unison followed by a period of spike inactivation and e) states similar to d but in which the inhibitory cells never produce action potentials. Solutions b, c, d, and e qualitatively resemble the different firing patterns observed during experimental seizures. It is shown that changes in those parameters that are functions of potassium concentration can induce changes in the type of solution. It is therefore proposed that the increase in extracellular potassium concentration during seizures may be responsible for the progressive changes observed in firing patterns and particularly for the transition from tonic to clonic patterns. A method is also outlined for testing the predictions of the model. 相似文献
4.
Tateki Hayashi Mitsuo Namiki Keiichi Tsuji 《Bioscience, biotechnology, and biochemistry》2013,77(9):1955-1960
During the formation of radical A (2) and its precursor (tris(2-deoxy-2-L-ascorbyl)amine, 1) by the reaction of dehydroascorbic acid (DHA) with amino acid, ascorbic acid (AsA) and the reduced red pigment (3) were newly identified, in addition to scorbamic acid (SCA) and the red pigment (4), as intermediate products. The addition of AsA to the DHA-amino acid reaction, as well as to the DHA-SCA reaction, greatly increased the formation of 3 and 1. The reaction of AsA with 4 gave rapidly 3, followed by the gradual production of 1. From these results, a reaction pathway is proposed that 3 formed by the reduction of 4 with AsA is a key intermediate and its condensation with DHA followed by reduction with AsA might produce 2 and 1. 相似文献
5.
Subramony Mahadevan 《Journal of biosciences》1997,22(4):505-513
The product of the
bglG
gene of Escherichia
coli
was among the first bacterial antiterminators to be identified and characterized. Since the elucidation ten years ago of its
role in the regulation of the
bgl
operon
of E. coli,a large number of homologies have been discovered in both Gram-positive and Gram-negative bacteria. Often the homologues of
BglG in other organisms are also involved in regulating β-glucoside utilization. Surprisingly, in many cases, they mediate
antitermination to regulate a variety of other catabolic functions. Because of the high degree of conservation of the
cis-acting regulatory elements, antiterminators from one organism can function in another. Generally the antiterminator protein
itself is negatively regulated by phosphorylation by a component of the phosphotransferase system. This family of proteins
thus represents a highly evolved regulatory system that is conserved across evolutionarily distant genuses. 相似文献
6.
7.
Karim Christina Scopinho Furquim Gervásio Henrique Bechara Maria Izabel Camargo Mathias 《Experimental & applied acarology》2010,50(1):59-70
This study describes the changes undergone by cells of the salivary glands of unfed and feeding (at day two and four post-attachment)
Rhipicephalus sanguineus males, as well as new cell types. In unfed males, types I and II acini are observed with cells “undifferentiated”, undefined
1 and 2 (the latter, with atypical granules), a, c1 and c3; type III is composed of cells d and e; and type IV present cells g. In males at day two post-attachment, type I acini exhibit the same morphology of unfed individuals. An increase in size
is observed in types II, III, and IV, as cells are filled with secretion granules. Some granules are still undergoing maturation.
In type II acinus, cells a, b and c1–c8 are observed. Cells c7 and c8 are described for the first time. Cells c7 are termed as such due to the addition of polysaccharides in the composition of the secretion granules (in unfed individuals,
they are termed undefined
1). Type III acini exhibit cells d and e completely filled with granules, and in type IV, cells g contain granules in several stages of maturation. In males at day four post-attachment, type I acini do not exhibit changes.
Granular acini exhibit cells with fewer secretion granules, which are already mature. In type II acini, cells a, b, c1–c5 are present, type III exhibit cells d and e, and type IV contain cells g with little or no secretion. This study shows that in the salivary glands of R.
sanguineus males, cells a, c1, and c3 of type II acinus, and cells d and e of type III do not exhibit changes in granular content, remaining continuously active during the entire feeding period. This
indicates that during the intervals among feeding stages, gland cells reacquire the same characteristics found in unfed individuals,
suggesting that they undergo reprogramming to be active in the next cycle. 相似文献
8.
