RESUMEN
Two series of novel functionalized polyhydroisoquinoline derivatives have been synthesized via the three-component domino reaction of glutaraldehyde and malononitrile with a series of ß-ketoamides under microwave irradiation conditions in the presence of a catalytic amount of Et3N (10 mol%). This reaction represents the first reported process for the facile conversion of a ß-ketoamide to a hydroisoquinoline via a C-N bond cleavage reaction without the need for a multistep reaction process.
Asunto(s)
Isoquinolinas/síntesis química , Amidas/química , Amidas/efectos de la radiación , Catálisis , Glutaral/química , Glutaral/efectos de la radiación , Isoquinolinas/química , Microondas , Nitrilos/química , Nitrilos/efectos de la radiaciónRESUMEN
All lit up: A novel and efficient desulfonylation method of tosyl amides has been developed by means of visible-light-promoted reductive cleavage of N-S bonds. This method has a broad substrate scope, good functional group tolerance, and excellent yields.
Asunto(s)
Amidas/química , Luz , Procesos Fotoquímicos , Compuestos de Tosilo/química , Amidas/efectos de la radiación , Catálisis , Estructura Molecular , Oxidación-Reducción , Fotoquímica , Compuestos de Tosilo/efectos de la radiaciónRESUMEN
Scalar coupling relaxation, which is usually only associated with closely resonant nuclei (e.g., (79)Br-(13)C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-(13)C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T(1) shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar (14)N adjacent to the (13)C nucleus in the amide group. This contribution is only effective in low magnetic fields (i.e., less than 800 µT) and prevents the use of molecules bearing the (13)C-amide group as hyperpolarized MRS/MRI probes. In the present work, this hypothesis is explored both theoretically and experimentally. The results show that high hyperpolarization levels can be retained using either a (15)N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner.
Asunto(s)
Amidas/química , Isótopos de Carbono/química , Planeta Tierra , Espectroscopía de Resonancia Magnética/métodos , Magnetometría/métodos , Nitrógeno/química , Amidas/efectos de la radiación , Isótopos de Carbono/efectos de la radiación , Campos Magnéticos , Nitrógeno/efectos de la radiaciónRESUMEN
Transport behaviour of actinides viz. Am(3+), Pu(4+) and UO(2)(2+) was investigated from nitric acid feed conditions using PTFE (polytetrafluoroethylene) flat sheet supported liquid membranes (SLM) containing an irradiated solvent system comprising of N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) as the carrier extractant and N,N-di-n-hexyloctanamide (DHOA) as the phase modifier. The present studies were carried out in order to understand the effect of irradiation on the long term reusability of the SLM and the decontamination behaviour in the absorbed dose range of 0-100 MRad. The studies using irradiated carrier included those with irradiated TODGA without any phase modifier and with 0.1M as well as 0.5M DHOA as the phase modifier. Transport behaviour of all the metal ions were found to be seriously affected with increasing radiation dose which was reflected in the decreasing percentage transport (%T) as well as permeability co-efficient (P) values. Though Sr(II) transport was quite significant with all the three unirradiated solvent systems, it was surprisingly low (<5%) when solvents exposed to 100 MRad dose were used in the SLM. Separation factors (S.F.) of the actinides over Sr(II) were calculated and were found to increase at higher radiation doses suggesting possibility of getting better decontamination on prolonged use of the supported liquid membrane system.
Asunto(s)
Elementos de Series Actinoides/química , Rayos gamma , Glicolatos/efectos de la radiación , Membranas Artificiales , Estroncio/química , Amidas/química , Amidas/efectos de la radiación , Glicolatos/química , Politetrafluoroetileno/químicaRESUMEN
Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.
Asunto(s)
Amidas/química , Calcógenos/química , Calcógenos/efectos de la radiación , Iluminación/métodos , Nanoestructuras/química , Puntos Cuánticos , Plata/química , Amidas/efectos de la radiación , Coloides/química , Coloides/efectos de la radiación , Cristalización/métodos , Rayos Infrarrojos , Luz , Ensayo de Materiales , Nanoestructuras/efectos de la radiación , Nanoestructuras/ultraestructura , Plata/efectos de la radiación , Propiedades de SuperficieRESUMEN
An ultrasound-assisted preparation of a series of novel 3,5-diaryl-4,5-dihydro-1H-pyrazole-1-carboximidamides that proceeds via the efficient reaction of chalcones with aminoguanidine hydrochloride under clean conditions is described.
