Proton transfer reactions in aqueous solution of 2-vinylquinoline copolymers

Fluorescence spectra of atactic and isolaclic poly-2-vinylquinoline and copolymers of 2-vinylquinoline and four non fluorescent comonomers have been measured as a function of pH. The homopolymers and the copolymers with pyrrolidone show two band fluorescence spectra; their intensity ratio changes with pH, polymer concentration and excitation wavelength. For the other copolymers the emission of the protonated heterocycle is only a shoulder of the emission of the neutral form. A kinetic scheme has been proposed to explain these results.     

Quinoline-based molecular clips for selective fluorescent detection of Zn2+

New selective Zn2+ fluorescent sensors, di(2-quinoline-carbaldehyde)-2,2'-bibenzoyl-hydrazone (QB1) and di(2-quinolinecarbaldehyde)-6,6'-dicarboxylic acid hydrazone-2,2'-bipyridine (QB2), have been designed and prepared. Both QB sensors exhibit an emission band centered at 405 nm (excitation at 350 nm) with low quantum yield. Zinc binding not only red-shifts the emission band to 500 nm, but also enhances the fluorescence intensity by an order of magnitude based on the deprotonization strategy via self-assembly. These probes are highly selective for Zn2+ over biologically relevant alkali metals, alkaline earth metals and the first row transition metals such as Mn2+, Fe2+, Co2+ and Ni2+ in buffered aqueous DMSO solution.     

Highly selective fluorescent recognition of phenyl amino alcohol based on ferrocenyl macrocyclic derivatives

Four ferrocenyl macrocyclic derivatives 3 and 4 containing anthracene fluorophores have been synthesized. The fluorescent properties of these receptors have been studied in three organic solvents, both in the absence and presence of phenyl amino alcohols. All receptors exhibit sensitive fluorescence response to l- or d-phenylglycinol, a strong emission band is produced due to the intermolecular exciplex between host and guest. These special phenomena were not observed when other species were used as the guests; such highly selective fluorescent response indicates that these receptors can easily discriminate phenylglycinol from other similar species. Solvent comparative experiments also indicate that acetonitrile is the most appropriate solvent to detect this fluorescent change. The intramolecular energy transfer between excited anthracene and ferrocene, and π–π stacking interaction between the aromatic rings play critical roles in this special fluorescence enhancement. Model calculations at DFT level further suggest the possible interaction modes, structures and relatively steric position between the host and guest also influence the optical response.     

Atlas of Fluorescence Spectra and Lifetimes of Dyes Attached to Protein

Abstract

Fluorescence spectra and lifetimes of ovalbumin labeled with a variety of fluorescent reagents have been measured. The peak positions of the emission spectrum and the long wavelength band of the excitation spectrum as well as the fluorescence lifetimes, are tabulated. Heterogeneity of binding sites is shown by the broadness of some emisison spectra and the presence of multiexponential decay. The atlas may serve as a guide to the properties of these dyes attached to proteins in general.     

A highly selective and sensitive BODIPY-based colourimetric and turn-on fluorescent sensor for Hg2+ ions

A series of monostyryl boron dipyrromethenes appended with an NO(4), NO(2)S(2), N(3)O(4), or N(3)O(2)S(2)-type ligand have been prepared and characterised. While the UV-Vis spectra of the former three compounds in CH(3)CN/H(2)O (2?:?3 v/v) do not respond towards a wide range of metal ions, the derivative with an N(3)O(2)S(2)-ligand exhibits a highly selective and sensitive spectral response towards Hg(2+) ions. The absorption band is blue-shifted by 40 nm due to inhibition of the intramolecular charge transfer process upon metal complexation. The fluorescence is also turned on giving a strong emission band at 572 nm. The colour changes can be easily detected by the naked eye. The results suggest that this compound serves as a promising colourimetric and fluorescent sensor for Hg(2+) ions in this mixed aqueous medium.     

Preparation and properties of FeAs2 and FeSb2

Single crystals of FeAs₂ and FeSb₂ were prepared by chemical vapor transport using chlorine as the transporting agent. Electrical and magnetic measurements have been made on well-characterized samples. FeAs₂ was found to be a diamagnetic semiconductor with a band gap of 0.22 eV. FeSb₂ has an extremely narrow band gap and shows unusual electrical and magnetic properties. Aproposed band model is used to explain the experimental results.     

