Absorption spectrum of monomeric pseudoisocyanine: A new perspective and its implications for formation and spectral response of J-aggregates in solution and in thin films

We argued against the current spectral assignment for absorption spectrum of monomeric PIC which is widely accepted since the pioneering works of Scheibe and Jelley [G. Scheibe, Angew. Chem. 49 (1936) 563; E.E. Jelly, Nature 138 (1936) 1009]. A new spectrum is presented along with its conceptual basis. The hypothesized spectrum attributes the previous 0–0 (≈525 nm) and 0–1 (≈490 nm) assignments, respectively, to intermediates acting as the precursor of J-aggregates and to the 0–0 transition of monomeric PIC and brings the spectrum in accord with the seemingly universal spectral fingerprint of cyanines. The hypothesis is used to analyze and interpret the temperature dependence of the UV–vis absorption of PIC aggregates in saline aqueous solution by incorporating the J-band simulations within frenkel exciton formalism. Its implications for aggregate formation kinetics are given on the basis of current spectroscopic evidence. The hypothesis readily answers several long-standing questions: Why compared to many other cyanines at least an order of magnitude higher dye concentration is needed to form J-aggregates of PIC? Why are there no precursors, since aggregation is expected to be a consecutive process? A large number of observations on steady-state and time-resolved spectral properties, and aggregation kinetics in solution/thin films are likely to find reasonable explanations within this hypothesis.     

Liquid phase oxidation of benzyl alcohol to benzaldehyde over chromium borophosphate catalyst synthesized by solution combustion method using different types of fuel

In this paper, chromium borophosphates have been prepared by the solution combustion method using different types of fuel and enhanced as a catalyst for liquid-phase oxidation of benzyl alcohol to benzaldehyde for the first time. Carbohydrazide, citric acid, hexamethylenetetramine, oxalyldihydrazide and urea used as an organic fuel and the obtained chromium borophosphates were systematically characterized by infrared spectroscopy, X-ray powder diffraction, thermogravimetry, scanning electron microscopy, and surface analysis techniques. They are structurally identical and thermally stable up to 1000 °C. According to fuel, their surface properties differ from each other and the long and short rod-like particles, which have a surface area between 7 and 19 m² g^?1, are formed. The effects of solvent type, reaction temperature, reaction time, peroxide amount and catalyst amount were also examined for catalytic studies, and the reaction conditions were optimized. As compared with the other fuels, hexamethylenetetramine-assisted synthesized chromium borophosphate catalyst provides high benzaldehyde conversion (52.09%) and selectivity (100%) under the optimized condition and has potential as a heterogeneous catalyst for oxidation reactions.

     

A Diverse‐Stimuli Responsive Chemiluminescent Probe with Luminol Scaffold and Its Electropolymerization

A diverse‐stimuli responsive chemiluminescent system, SNS‐Lum, and its electropolymerization to give PSNS‐Lum, which is the first example of conjugated polymers with pendant luminol arms inducing chemiluminescence in the presence of super oxide radical anion under neutral conditions, are highlighted.     

Investigation of nucleation and grain growth in 2-dimensional systems by using generalized Monte Carlo simulations

In this study, nucleation and grain growth was studied by using 2-dimensional generalized Monte Carlo simulations and experiments. As an attempt to improve the JMAK model, we proposed a new differential equation to be able to model nucleation and growth phenomena using nonextensive thermostatistics. One of the reasons that we would like to perform generalized Monte Carlo simulations in studying of nucleation and grain growth phenomena is that the generalized Monte Carlo algorithm was shown to be more effective than the standard Monte Carlo algorithm and also than the standard Molecular Dynamic algorithm in locating the minimum energy configuration. Therefore, for a given temperature, the fact that a configuration of the system with lower energy could be obtained by using the generalized Monte Carlo simulation means that a different textural configuration of grain growth could be also expected. In this respect, it is possible to say that the nonextensive statistics might be an appropriate tool in studying of nucleation and growth phenomena.     

Novel Multiporphyrin Functionalized Single-Walled Carbon Nanotubes

Porphyrin monomers, 5,15–bis(4-(2,5,8,11-tetraoxatridecan-13-yloxy)phenyl)-10,20-bis(3-iodophenyl)porphyrin zinc (5a) and 5,10–bis(4-(2,5,8,11-tetraoxatridecan-13-yloxy)phenyl)-15,20-bis(3-iodophenyl)porphyrin zinc (5b), and their oligomers 6a and 6b were synthesized and characterized. The titration experiment of the monomers was carried out in THF by changing the solution percent of water. The optical properties (UV–vis and fluorescence spectra) of the monomers that possess slightly red-shifted optical spectra in water compared to the spectra obtained in THF are reported. The newly prepared porphyrin constructs were also mixed with SWCNTs to generate noncovalent hybrid materials.     