Marcus Lehnert 《Brittonia》2011,63(1):11-45
A summary is presented of all Peruvian species of scaly tree ferns (Cyatheaceae). A total of 83 species is native to Peru
(Sphaeropteris 1 sp., Alsophila sect. Alsophila 9 spp., Alsophila sect. Gymnosphaera 1 sp., Cyathea 72 spp.), with 13 endemic species in Cyathea and one in Alsophila. The following new species are described and illustrated: Alsophila gastonyi, Cyathea chontilla, C. nephele, C. polliculi, and C. praetermissa. The genera Cnemidaria and Trichipteris are no longer recognized and merged in Cyathea. Necessary combinations are made for Cyathea alatissima, C. nervosa, and C. uleana. Cyathea serpens is presented in detail and its relationship is discussed. An artificial key to the Peruvian species of Cyatheaceae is provided. 相似文献
9.
T. C. Onstott L.-H. Lin M. Davidson B. Mislowack M. Borcsik J. Hall 《Geomicrobiology journal》2013,30(6):369-414
Water residing within crustal fractures encountered during mining at depths greater than 500 meters in the Witwatersrand basin of South Africa represents a mixture of paleo-meteoric water and 2.0–2.3 Ga hydrothermal fluid. The hydrothermal fluid is highly saline, contains abiogenic CH 4 and hydrocarbon, occasionally N 2 , originally formed at ~ 250–300°C and during cooling isotopically exchanged O and H with minerals and accrued H 2 , 4 He and other radiogenic gases. The paleo-meteoric water ranges in age from ~ 10 Ka to > 1.5 Ma, is of low salinity, falls along the global meteoric water line (GMWL) and is CO 2 and atmospheric noble gas-rich. The hydrothermal fluid, which should be completely sterile, has probably been mixing with paleo-meteoric water for at least the past ~100 Myr, a process which inoculates previously sterile environments at depths > 2.0 to 2.5 km. Free energy flux calculations suggest that sulfate reduction is the dominant electron acceptor microbial process for the high salinity fracture water and that it is 10 7 times that normally required for cell maintenance in lab cultures. Flux calculations also indicate that the potential bioavailable chemical energy increases with salinity, but because the fluence of bioavailable C, N and P also increase with salinity, the environment remains energy-limited. The 4 He concentrations and theoretical calculations indicate that the H 2 that is sustaining the subsurface microbial communities (e.g. H 2 -utilizing SRB and methanogens) is produced by water radiolysis at a rate of ~1 nM yr ?1 . Microbial CH 4 mixes with abiogenic CH 4 to produce the observed isotopic signatures and indicates that the rate of methanogenesis diminishes with depth from ~ 100 at < 1 kmbls, to < 0.01 nM yr ?1 at > 3 kmbls. Microbial Fe(III) reduction is limited due to the elevated pH. The δ13C of dissolved inorganic carbon is consistent with heterotrophy rather than autotrophy dominating the deeper, more saline environments. One potential source of the organic carbon may be microfilms present on the mineral surfaces. 相似文献
10.
Evidence for the non-enzymatic phosphorylation of bovine serum albumin (BSA) by sodium bis(2-ethyl-2-hydroxybutyrato)oxochromate(V), Na[CrVO(ehba)2], 1, sodium bis(2-hydroxy-2-methylbutyrato)oxochromate(V), Na[CrVO(hmba)2], 2 and potassium dichromate, K2Cr2O7, 3 in the presence of labeled adenosine-5′-triphosphate (ATP) under conditions of physiological pH is presented. Aggregation and extent of phosphorylation of BSA mediated by 1, 2 or 3 seems to increase with the concentration and time of incubation of the reaction mixture containing all the reactants. The [γ-32P] label in ATP is incorporated into aggregates of BSA in the in vitro reaction of the protein with ATP in the presence of 1, 2 or 3. Phosphorylation of BSA by ATP in the absence of 1, 2 or 3 is negligible. Addition of EDTA reverses aggregation of protein and liberates partially the incorporated phosphate label. The stoichiometry of phosphorylation is found to be the highest and is equal to 12.25 mol PO43−/mol BSA in the presence of 500 μM of 1, which decreases to 10.56 mol PO43−/mol BSA after EDTA treatment. Resistance to the removal of phosphate label by EDTA increases with increase in time of incubation. Dialysis of phosphorylated BSA reverses the incorporated [γ-32P] label only partially, indicating the formation of covalent links of phosphate groups to BSA. Evidence for the site of phosphorylation in the reaction mediated by 1, 2 or 3 being hydroxyl side groups of tyrosine and serine/threonine residues has been gained. Based on the results, a possibility that 1, 2 and 3 mimic the function of tyrosine and serine/threonine kinases has been invoked. 相似文献
11.