Asunto(s)
Amidas/síntesis química , Amidas/efectos de la radiación , Chalconas/química , Chalconas/efectos de la radiación , Guanidinas/química , Guanidinas/efectos de la radiación , Sonicación/métodos , Dosis de RadiaciónRESUMEN
A simple colorimetric and fluorescent anion chemosensor based on amide moieties, 6-nitro-1,4-dihydroquinoxaline-2,3-dione has been designed, synthesized and characterized by (1)H NMR, ESI-MS and elemental analyses. The strong basic anions such as F(-) and AcO(-) resulted in significant decrease in fluorescent emission intensity of the compound 1, accompanied synchronously with a dramatic color change from colorless to deep yellow in organic medium. (1)H NMR titration experiments shed light on the nature of the interactions between 1 and the anions.
Asunto(s)
Amidas/química , Aniones/química , Técnicas Biosensibles/métodos , Colorantes Fluorescentes/química , Quinoxalinas/química , Acetatos/química , Amidas/síntesis química , Amidas/efectos de la radiación , Colorimetría , Colorantes Fluorescentes/síntesis química , Colorantes Fluorescentes/efectos de la radiación , Fluoruros/química , Quinoxalinas/síntesis química , Quinoxalinas/efectos de la radiación , Espectrofotometría UltravioletaRESUMEN
Laser-light-induced surface relief grating inscription was carried out in the newly synthesized azobenzene-functionalized poly(amide-imide)s having the same main- and side-chain structures but different substituents in the azobenzene groups. The gratings were inscribed employing the two-wave mixing technique with linearly polarized laser beams. Three different polarization configurations were used: s-s, p-p, and s-p. The relatively deep surface relief gratings of period Lambda were formed for the case of s-s and p-p polarizations, whereas the s-p inscription resulted in the half-period grating (Lambda/2) with the weak surface modulation. The origin of the formation of Lambda/2 structure for s-p configuration results from the interference between zeroth- and first-order beams scattered on the polarization refractive index grating and having the same polarization. On the basis of this idea, we presented the simple kinetic model predicting and modeling the half-period grating formation with its temporal evolution. The proposed model is consistent with the experimental findings.
Asunto(s)
Amidas/química , Compuestos Azo/química , Imidas/química , Polímeros/química , Amidas/efectos de la radiación , Compuestos Azo/efectos de la radiación , Imidas/efectos de la radiación , Rayos Láser , Estructura Molecular , Polímeros/efectos de la radiación , Propiedades de Superficie , Factores de TiempoRESUMEN
Photo-responsive gel droplets having nano- or pico-L volume that showed photo-induced gel-sol transition were successfully developed, for which the inter-droplet mass transport and the subsequent enzymatic reactions in the interior of the gel droplets were photo-triggered.
Asunto(s)
Hidrogeles/química , Nanoestructuras/química , Amidas/química , Amidas/efectos de la radiación , Fumaratos/química , Fumaratos/efectos de la radiación , Hidrogeles/efectos de la radiación , Sustancias Macromoleculares/química , Sustancias Macromoleculares/efectos de la radiación , Estructura Molecular , Nanoestructuras/efectos de la radiación , Tamaño de la Partícula , Fotoquímica , Estereoisomerismo , Propiedades de Superficie , Factores de Tiempo , Rayos UltravioletaRESUMEN
A safe, functional-group-tolerant and high-throughput version of the trimethylaluminium mediated amide bond formation reaction has been developed in a microreactor system; rimonabant and efaproxiral were prepared to illustrate the utility of the method.