Binding of methyl orange and the hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate,by 2-dialkylaminoethyl methacrylate-N-vinyl-2-pyrrolidone and related copolymers

The copolymers of N-vinyl-2-pyrrolidone and 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, or 2-dimethylaminopropyl acrylamide have been prepared. Studies were made of the binding of a “binding probe,” methyl orange, by the copolymers in aqueous solution. The first binding constants accompanying the binding were evaluated. Furthermore, the intensity of fluorescence of a hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate, in the presence of these polymers was investigated. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed.     

Vibrational spectra of imidazoline-2-thione and imidazoline-2-one

Raman and infrared spectra of imidazoline-2-thione (IMZT) and imidazoline-2-one (IMZO) have been recorded. Normal coordinate analyses have been performed for all the fundamental vibrations of IMZT, IMZT-d₂ and IMZO employing a Urey—Bradley potential function supplemented with valence type force constants for the out of plane modes. The results of the vibrational analyses are discussed in relation to the assignments in related molecules. The vibrational assignments for IMZT and IMZO have been compared with those in structurally similar molecules and the need to obtain more reliable band assignments for some of the molecules considered is emphasised.     

Electronic spectra of 2-methoxypyridine and 2-methoxy-d3-pyridine

The electronic absorption spectrum of 2-methoxypyridine in the vapour and solution phases and 2-methoxy-d₃-pyridine in the vapour state in the region 3000–2450 Å and the luminescence spectra of 2-methoxypyridine in ethanol at 77 K have been measured and analysed. The oscillator strength of the absorption band system due to the π → π* transition and the excited state dipole moment in the ¹π,π* state have been estimated for 2-methoxypyridine.     

Ultraviolet absorption and vibrational spectra of 2-fluoro-5-bromopyridine

The ultraviolet absorption spectrum in the range 340-185 nm in the vapour and solution phase has been measured for 2-fluoro-5-bromopyridine. Three fairly intense band systems identified as the pi* <-- pi transitions II, III and IV have been observed. A detailed vibronic analysis of the vapor and solution spectra is presented. The first system of bands is resolved into about sixty-two distinct vibronic bands in the vapour-phase spectrum. The 0,0 band is located at 35944 cm(-1). Two well-developed progressions, in which the excited state frequencies nu'25 (283 cm(-1)) and nu'19 (550 cm(-1)) are excited by several quanta, have been observed. The corresponding excited state vibrational and anharmonicity constants are found to be omega'i = 292 cm(-1), x'ii = 4.5 cm(-1) (i = 25) and omega'i = 563.8 cm(-1), x'ii = 6.9 cm(-1) (i = 19). The other two band systems show no vibronic structure, the band maxima being located at 48346 and 52701 cm(-1), respectively. The oscillator strength of the band systems in different solutions and the excited state dipole moments associated with the first two transitions have been determined by the solvent-shift method. The infrared spectrum in the region 4000-130 cm(-1) and the laser Raman spectrum of the molecule in the liquid state have been measured and a complete vibrational assignment of the observed frequencies is given. A correlation of the ground and excited state fundamental frequencies observed in the UV absorption spectrum with the Raman or infrared frequencies is presented.     

Spectral and fluorescent study of the interaction of cyanine dyes Cyan 2 and Cyan 45 with DNA

The noncovalent interaction of the cyanine dyes Cyan 2 and Cyan 45 with DNA (in a pH 7 phosphate buffer) was studied by spectral and fluorescent methods. Upon titration of dye solutions with a concentrated DNA solution, a drop in the absorption band of the initial dye, a long-wavelength shift, and a rise of the absorption of the dye bound to DNA occur. Simultaneously, a growth of dye fluorescence is observed. Mathematical modeling of the fluorescence growth has been performed on the basis of the formation of one or two types of dye complexes with DNA. The experimental results are adequately described by the model involving one type of the dye-DNA complex. It is shown that Cyan 2 binds to DNA probably as the cis-isomer, whereas Cyan 45 as the trans-isomer.     