Bruno RD Vasaitis TS Gediya LK Purushottamachar P Godbole AM Ates-Alagoz Z Brodie AM Njar VC 《Steroids》2011,76(12):1268-1279
In a continuing study of our clinical candidate 5 VN/124-1 (TOK-001) and analogs as potential agents for prostate cancer therapy, putative metabolites (10, 15 and 18) of compound 5 were rationally designed and synthesized. However, none of these agents were as efficacious as 5 in several in vitro studies. Using western blot analysis, we have generated a preliminary structure–activity relationship (SAR) of 5 and related analogs as androgen receptor ablative agents (ARAAs). In vivo using the androgen-dependent LAPC-4 prostate cancer xenograft model, we demonstrated for the first time that 5 is more efficacious than the 17-lyase inhibitor 3 (abiraterone)/4 (abiraterone acetate) that is currently in phase III clinical trials. In our desire to optimize the potency of 5, compounds 6 (3ξ-fluoro-) and 9 (3β-sulfamate-) designed to increase the stability and oral bioavailability of 5, respectively were evaluated in vivo. We showed, that on equimolar basis, compound 6 was ∼2-fold more efficacious versus LAPC-4 xenografts than 5, but the toxicity observed with 6 is of concern. These studies further demonstrate the efficacy of 5 in a clinically relevant prostate cancer model and justify its current clinical development as a potential treatment of prostate cancer. 相似文献
12.
Onorato A Pavlik C Invernale MA Berghorn ID Sotzing GA Morton MD Smith MB 《Carbohydrate research》2011,(13):1662-1670
The polymer PEDOT+ (1 or 2) mediates a cyclodehydration reaction with alditols 3, 5, 7, 9, in hydrocarbon solvents, to give cyclic ethers 4, 6, 8, or 10, respectively, in high yield with a trivial isolation protocol. Polymers 1 or 2 also mediate the cyclodehydration of ketohexoses such as d-fructose, but not aldohexoses, to the important industrial intermediate 5-hydroxymethylfurfural (17), under milder conditions when compared to reactions mediated by mineral acids. A cascade reaction with ketohexoses is observed in toluene via cyclodehydration followed by Friedel–Crafts alkylation of the initially formed benzylic alcohol to give 16. 相似文献
13.
14.
Ramirededy Nageswara Reddy Ravichandra Reddy Mutyala Polamarasetty Aparoy Pallu Reddanna Mutyala Rami Reddy 《Journal of molecular modeling》2010,16(2):203-209
Since the human body for many reasons can adapt and become resistant to drugs, it is important to develop and validate computer
aided drug design (CADD) methods that could help predict binding affinity changes that can result from these resistant enzymes.
The free energy perturbation (FEP) methodology is the most accurate means of estimating relative binding affinities between
inhibitors and protein variants. In this paper, we describe the role played by hydrophobic residues lining the active site
region, particularly
79
Ile and
176
Phe, in the binding of methotrexate to the Escherichia coli (E. coli) thymidylate synthase (TS) enzyme, using the thermodynamic cycle perturbation (TCP) approach. The computed binding free energy
differences on the binding of methotrexate to the native and some mutant E. coli TS structures have been compared with experimental results. Computationally, four different ‘mutations’ have been simulated
on the TS enzyme with methotrexate (MTX):
79
Ile →
79
Val;
79
Ile →
79
Ala;
79
Ile →
79
Leu; and
176
Phe →
176
Ile. The calculated results indicate that in each of these cases, the native residues (
79
Ile and
176
Phe) interact more favorably with methotrexate than the mutant residues and these results are corroborated by experimental measurements.
Binding preference to wild type residues can be rationalized in terms of their better hydrophobic contacts with the phenyl
ring of methotrexate. 相似文献
15.
16.
