398 research outputs found
Highly Sensitive Fluorescence Probe Based on Functional SBA-15 for Selective Detection of Hg2+
An inorganic–organic hybrid fluorescence chemosensor (DA/SBA-15) was prepared by covalent immobilization of a dansylamide derivative into the channels of mesoporous silica material SBA-15 via (3-aminopropyl)triethoxysilane (APTES) groups. The primary hexagonally ordered mesoporous structure of SBA-15 was preserved after the grafting procedure. Fluorescence characterization shows that the obtained inorganic–organic hybrid composite is highly selective and sensitive to Hg2+ detection, suggesting the possibility for real-time qualitative or quantitative detection of Hg2+ and the convenience for potential application in toxicology and environmental science
Coordinatively Saturated Tris(oxazolinyl)borato Zinc Hydride-Catalyzed Cross Dehydrocoupling of Silanes and Alcohols
The four-coordinate zinc compound ToMZnH (1, ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) catalyzes selective alcoholysis of substituted hydrosilanes. The catalytic reaction of PhMeSiH2 and aliphatic alcohols favors the monodehydrocoupled product PhMeHSi–OR. With the aryl alcohol 3,5-C6H3Me2OH, the selectivity for mono(aryloxy)hydrosilane PhMeHSiOC6H3Me2 and bis(aryloxy)silane PhMeSi(OC6H3Me2)2 is controlled by relative reagent concentrations. Reactions of secondary organosilanes and diols provide cyclic bis(oxo)silacycloalkanes in high yield. The empirical rate law for the ToMZnH-catalyzed reaction of 3,5-dimethylphenol and PhMeSiH2 is −d[PhMeSiH2]/dt = k′obs[ToMZnH]1[3,5-C6H3Me2OH]0[PhMeSiH2]1 (determined at 96 °C) which indicates that Si–O bond formation is turnover-limiting in the presence of excess phenol
Self-structuring of lamellar bridged silsesquioxanes with long side spacers
Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers
Lewis Base Mediated β-Elimination and Lewis Acid Mediated Insertion Reactions of Disilazido Zirconium Compounds
The reactivity of a series of disilazido zirconocene complexes is dominated by the migration of anionic groups (hydrogen, alkyl, halide, OTf) between the zirconium and silicon centers. The direction of these migrations is controlled by the addition of two-electron donors (Lewis bases) or two-electron acceptors (Lewis acids). The cationic nonclassical [Cp2ZrN(SiHMe2)2]+ ([2]+) is prepared from Cp2Zr{N(SiHMe2)2}H (1) and B(C6F5)3 or [Ph3C][B(C6F5)4], while reactions of B(C6F5)3 and Cp2Zr{N(SiHMe2)2}R (R = Me (3), Et (5), n-C3H7 (7), CH═CHSiMe3 (9)) provide a mixture of [2]+ and [Cp2ZrN(SiHMe2)(SiRMe2)]+. The latter products are formed through B(C6F5)3 abstraction of a β-H and R group migration from Zr to the β-Si center. Related β-hydrogen abstraction and X group migration reactions are observed for Cp2Zr{N(SiHMe2)2}X (X = OTf (11), Cl (13), OMe (15), O-i-C3H7 (16)). Alternatively, addition of DMAP (DMAP = 4-(dimethylamino)pyridine) to [2]+ results in coordination to a Si center and hydrogen migration to zirconium, giving the cationic complex [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}H]+ ([19]+). Related hydrogen migration occurs from [Cp2ZrN(SiHMe2)(SiMe2OCHMe2)]+ ([18]+) to give [Cp2Zr{N(SiMe2DMAP)(SiMe2OCHMe2)}H]+ ([22]+), whereas X group migration is observed upon addition of DMAP to [Cp2ZrN(SiHMe2)(SiMe2X)]+ (X = OTf ([12]+), Cl ([14]+)) to give [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}X]+ (X = OTf ([26]+), Cl ([20]+)). The species involved in these transformations are described by resonance structures that suggest β-elimination. Notably, such pathways are previously unknown in early metal amide chemistry. Finally, these migrations facilitate direct Si–H addition to carbonyls, which is proposed to occur through a pathway that previously had been reserved for later transition metal compounds