A New Fluorescent Chemosensor for Cu2+ Based on a Dianthracene-Derivative

Abstract

Besides being of interest in photochemistry, photoinduced electron transfer (PET) is a process largely used in the design of fluorescent ion sensing molecules. One of the simplest systems is based on fluorescent aromatic groups linked to amino groups and proposed as possible fluorescent transition metal ion chemosensor [1]. In this case, the fluorescence of the fluorophore “ligths on” when the amino group is complexed. On the other hand, in the absence of metal ions, the fluorescence is quenched by a PET originating from the nitrogen lone electron pairs [2]. We prepared a new fluorescent chemosensor, abbreviated as Ant-NH-O-O-NH-Ant (shown in Fig. 1) in which the intramolecular PET is expected to be efficient. The chemosensor consists of a metal-binding dioxodiamino unit linked to two light-emitting anthracene fragments. This type of supramolecules when irradiated in methanol solution (conc. 1.89—10^?5 M.) at 368 nm displays a characteristic fluorescence spectrum for anthracene group with the most intensive band at 415 nm [Fig. 2(a)]. The emission is slightly enhanced upon coordination of such metal ions as Ni²⁺ and Zn²⁺ by the ligand fragment of the Ant-NH-O-O-NH-Ant molecule [Fig. 2(b) and (d)]. However, much higher intensity of emission is observed in the case of Cu²⁺ complex [see Fig 2(c)]. The fluorescence enhancement is presumably due to suppression of photoinduced fluorophore-to-metal electron-transfer mechanism.     

Reactive bands and rebounding trajectories in collinear F + H2

Bands of reactive and unreactive trajectories have been mapped for classical collinear F + H₂ (υ = 0). The edges of the band are characterized by trajectories which undergo several reflections in the corner of the potential energy surface. Multiple reflections are seen to lead to less sharply defined band edges.     

Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3-ZnO-PbO glasses

This paper reports on the spectral properties of Mn2+, Co2+ and Ni2+ ions doped B2O3-ZnO-PbO glasses. XRD, FT-IR spectra and DSC profiles of these glasses have also been carried out, and the FT-IR profiles have shown the presence of both BO3 and BO4 units. It is interesting to notice that the FT-IR peak positions are slightly shifted towards higher energy with an increase in transition metal ion concentration change. From the measured DSC thermograms, glass transition (T(g)), crystallization (T(c)) and temperature of melting (T(m)) have been evaluated. From the UV absorption spectra of Mn2+, Co2+ and Ni2+ ions doped glasses, both direct and indirect optical band gaps have been calculated. The visible absorption spectra of Mn2+:glasses have shown a broad absorption band at 520 nm (6A1g(S) --> 4T1g(G)); with Co2+ ions one absorption band at 605 nm (4A2(4F) --> 4T1(4P)) and another at 1450 nm (4A2(4F) --> 4T1(4F)); and for Ni2+:glasses three absorption bands at 420 nm (3A2g(F) --> 3T1g(P)), 805 nm (3A2g(F) --> 1Eg(D)) and 880 nm (3A2g(F) --> 3T1g(F)) have been observed. For Mn2+:glasses, upon excitation with 262 nm, a green emission (539 nm) with a slight blue shift; and with 392 nm, a green emission (534 nm) with a slight red shift with Mn2+ ions concentration change (0.2-0.5 mol%) has been observed. This green emission has been assigned to (4T1(G) --> 6A1(S)) d-d transition of Mn2+ ions that are in tetrahedral co-ordination. For 0.5 mol% Co2+ ions doped glass, upon excitation with 580 nm, a red emission (625 nm) has been observed which originates from 2E(2G) --> 4A2(4F) transition of Co2+ ions in tetrahedral co-ordination. For Ni2+ ions doped glasses upon excitation with 420 nm, a green (577 nm) and red (670 nm) emissions are observed and are assigned to (1T2g(D) --> 3A2g(F)) and (1T2g(D) --> 3T2g(F)) d-d transitions of Ni2+ ions in octahedral co-ordination.     

Shape-controlled synthesis of semiconducting CuFeS2 nanocrystals

Nanocrystals of the semiconducting chalcopyrite CuFeS₂ have been synthesized utilizing a facile solution-based method. Depending on the choice of precursors and synthesis conditions, the nanocrystals exhibit either a spherical (～12 nm) or pyramidal morphology (～30 nm), with a narrow size distribution. The band gap of the pyramidal nanocrystals is very close to the bulk value, but a larger band gap is obtained for the spherical nanocrystals likely because of size confinement effect.     