M. Gabriela Mángano Noelia B. Carmona Luis A. Buatois Fernando Muñiz Guinea 《Ichnos》2013,20(3):179-190
A new ichnospecies of Arthrophycus Hall 1852, A. minimus , is described from Upper Cambrian-Lower Tremadocian, shallow-marine strata of northwest Argentina. This new ichnospecies consists of small, long, regularly annulated hypichnial elements displaying subcircular to squarish cross-section and a ventral median groove. Side branches are occasionally present, but palmate, fan-like structures and scribbling patterns are absent. We adopt a relatively narrow diagnosis of Arthrophycus , suggesting that roughly annulated, cylindrical structures should not be included in this ichnogenus, unless other diagnostic features (i.e., squarish cross-section, median groove, zipper-like annulations) are also present. Arthrophycus is a common ichnotaxon in Ordovician-Silurian shallow-marine siliciclastic environments. Post-Paleozoic occurrences are removed from Arthrophycus . Arthrophycus has been proposed as a biostratigraphic index fossil in Ordovician-Silurian rocks. The presence of A. minimus in the Santa Rosita Formation of northwest Argentina indicates that Arthrophycus ranges at least from the Upper Cambrian-Lower Tremadocian with probable representatives in the Lower Cambrian and, therefore, its biostratigraphic utility is extended. Arthrophycus minimus represents the first Cambrian occurrence exhibiting not only fine, diagnostic morphologic features, but also the classical Arthrophycus behavioral pattern in dense monoichnospecific assemblages. The exploratory behavioral pattern displayed by A. minimus is simpler than that of the younger ichnospecies, particularly A. brogniartii, A. alleghaniensis, and A. lateralis . This is consistent with the basal position of A. minimus within the arthrophycid lineage. 相似文献
17.
目的 了解乡镇卫生院各项收支及药品补偿状况,探讨基本药物制度实施后,取消药品加成对乡镇卫生院的影响。方法 收集华东三省49家乡镇卫生院财务及药品收支数据,对定量资料进行统计分析。结果 乡镇卫生院主要的补偿渠道依然是药品收入,乡镇卫生院收入增长主要归因于增加药品收入。在财政补助收入大幅增加的情况下,乡镇卫生院对药品收入的依赖程度有所降低。结论 基本药物制度的实施对乡镇卫生院的平稳运行有影响,可采取加强财政补助、建立综合补偿机制、遏制药品价格虚高等措施保证乡镇卫生院在改革中的平稳运行。 相似文献
18.
M. Blumauerová V. Přikrylová Z. Stoycheva N. Vesselinova T. K. Todorov 《Folia microbiologica》1991,36(6):533-537
The production of erythromycin A (1) and free erythronolide B (2) inSaccharopolyspora erythraea BTCC-2 is accompanied by formation of erythromycin A N-oxide (3) and other minor components, the ratio of yields of1 and3 being 97:3. Erythromycin-blocked mutants of type I (impaired in some unidentified steps prior to lactone synthesis) and type
II (accumulating only2) cosynthesized both1 and the accompanying metabolites, but the ratio of1 and3 changed to 70:30. In pure cultures of type I, exogenous2 was converted to1 and minor components in ratios typical of the strain BTCC-2, whereas mutants of type II were effective convertors of1 to3. 相似文献
19.
Michael A. Sundue 《Brittonia》2010,62(4):357-399
This paper describes Ascogrammitis, a new genus of grammitid ferns formerly combined under Terpsichore. Seventeen species are recognized, including five new ones: A. clavigera, A. colombiensis, A. loxensis, A. oxapampensis, and A. tungurahuae. New combinations are made for A. alan-smithii, A. anfractuosa, A. angustipes, A. athyrioides, A. clathrata, A. cuencana, A. david-smithii, A. dilatata, A. nana, A. pichinchae, A. pichinchensis, A. stuebelii, and a lectotype is chosen for Polypodium induens. A key is provided to distinguish the species, and illustrations are provided for 12 species. The genus occurs primarily
in neotropical cloud forests, with the greatest diversity in the Andes. Ascogrammitis is one of two monophyletic groups of grammitid ferns that are consistently associated with Acrospermum, an epibiotic bitunicate ascomycete that produces black clavate fruiting bodies. 相似文献
20.
Khairuzzaman B. Mullah Wesley G. Bentrude 《Nucleosides, nucleotides & nucleic acids》2013,32(1-3):127-153
Abstract Photo-Arbuzov rearrangement of the benzylic phosphite 18 affords the benzylphosphonate 19 which is converted to the bromo derivative 21. The latter is a common precursor for the preparation of a series of branched-chain, acyclic nucleoside-based, benzylphosphonic acids, 25, 28, 32, and 35. 相似文献