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51.
Silla JM Cormanich RA Duarte CJ Freitas MP Ramalho TC Barbosa TM Santos FP Tormena CF Rittner R 《The journal of physical chemistry. A》2011,115(35):10122-10127
Suitable (3)J(H,H) coupling constants and theoretical calculations were used to define the conformational preferences of trans-2-bromoalkoxycyclohexanes (alkoxy = OMe, OEt, O(i)Pr, and O(t)Bu) for the isolated molecule and as a function of the medium. The diaxial conformer was preponderant, or at least similarly populated to the diequatorial form, for the tert-butoxy derivative only, while the diequatorial conformer was prevalent for the remaining alkoxy derivatives (except for the OMe derivative in CCl(4) solution). The conformational behavior of these compounds was analyzed on the basis of classical steric effects and attractive electron delocalizations, by means of natural bond orbital analysis. 相似文献
52.
The intermediacy of the geminate base-proton pair (A*···H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH(+)* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base-proton pair A*···H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*···H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec), of A*···H(+)) from the diffusion controlled rates (dissociation, k(diss), and formation, k(diff)[H(+)], of A*···H(+)), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)). 相似文献
53.
We study the spectrum of the Laplace operator of a complete minimal properly immersed hypersurface M in \({\mathbb{R}^{n+1}}\). (1) Under a volume growth condition on extrinsic balls and a condition on the unit normal at infinity, we prove that M has only essential spectrum consisting of the half line [0, +∞). This is the case when \({{\rm lim}_{\tilde{r}\to +\infty}\,\tilde{r}\kappa_i=0}\), where \({\tilde{r}}\) is the extrinsic distance to a point of M and κ i are the principal curvatures. (2) If the κ i satisfy the decay conditions \({|\kappa_i|\leq 1/\tilde{r}}\) and strict inequality is achieved at some point \({y\in M}\), then there are no eigenvalues. We apply these results to minimal graphic and multigraphic hypersurfaces. 相似文献
54.
55.
Schuquel IT Pontes RM Freitas MP Rittner R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,81(1):135-139
The infrared spectra of 3-X-2-methylpropenes (X = Cl, Br, I, NMe(2), NEt(2), OH, OMe, OEt, SH, SMe and SEt) have been recorded at room temperature in CCl(4) solution. The C=C stretching mode was analyzed and compared to theoretically calculated data to give insight about the conformational isomerism of these compounds. A combination band systematically appears in all spectra (except for amines); the remaining ν(C=C) band and the corresponding intensities were used to obtain the conformer populations. For second-period atoms bonded to C-3, two or more conformers are observed in CCl(4) solution, but when substitution by heavier atoms takes place, only one conformer is observed under the tested conditions, i.e., the gauche form with respect to the C=C-C-X dihedral angle. Therefore, steric hindrance between X and =CH(2) in the s-cis form is strongly dependent on the heteroatom size, while the effect of the alkyl chain bonded to the heteroatom seems to be of secondary importance. 相似文献
56.
Rangel TB Assreuy AM Pires Ade F Carvalho AU Benevides RG Simões Rda C Silva HC Bezerra MJ Nascimento AS Nascimento KS Nagano CS Sampaio AH Delatorre P Rocha BA Fernandes PM Cavada BS 《Molecules (Basel, Switzerland)》2011,16(6):5087-5103
DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins. 相似文献
57.
This work proposes two simple dynamic methods that provide an accurate method for measurement of diffusion coefficients in
building materials. Experimental measurements of moisture diffusion coefficients covered three commonly used building materials
and they were carried out for a range of the relevant parameters, as temperature and relative humidity. The diffusion coefficients
obtained by the two dynamic methods show a deviation comparatively to the steady-sate cup method; however, this variance is
in accordance with the results presented in literature. 相似文献
58.
Jamile Silva da Costa Jofre Jacob da Silva Freitas William N. Setzer Joyce Kelly R. da Silva Jos Guilherme S. Maia Pablo Luis B. Figueiredo 《Molecules (Basel, Switzerland)》2022,27(24)
Myrcia sylvatica (G. Mey) DC. is known as “insulin plant” because local communities use the infusions of various organs empirically to treat diabetes. The leaves of seven specimens of Myrcia sylvatica (Msy-01 to Msy-07) were collected in the Brazilian Amazon. Furthermore, the essential oils were extracted by hydrodistillation and analyzed by gas chromatography coupled to mass spectrometry, and their chemical compositions were submitted to multivariate analysis (Principal Component Analysis and Hierarchical Cluster Analysis). The multivariate analysis displayed the formation of four chemical profiles (chemotypes), described for the first time as follows: chemotype I (specimen Msy-01) was characterized by germacrene B (24.5%), γ-elemene (12.5%), and β-caryophyllene (10.0%); chemotype II (specimens Msy-03, -06 and -07) by spathulenol (11.1–16.0%), germacrene B (7.8–20.7%), and γ-elemene (2.9–7.6%); chemotype III (Msy-04 and -05) by spathulenol (9.8–10.1%), β-caryophyllene (2.5–10.1%), and δ-cadinene (4.8-5.6%); and chemotype IV, (Msy-02) by spathulenol (13.4%), caryophyllene oxide (15.0%), and α-cadinol (8.9%). There is a chemical variability in the essential oils of Myrcia sylvatica occurring in the Amazon region. 相似文献
59.
Ana Fernandes Sara Simes Isabel M. P. L. V. O. Ferreira Maria Joo Alegria Nuno Mateus Anabela Raymundo Victor de Freitas 《Molecules (Basel, Switzerland)》2023,28(1)
This work explores the potential of Rocha do Oeste pear pomace to be used as a sustainable and healthy food ingredient. Moreover, the enrichment with yeast protein extract (YPE) may be useful to design innovative food products. The main goals of this study were to assess pear pomace concerning: (i) chemical composition and antioxidant capacity; (ii) rheology, texture, and microstructure characterization (alone or enriched with YPE), before and after heating. The results showed that pear pomace was a rich source of dietary fibers (74.5% DW), with phenolic compounds (3.9 mg chlorogenic acid equivalents/g dry weight), also presenting antiradical activity (3.90 μmol Trolox equivalents/g DW). Pear pomace showed a shear thinning behavior and a typical soft-gel behavior, which was not affected by YPE enrichment, thus suggesting that YPE did not affect pear pomace technological properties. Thermal treatment also did not alter pear pomace rheological properties. YPE addition induced a decrease in the apparent viscosity and a destabilizing effect, compared to the samples that were subjected to thermal processing. These results highlight the importance of pear pomace and the use of YPE for protein enrichment, opening new opportunities for their exploitation. 相似文献
60.
Sunny K. S. Freitas Felipe L. Oliveira Thiago C. dos Santos Danilo Hisse Claudia Merlini Célia M. Ronconi Prof. Dr. Pierre M. Esteves 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2342-2347
A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m2 g−1 and pore size of 10.3 Å. The material has CO2 uptake of 2.14 mmol g−1 (0.5 bar), 2.7 mmol g−1 (1 bar), and 6.8 mmol g−1 (20 bar), the latter corresponding to 3 CO2 molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10−7 S cm−1, which increases to 5.26×10−4 S cm−1 upon exposure to I2 vapor. DFT calculations using periodic conditions support the findings. 相似文献