Polyimides for electronics applications

A variety of options exists for lithographically defining polyimides for microelectronics applications. The two investigated here, photosensitive polyimide and wet etching of low-stress polyimides, offer lower cost, higher throughput solutions compared with dry etch processes. Via sizes of less than 25 μm and film thicknesses of greater than 14 μm are difficult to process using these techniques: however, for applications such as interlayer dielectrics for high-density packaging or solder masks for flip chip die attachment, these limitations may not be insurmountable. Photosensitive polyimide can be patterned with fewer steps, but the overall quality of the film in terms of surface planarity and residual stress is not as good as wet etching of conventional polyimide.     

Phase Transitions in Pure and Hybrid Hydrogels: A Fluorescence Study

Summary: Recent observations on phase transitions around the critical point showed that the critical exponents differed drastically from percolation results and classical results for pure hydrogel systems, depending on monomer concentration. In addition to pure hydrogels, the sol-gel phase transition during radical crosslinking copolymerization of acrylamide (AAm) and N-isopropylacrylamide (NIPA) hybrid was studied by using the steady state fluorescence (SSF) technique. N,N′-methylenebis(acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and initiator, respectively. Pyranine (trisodium 8-hydroxypyrene-1,3,6-trisulfonate acid, HPTS) was added as a fluoroprobe for monitoring the polymerization. It was observed that pyranine binds to AAm and NIPA chains on the initiation of the polymerization, thus the fluorescence spectra of the bonded pyranines shift to shorter wavelengths. Fluorescence spectra of the bonded pyranines allowed to monitor the sol-gel phase transition without disturbing the system mechanically and to test the universality of the sol-gel transition as a function of polymer concentration ratios. The observations around the gel point of PAAm-PNIPA hybrid show that the gel fraction exponent β obeyed the percolation result.     

Selective and sensitive determination of dopamine via suppressing ascorbic acid using an N-(1-H-indole-3yl) methylene thiazole-2-amine thin film-modified glassy carbon electrode

The selective determination of dopamine (DA) was performed using a glassy carbon (GC) electrode modified with N-(1-H-indole-3yl) methylene thiazole-2-amine (IMT2A). IMT2A was deposited on the GC electrode by cyclic voltammetry. This modified electrode demonstrated an electrocatalytic effect on the oxidation of DA in the presence of uric acid (UA) and ascorbic acid (AA) using differential pulse voltammetry (DPV) method in 0.1 M phosphate buffer solution (PBS) of pH 7. Selective determination was realized in elimination of AA response on the IMT2A-modified electrode. The oxidation peak currents increased linearly with two concentration intervals of DA at pH 7 phosphate buffer. One of them is 0.25–9.15 μM, and the other is 9.15–95.1 μM. The limit of detection (LOD) was found as 0.086 μM. The proposed electrode was applied to the determination of DA in pharmaceutical preparations and human urine sample with satisfactory results.

     

One‐Component Thioxanthone Acetic Acid Derivative Photoinitiator for Free Radical Polymerization

Acetic acid–based thioxanthone (TXCH₂COOH) was synthesized and characterized and used as a photoinitiator for free radical photopolymerization of methyl methacrylate (MMA) in the absence and presence of a tertiary amine (MDEA) in different solvents. Different absorption properties were observed depending on the solvent. Fluorescence and phosphorescence experiments were also carried out successfully. The fluorescence quantum yield was found to be 0.09 and the phosphorescence lifetime was calculated as 138 ms at 77 K. The photoinitiator undergoes efficient intersystem crossing into the triplet state and the lowest triplet state possesses π–π* configuration. Laser flash photolysis experiments show that transient absorption of TXCH₂COOH is similar to the parent thioxanthone and the triplet lifetime was calculated as 2.3 μs at 630 nm.     

Spectral Characterization and Antimicrobial Activity of Some Schiff Bases Derived from 4‐Methyl‐2‐aminophenol

A series of N‐(5‐methyl‐2‐hydroxyphenyl)‐(2/3/4/5‐substituted)‐benzaldimines ( I – XIII ) were synthesized using appropriate synthetic route. Their structures were characterized by FT‐IR, UV‐Visible, ESI‐MS, ¹H‐ and ¹³C‐NMR spectroscopic techniques and analytical methods. The crystal structure of N‐(5‐methyl‐2‐hydroxyphenyl)‐3,4‐dimethoxybenzaldimine ( XIII ) was determined by X‐ray diffraction at room temperature. Relationship between the melting points and the structures of the compounds were examined. Antibacterial activities of the compounds were evaluated against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and Proteus mirabilis. Antifungal activities were reported for Candida albicans. Some of the Schiff bases showed considerable antimicrobial activity against S. aureus and C. albicans.