Asunto(s)
Alcanos/química , Aluminio/química , Amidas/síntesis química , Compuestos de Anilina/síntesis química , Piperidinas/síntesis química , Propionatos/síntesis química , Pirazoles/síntesis química , Amidas/química , Amidas/efectos de la radiación , Compuestos de Anilina/química , Compuestos de Anilina/efectos de la radiación , Diseño de Equipo , Microondas , Miniaturización , Estructura Molecular , Piperidinas/química , Piperidinas/efectos de la radiación , Propionatos/química , Propionatos/efectos de la radiación , Pirazoles/química , Pirazoles/efectos de la radiación , Rimonabant , EstereoisomerismoRESUMEN
During the last decade far-field fluorescence microscopy methods have evolved that have resolution far below the wavelength of light. To outperform the limiting role of diffraction, all these methods, in one way or another, switch the ability of a molecule to emit fluorescence. Here we present a novel rhodamine amide that can be photoswitched from a nonfluorescent to a fluorescent state by absorption of one or two photons from a continuous-wave laser beam. This bright marker enables strict control of on/off switching and provides single-molecule localization precision down to 15 nm in the focal plane. Two-photon induced nonlinear photoswitching of this marker with continuous-wave illumination offers optical sectioning with simple laser equipment. Future synthesis of similar compounds holds great promise for cost-effective fluorescence nanoscopy with noninvasive optical sectioning.
Asunto(s)
Amidas/química , Rayos Láser , Microscopía Fluorescente/métodos , Nanotecnología/métodos , Óptica y Fotónica , Rodaminas/química , Amidas/síntesis química , Amidas/efectos de la radiación , Microscopía Fluorescente/instrumentación , Estructura Molecular , Nanotecnología/instrumentación , Fotoquímica , Fotones , Rodaminas/síntesis química , Rodaminas/efectos de la radiaciónRESUMEN
Secondary amide derivatives of coumaric and ferulic acid are shown to undergo photoisomerization, forming a photostationary mixture of E- and Z-isomers. When the same chromophores are incorporated in rotaxanes, the extent of conversion to the Z-isomers is much smaller. Low temperature fluorescence experiments show that the energy barrier for non-radiative decay of the excited state is higher in the rotaxanes than in the corresponding threads, but the barriers are low in all cases.
Asunto(s)
Amidas/química , Ácidos Cumáricos/química , Rotaxanos/química , Amidas/efectos de la radiación , Simulación por Computador , Ácidos Cumáricos/efectos de la radiación , Enlace de Hidrógeno , Espectroscopía de Resonancia Magnética/métodos , Espectroscopía de Resonancia Magnética/normas , Estructura Molecular , Fotoquímica , Estándares de Referencia , Rotaxanos/efectos de la radiación , Sensibilidad y Especificidad , Espectrometría de Fluorescencia/métodos , Estereoisomerismo , Temperatura , Rayos UltravioletaRESUMEN
In this study, we synthesized two novel carboxylic acid and carboxylate compounds, both of which had an amide group linked with an azomethine moiety to introduce photoinduced switching of the intramolecular NH...O hydrogen bond. We suggest that the cis-carboxylate compound forms a stronger intramolecular NH...O hydrogen bond than the cis-carboxylic acid compound.
Asunto(s)
Amidas/química , Ácidos Carboxílicos/química , Enlace de Hidrógeno , Amidas/efectos de la radiación , Ácidos Carboxílicos/efectos de la radiación , Cinética , Luz , Espectroscopía de Resonancia Magnética , Modelos Moleculares , FotoquímicaRESUMEN
[reaction: see text] The N-Boc-protected N-3-alkenyltetronic acid amides 9 and 12 were prepared from tetronic acid bromide (7) and the corresponding amines 6 and 10 by nucleophilic substitution and subsequent acylation in 71% and 39% overall yield. They underwent an intramolecular [2 + 2]-photocycloaddition upon direct irradiation (lambda = 254 nm) to yield diastereoselectively the strained lactones 15 (76%) and 16 (91%) with a 2-azabicyclo[3.2.0]heptane core. In attempts to defunctionalize the 1-hydroxymethyl substituent of the 2-azabicyclo[3.2.0]heptane skeleton, lactone 15 was converted into mesylate 18 (74% overall yield). Intermolecular substitution reactions on this mesylate, however, proceeded sluggishly or failed completely. Lactone 15 could be opened reductively (Dibal-H) or by substitution with benzylamine to the N-Boc-protected 2-azabicyclo[3.2.0]heptanes 21 (71%) and 22 (81%). Conformationally constrained beta-amino acid derivatives were obtained by quantitative N-Boc deprotection of photocycloaddition product 15, followed by N-functionalization and subsequent lactone ring opening. The N-functionalization was conducted by acylation (to 24-26), alkylation (to 27), tosylation (to 28), and isocyanate addition (to 30). The reactions proceeded in yields of 70-84%. Lactone ring opening reactions were conducted with amines to establish the suitability of this process for library synthesis. As an example, the tripeptide 38 was obtained from photocycloaddition product 15 in an overall yield of 51%.