Role of non-nitric oxide non-prostaglandin endothelium-derived relaxing factor(s) in bradykinin vasodilation
The influence of addition of a catalyst and chelating agent on the properties of titanium dioxide synthesized via the sol–gel method
Estudo biológico e comportamental de lagartas de Spodoptera frugiperda visando à produção de Baculovírus spodoptera
A utilização de bioinseticida a base de Spodoptera frugiperda
multiple nucleopolyhedrovirus (SfMNPV) possui potencial para o controle de
Spodoptera frugiperda (Lepidoptera: Noctuidae), porém sua obtenção em larga
escala depende da maximização da produção in vivo. Assim, alguns fatores
biológicos e comportamentais devem ser estudados para aperfeiçoar a
produção de SfMNPV com intuito de disponibilizar um bioinseticida eficiente,
economicamente viável e que possa ser usado no manejo de S. frugiperda nos
mais diversos sistemas agrícolas. Entre os fatores relacionados ao hospedeiro,
a temperatura e a idade para inoculação do vírus são de extrema importância,
pois interferem diretamente no ciclo de vida e na replicação viral. O
comportamento também deve ser avaliado, para evitar condições de criação do
hospedeiro que favoreçam o canibalismo e causa prejuízo na multiplicação in
vivo do SfMNPV. Assim, objetivou-se determinar a melhor condição térmica
para criar as lagartas e a idade ideal, para inocular e multiplicar o vírus no
hospedeiro, bem como, verificar a ocorrência do comportamento canibal em
lagartas de S. frugiperda. Os experimentos foram conduzidos no Laboratório de
Controle Microbiano de Insetos do Núcleo de Desenvolvimento Científico e
Tecnológico em Manejo Fitossanitário de Pragas e Doenças (NUDEMAFI),
localizado no Centro de Ciências Agrárias da UFES, em Alegre, Espírito Santo,
Brasil. A pesquisa foi desenvolvida em duas etapas, a primeira para determinar
a condição térmica e a idade ideais para criar e inocular, respectivamente, o
hospedeiro com o vírus, para multiplicação in vivo de SfMNPV. A segunda
etapa foi para avaliar o comportamento canibal de lagartas da espécie S.
frugiperda criadas a 22, 25 e 31°C, inoculadas com SfMNPV quando com
idades de 10, 8 e 4 dias, respectivamente, e mantidas em diferentes
densidades populacionais (5, 10, 25 e 50 lagartas por recipiente). A
mortalidade diminuiu com o aumento da temperatura e da idade do hospedeiro
nas temperaturas de 25, 28 e 31 °C. O aumento na taxa de canibalismo foi
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diretamente proporcional à densidade populacional quando as lagartas foram
criadas a 22 °C, inoculadas aos 10 dias de idade e 25 ºC, inoculadas aos 8
dias e atingiram 63,5 e 62,5%, respectivamente na densidade populacional de
50 lagartas. Mas, quando as lagartas foram criadas a 31ºC e inoculadas com
idade de 4 dias, a densidade populacional não afetou o comportamento
canibal, taxa média de 24%, inferior aos outros tratamentos com 50 lagartas
por recipiente. Demonstrando que é viável para a multiplicação viral, criar
lagartas a 31 °C e aos 4 dias de idade inocular o vírus, podendo a partir de
então colocar até 50 lagartas por recipiente, o que reduz a mão-de-obra
necessária para individualizar as lagartas e otimiza o espaço físico em uma
biofábrica. Portanto, se para otimizar o processo produção viral e o serviço em
uma biofábrica, é preciso maximizar a produção viral, reduzir o tempo de
multiplicação do vírus e o canibalismo entre as lagartas, com ausência de
contaminação da criação, a temperatura e idade ideais para criação massal de
S. frugiperda e inoculação do vírus nas lagartas, respectivamente, visando
produção de baculovírus em larga escala são de 31 ºC e 4 dias
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