2-Aryl-4-methyl-4-chlorocarbonyl-oxymethyl-2-oxazolines Chemical reactivity and infra-red spectra

2-Aryl-4-methyl-4-chlorocarbonyl-oxymethyl-2-oxazolines have been shown to exhibit a particular reactivity towards nucleophilic reagents. This reactivity is to be attributed to the presence of the chlorocarbonic ester function. Reaction of the above 2-oxazolines with ammonia (or dimethylamine) results in ring opening, with the formation of benzamide (or N,N-dimethyl-benzamide) and 4-methyl-4-chloromethyl-oxazolidin-2-one (or 4-methyl-4-N,N-dimethylaminomethyl-oxazolidin-2-one). The presence of the chlorocarbonic ester function also affects the position of the C=N band in the infra-red spectrum of these 2-oxazoline derivatives; this band is shifted approximately 40 cm⁻¹ towards lower wavelengths in comparison with the absorption band of structurally related compounds which do not possess the chlorocarbonic ester group. A possible reaction mechanism is proposed together with a correlation of the chemical and spectroscopical findings.     

给体-受体-给体窄带隙染料掺杂聚芴发光二极管

合成了一系列给体-受体-给体型窄带隙荧光分子, 并将其作为掺杂剂与主体(Host)宽带隙聚芴共混制备发光二极管. 荧光分子为4,7-二呋喃-苯并噻二唑(O-S)、4,7-二噻吩-苯并噻二唑(S-S)、4,7-二(N-甲基吡咯)-苯并噻二唑(N-S)、4,7-二硒吩-苯并噻二唑(Se-S)和4,7-二(N-甲基吡咯)-苯并硒二唑(N-Se). 溶液中荧光分子的紫外-可见吸收峰位于447~472 nm, 荧光发射峰位于563~637 nm. 该系列荧光分子掺杂聚芴(PFO)发光器件的电致发光峰位于580~633 nm. 当器件结构为ITO/PEDOT/PVK/PFO+N-Se/Ba/Al时, 最大外量子效率为1.28%, 电流效率1.31 cd/A.     

The electronic structure ofα-B12, B12P2 and B12AS2

The electronic band structures of the rhombohedral-based boron compounds -B₁₂, B₁₂P₂ and B₁₂ As₂ have been investigated along all symmetry directions. The calculations show that the band gap, in all cases, is of the order of 2 eV, which correlates with the known color of -rhombohedral boron. The materials should be intrinsic semi-conductors, as has recently been shown experimentally. The states around the band gap in -B₁₂ are dominated by the boron 2p atomic states. The bonding in the icosahedra, as illuminated by cluster calculations, is shown to be rather similar to that in the isolated B₁₂ icosahedron. Of the intericosahedron interactions, those between B(2) and B(2) atoms are the strongest and have a bond index just above unity. In B₁₂P₂ the orbitals of the P₂ moiety make a significant contribution to the valence band edge states and the conduction band edge states also incorporate considerable (55%) phosphorus 3d orbital character. In B₁₂As₂ the arsenic 4d orbitals do not have as much effect in that crystal as do the 3d orbitals in B₁₂P₂.     

Photochromic Dihetarylethenes. 12. Synthesis of 5-Alkyl-2-(1,3,4-oxadiazol-2-yl)thiophenes and Their Photochromic Derivatives

Photochromic derivatives of 5-alkyl-2-(1,3,4-oxadiazol-2-yl)thiophenes have been synthesized for the first time. Their photochromic and fluorescent properties have been studied.     

Vibrational and electronic absorption spectra of 4-chloro 2-methyl, 4-chloro 3-methyl and 6-chloro 3-methyl phenols

The infrared spectra of 4-Cl 2-Me, 4-Cl 3-Me and 6-Cl 3-Me phenols have been recorded. The vibrational spectrum has been analysed assuming that the molecules belong toC _s point group and a tentative assignment of the observed frequencies to various modes of vibration has been proposed. The near ultraviolet absorption spectrum of these compounds has also been recorded. Assuming the transition to be electronically allowed the strongest band on the longer wavelength side has been assigned as the (0, 0) band in each case. The spectrum has been analysed in terms of several excited state frequencies which have been correlated with the ground state frequencies observed in the infrared spectrum.