Asunto(s)
Amidas/síntesis química , Aminoácidos/química , Furanos/química , Lactonas/síntesis química , Amidas/química , Amidas/efectos de la radiación , Aminoácidos/efectos de la radiación , Ciclización , Furanos/efectos de la radiación , Lactonas/química , Lactonas/efectos de la radiación , Conformación Molecular , Fotoquímica , Estereoisomerismo , Rayos UltravioletaRESUMEN
Rapid synthesis of quinoline-4-carboxylic acid derivatives has been achieved by reaction of 2-methoxy acrylates or acrylamides with N-arylbenzaldimines in acetonitrile under InCl3 catalysis and microwave irradiation. Isolated yields up to 57% within 3 min have been obtained. The Lewis acid and the microwave activation appeared as crucial parameters for the reaction. The role of indium chloride and ytterbium triflate was specified using 13C NMR data and model theoretical studies.
Asunto(s)
Acrilatos , Amidas , Iminas , Indio/química , Quinolinas/síntesis química , Acrilatos/química , Acrilatos/efectos de la radiación , Alquilación , Amidas/química , Amidas/efectos de la radiación , Simulación por Computador , Iminas/química , Iminas/efectos de la radiación , Microondas , Estructura Molecular , Quinolinas/química , Quinolinas/efectos de la radiación , EstereoisomerismoRESUMEN
Fourier transform infrared microscopy was used to investigate human cortical bone samples before and after treatment with increasing doses of X-ray radiation. Especially the spectral region of the v1 and v3 phosphate vibrations of hydroxyapatite, the main mineral component of bone, and the region of the amide I and amide II vibrational bands due to the collagen extracellular matrix were examined. Major spectral changes in the phosphate region between 1250-1000 cm(-1) occur after irradiation doses between 1 and 4 Gray. These findings are explained by a decrease in size of mineral crystallites and by variances of the toichiometric/non-stoichiometric apatite composition. The Ca2+ /PO4(3-) /HPO4(2-) composition in the biological apatite is altered near the bone surface. The secondary structure of the collagen matrix is not affected by cumulative irradiation up to doses of 15 Gray as indicated by the unchanged frequency maximum and contour shape of the amide I band between 1600-1700 cm(-1) . However, side chain carboxylate groups of the collagen matrix that are involved in coordination with apatite bound calcium ions are partially removed by decarboxylation upon irradiation. Concomitantly, a loss of acidic phosphate groups due to a formation of phosphate groups with bound calcium is observed. These changes on a molecular level can be correlated with alterations in the mechanical properties of the bone samples, e.g. with an increased embrittlement as deduced from experiments with a scanning acoustic microscope.
Asunto(s)
Huesos/efectos de la radiación , Amidas/química , Amidas/efectos de la radiación , Huesos/química , Calcio/química , Calcio/efectos de la radiación , Ácidos Carboxílicos/química , Ácidos Carboxílicos/efectos de la radiación , Colágeno/química , Colágeno/efectos de la radiación , Cristalografía , Durapatita/química , Durapatita/efectos de la radiación , Humanos , Microespectrofotometría , Fosfatos/química , Fosfatos/efectos de la radiación , Dosis de Radiación , Espectroscopía Infrarroja por Transformada de Fourier , Rayos XRESUMEN
The effects of exposure to a 50 Hz magnetic field (maximum of 41.7 to 43.6 mT) on the membrane protein structures of living HeLa cells were studied using attenuated total reflection infrared spectroscopy. One min of such exposure shifted peak absorbance of the amide I band to a smaller wave number, reduced peak absorbance of the amide II band, and increased absorbance at around 1600 cm(-1). These results suggest that exposure to the ELF magnetic field has reversible effects on the N-H inplane bending and C-N stretching vibrations of peptide linkages, and changes the secondary structures of alpha-helix and beta-sheet in cell membrane proteins.
