Studies of third-order optical nonlinearities and optical limiting properties of azo dyes

In order to protect optical sensors and human eyes from debilitating laser effects, the intensity of the incoming laser light has to be opportunely reduced. Here, we report our results on the third-order optical nonlinearity and optical limiting properties of three azo dyes exposed to a 532nm continuous wave laser. We have observed low power optical limiting based on nonlinear refraction in our samples.     

Thiuram disulfide intercalated hybrid materials of layered lead and cadmium iodides

Thiuram disulfide intercalates of lead(II) and cadmium(II) were prepared by the reaction of binary layered metal iodides with five dithiocarbamates in air. The intercalates were characterized by elemental analysis, Powder X-ray diffraction (XRD), infrared (IR), ultraviolet–visible spectroscopy, diffuse reflectance spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) techniques. IR showed increased contribution of the thioureide bond and the presence of weak disulfide stretching frequency. Powder XRD showed the characteristic intermediate 2θ signal confirming the intercalation. Powder XRD clearly differentiated intercalates from the iodinated product of dithiocarbamate. As the bulkiness of substituents on disulfide increased, “d” also increased. The higher thermal stability associated with intercalates clearly suggests a strong ionic interaction and a difficult de-intercalation. SEM images of lead intercalates indicated crystalline nature. The intercalates appeared as rods or spheres. The diallyl-intercalate, [PbI₂](H₅C₃)₂NCSS-SSCN(C₃H₅)₂ (where (H₅C₃)₂NCSS-SSCN(C₃H₅)₂ is diallylthiuram disulfide), shows “net like structures.” Intercalation of oxidized dithiocarbamates in the “galleries” of layered PbI₂/CdI₂ is observed. HRTEM and AFM analysis of intercalates showed the particles to be nano-rods.     

传感器用镓掺杂氧化锌纳米盘/纳米花状结构催化剂的制备及表面表征

采用简便的旋涂过程和一步水热法在压电基片上制备了Ga掺杂的ZnO纳米薄膜(GZO)。在水热处理过程中,通过添加不同的聚合物可形成纳米盘和纳米花状形貌的薄膜。采用场发射扫描电镜(Fe-SEM)、X射线衍射(XRD)和Raman光谱表征了样品的形貌、微结构和组成。 XRD和FE-SEM结果证明,在AlN/Si压电基片上形成的纳米盘、纳米棒和纳米花状GZO均为纤维锌矿相。采用浸渍法进一步在所制GZO样品上固定了绿色的荧光蛋白质(GFP)。运用原子力显微镜和荧光光谱分析了GFP与GZO表面结合的性质,考察了其用于传感器和生物成像技术的可行性。痕量GFP的固定使该材料产生荧光响应,表明其用于紫外光传感器时具有较好活性。     

Mechanistic investigation of oxidation of aromatic anils by isonicotinium dichromate in acidic medium. A kinetic study

Abstract Under identical experimental conditions the kinetics of oxidation of aromatic anils to benzaldehyde and nitrosobenzene, by isonicotinium dichromate, has been studied in aqueous acetic acid medium. The low dielectric constant of the medium facilitates the reactivity. Ionic strength has no significant effect on the conversion. The added Mn(II) decreases the rate of the reaction. The added acrylonitrile has no effect on the reaction rate indicating the absence of free radical mechanism. Highly negative ΔS ^# values indicate a structured transition state. The deviation of Hammett plot is noted and a concave downward curve is obtained for the anils with substituents in the aniline moiety. The observed break in the log k _obs versus σ is attributed to the change in the transition state whereas the linear plot is observed for the substituents in the benzaldehyde moiety. A suitable mechanism has been proposed. Graphical Abstract Mechanistic investigation of oxidation of aromatic anils by isonicotinium dichromate in acidic medium. A kinetic study.      

Copper(I) complexes of bis(2-(diphenylphosphino)phenyl) ether: synthesis, reactivity, and theoretical calculations

The tricoordinated cationic Cu(I) complex [Cu(kappa2-P,P'-DPEphos)(kappa1-P-DPEphos)][BF4] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl) ether) containing a dangling phosphorus center was synthesized from the reaction of [Cu(CH3CN)4][BF4] with DPEphos in a 1:2 molar ratio in dichloromethane. When complex 1 is treated with MnO2, elemental sulfur, or selenium, the uncoordinated phosphorus atom undergoes oxidation to form a P=E bond resulting in the formation of complexes of the type [Cu(kappa2-P,P'-DPEphos)(kappa2-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu-E bond. The zigzag polymeric CuI complex [Cu(kappa2-P,P'-DPEphos)(micro-4,4'-bpy)]n[BF4]n (5) was prepared by the reaction of [Cu(CH3CN)4][BF4] with DPEphos and 4,4'-bipyridine in an equimolar ratio. The stereochemical influences of DPEphos on its coordination behavior are examined by density functional theory calculations.     