Asunto(s)
Campos Electromagnéticos , Proteínas de la Membrana/química , Proteínas de la Membrana/efectos de la radiación , Conformación Proteica/efectos de la radiación , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Albúminas/química , Albúminas/efectos de la radiación , Amidas/química , Amidas/efectos de la radiación , Relación Dosis-Respuesta en la Radiación , Globulinas/química , Globulinas/efectos de la radiación , Células HeLa/química , Células HeLa/efectos de la radiación , Humanos , Concentración de Iones de Hidrógeno , Ondas de RadioAsunto(s)
2-Aminopurina/análogos & derivados , Análisis de Secuencia por Matrices de Oligonucleótidos/métodos , 2-Aminopurina/química , 2-Aminopurina/efectos de la radiación , Amidas/química , Amidas/efectos de la radiación , Técnicas Químicas Combinatorias/instrumentación , Glicoproteínas de Membrana , Oligonucleótidos/síntesis química , Oligonucleótidos/efectos de la radiación , Ácidos Fosfóricos/química , Ácidos Fosfóricos/efectos de la radiación , Fotólisis , Nucleósidos de Purina/química , Nucleósidos de Purina/efectos de la radiaciónRESUMEN
The effect of the neutron activation factors, i.e., admixture of samarium oxide (Sm2O3) and irradiation time, on the physico-chemical properties of the raw materials and the in vitro dissolution and disintegration of hydrophilic and lipophilic suppositories was investigated. It was possible to expose the pure bases and the model drugs (5-aminosalicylic acid [5-ASA] and ropivacaine hydrochloride) to 1 min of neutron irradiation in a flux of 1.1.1013 n cm-2s-1. The dissolution and disintegration of the corresponding suppositories showed that the physico-chemical properties and the fraction of incorporated drug together with the lipophilic/hydrophilic nature of the base were important factors. Sm2O3 increased the disintegration time of hydrophilic suppositories containing 5-ASA, while the dissolution of both drugs from these formulations remained unchanged. Sm2O3 did not alter the disintegration time of the lipophilic formulations, but it reduced the dissolution of both drugs from these suppositories. Irradiation induced different behaviour in the different bases.
Asunto(s)
Excipientes/efectos de la radiación , Neutrones , Óxidos , Samario , Supositorios/efectos de la radiación , Amidas/química , Amidas/efectos de la radiación , Excipientes/química , Reología , Ropivacaína , Ácido Salicílico/química , Ácido Salicílico/efectos de la radiación , Solubilidad , Supositorios/química , Factores de TiempoRESUMEN
The radicals produced by reactions of hydroxyl radicals with alkyl substituted ureas and amides in aqueous solutions have been investigated. Hydroxyl radicals were produced by U.V. photolysis of H2O2 and the short-lived amide and urea radicals were spin-trapped by t-nitrosobutane and identified by e.s.r. For all N-alkyl derivatives of urea and acetamide, and for N,N-dimethyl propionamide and N,N-diethyl formamide, only radicals centred on N-alkyl groups were detected. Radicals situated only on alkyl groups attached to the carbonyl carbon were observed for dimethyl acetamide, trimethyl acetamide and butyramide. However, for N,N-dimethyl butyramide, N, N-diethyl butyramide, N-methyl propionamide and N, N-diethyl propionamide, free radicals were formed which were localized on the alkyl group attached to the amide carbon as well as those attached to nitrogen. The hydrogen atom bound to the carbonyl carbon was abstracted in N-ethyl formamide. Acyl radicals formed by C-N scission due to direct U.V. photolysis of N, N-dimethyl butyramide and N,N-dimethyl propionamide were also detected.