Synthesis of macrocyclic conjugated ψ-disacharides via nitrile oxide cycloaddition: Alkenyl chain length controlled unprecedented formation of di-oxa heterocycles from monosaccharides

Various symmetrical and unsymmetrical isoxazoline embodied chiral macroheterocycles were synthesized from carbohydrate derived oximes. Our result shows that the mode of cycloaddition is dependent on the length and tether present in alkenyl chain of sugar moiety. Thus in some cases inter- and intramolecular cycloaddition of nitrile oxide were observed with high selectivity. The cycloadducts contains two sugar units linked via macrocycles thus they are considered as pseudo-disacharides. The stereochemistry of the newly formed chiral centers was established by 2D-NMR techniques and X-ray crystallographic studies.     

Comparison of Bacterial Communities in the Throat Swabs from Healthy Subjects and Pharyngitis Patients by Terminal Restriction Fragment Length Polymorphism

Terminal restriction fragment length polymorphism (T-RFLP) analysis was applied to characterize bacterial flora present in the throats of healthy subjects and pharyngitis patients. The 16S?rRNA genes of bacteria present in throat metagenome were amplified by PCR with 6-carboxy-fluorescein (6-FAM)-labeled universal forward primer (27?F) and a universal reverse primer (1513R). The 16S rDNAs were digested with restriction enzymes with 4-bp recognition sites (MspI or RsaI) and analyzed by using an automated DNA sequencer. T-RFLP patterns were numerically analyzed using computer programs. From analysis of the throat bacterial community, patterns derived from MspI and RsaI digested samples of healthy subjects and pharyngitis patients were grouped into different clusters, though RsaI digested samples showed some uncertainty. Pharyngitis throats generated an average species richness of 9 [±2.1 (SD)] and 10 (±2.9) for MspI and RsaI digests, respectively, whereas healthy throats generated 6.3 (±1.2) and 6.1 (±1.5) in MspI and RsaI digests, respectively. These results suggest that samples from pharyngitis patients contain an unexpected diversity of causative bacteria. The pharyngitis throats were colonized with a rich diversity of bacterial species than that of healthy throats. Using T-RFLP, we are able to detect a model bacterium, Streptococcus pyogenes SF370, and T-RF patterns were consistent with the Streptococcal T-RFLP patterns. Our study indicates that T-RFLP analysis is useful for the assessment of diversity of throat bacterial flora and rapid comparison of the community structure between subjects with and without pharyngitis.     

Role of dipole moment of solvents in formation and stabilization of the TICT states in Coumarin 445 under nitrogen laser excitation

In this paper we report the observation of dual Amplified Spontaneous Emission (ASE) from solutions of 7-ethylamino-4-methyl coumarin dye (Coumarin 445) in certain solvents such as n-butyl acetate, dioxane etc. when pumped by high power nitrogen laser. The two ASE bands appear to be from two different excited species (ICT and TICT conformation) one of which is the precursor of the other. The spectral characteristics of dye Coumarin 445 depend upon the solvent environment. The TICT coumarin photoisomers, which form exciplexes with the solvent molecules, have enough gain to produce amplified spontaneous emission even when there is apparently no detectable fluorescence. The behaviour of this dye in the excited state is studied by measuring the small signal gain and variation of the gain slope with temperature in different solvents. It is observed that polarity of the solvent plays a more dominant role in formation and stabilization of TICT states.     

Self-assembly,optical and electrical properties of fork-tailed perylene bisimides

Effect of side-chain length on self-assembly, optical and electrochemical properties of N,N′-di(1-pentylbutyl)perylene-3,4,9,10-tetracarboxylic bisimide and N,N′-di(1-hexylpentyl)perylene-3,4,9,10-tetracarboxylic bisimide has been studied. The photo-physical, thermal and electrochemical properties were studied using UV–Vis and fluorescence, differential scanning calorimetry, and cyclic voltammetry, respectively. The molecules self-assembled as 1D – rods and molecular bundles, self-assembly was studied using SEM, optical and fluorescence microscopic techniques. The results concluded that the compound with short tail exhibits low solubility and self-assembled faster. The photo-physical properties of the compounds were not much affected by varying the alkyl chain length. The compounds geometries were optimized at 6-31G^∗ using DFT and the potentials were correlated with molecular orbitals.     

Predicting insertion loss of large duct systems above the plane wave cutoff frequency

If the dimensions of a silencer or muffler component are small compared to an acoustic wavelength, plane wave propagation can be assumed. This is not the case for HVAC (heating, ventilation, and air conditioning) duct systems, and large diesel engine mufflers commonly used in ship and generator sets. For such applications, the wave behavior in the inlet and outlet ducts is three-dimensional. In this paper, the finite element method is utilized to simulate large duct systems with an aim to predict the insertion loss. The boundary condition on the source side is a diffuse field applied by determining a suitable cross-spectral force matrix of the excitation. At the termination, the radiation impedance is calculated utilizing a wavelet algorithm. Simulation results are compared to published measurement results for HVAC plenums and demonstrate good agreement.