Charged Porphyrin – dopa Melanin Interaction at Varied pH: Fluorescence Lifetime and Photothermal Studies

The influence of pH on the spectral forms of negatively and positively charged porphyrin dyes: tetrakis(4-sulfonatophenyl)porphyrin (TPPS₄) and tetra(4-N, N, N, N-trimethylanilinium) porphyrin (TAP) in the presence of dopa melanin is investigated. The interaction between dyes and dopa melanin is shown to be dependent on the kind of dye spectral forms and on environmental pH. The creation of different forms, deactivation of their electronic excited states, and their interaction with dopa melanin have been monitored by absorption, fluorescence, and photoacoustic spectroscopy in the pH range of 2–9. This article demonstrates that the TAP–dopa melanin complex is destroyed at the lowest pH because of competition between positively charged peripheral groups of TAP and protons, which interact with negative centers of dopa melanin. Otherwise, dopa melanin affects photothermal and fluorescence properties of monomeric dications (TAP and TPPS₄) rather weakly. It has also been suggested that the aggregated dicationic of TPPS₄ can serve as an acceptor in the energy transfer from dopa melanin. Presented results seem to be applicable to a photodynamic therapy of cancer.     

Synthesis of novel coumarin and benzocoumarin derivatives and their biological and photophysical studies

Several derivatives of coumarin‐3N‐carboxamides ( 3‐21 ) have been prepared via the reaction of the coumarin‐3‐carbonyl chloride ( 1 ) with a number of nucleophiles. Novel double‐headed coumarin‐3N‐carboxamides ( 26‐33 ) were also produced using the same method. The Pechmann‐Duisberg reaction was applied to prepare new benzo[f]‐ benzo[h]coumarins and 4‐(chloromethyl)‐pyrano[3,2‐c]coumarin‐2‐one ( 36‐42 ). The reaction of 1‐chloromethylbenzo[f]coumarins ( 36 ) with cyanide anion under different reaction conditions was also investigated in order to assess its suitability for nucleophilic substitution reactions as well as ring transformation products ( 43‐49 ). Synthesis of 1‐((benzo[d]thiazol‐2‐yl)methyl)‐9‐hydroxybenzo[ f ]coumarin ( 50 ) represented the first example of methylene bridge‐head heterocyclecontaining benzo[f]coumarin. Some of the newly prepared coumarins exhibited anti‐bacterial activity against Gram Positive and Gram negative bacteria. Compound 36d was found to be active against all the screened bacteria. Photophysical studies were performed on selected fluorescent benzo[f]‐ and benzo[h]coumarin and the quantum yields were also calculated. All new compounds were characterized by IR, MS, ¹H and ¹³C NMR, as well as elemental analysis.     

Three different spectrophotometric methods manipulating ratio spectra for determination of binary mixture of Amlodipine and Atorvastatin

Three simple, specific, accurate and precise spectrophotometric methods manipulating ratio spectra are developed for the simultaneous determination of Amlodipine besylate (AM) and Atorvastatin calcium (AT) in tablet dosage forms. The first method is first derivative of the ratio spectra ((1)DD), the second is ratio subtraction and the third is the method of mean centering of ratio spectra. The calibration curve is linear over the concentration range of 3-40 and 8-32 μg/ml for AM and AT, respectively. These methods are tested by analyzing synthetic mixtures of the above drugs and they are applied to commercial pharmaceutical preparation of the subjected drugs. Standard deviation is <1.5 in the assay of raw materials and tablets. Methods are validated as per ICH guidelines and accuracy, precision, repeatability and robustness are found to be within the acceptable limit.     

In situ synchrotron X‐ray powder diffraction for studying the role of induced structural defects on the thermoluminescence mechanism of nanocrystalline LiF

The correlation between the thermoluminescence (TL) response of nanocrystalline LiF and its microstructure was studied. To investigate the detailed TL mechanism, the glow curves of nanocrystalline LiF samples produced by high‐energy ball‐milling were analyzed. The microstructure of the prepared samples was analyzed by synchrotron X‐ray powder diffraction (XRPD) at room temperature. Then, the microstructure of a representative pulverized sample was investigated in detail by performing in situ XRPD in both isothermal and non‐isothermal modes. In the present study, the dislocations produced by ball‐milling alter the microstructure of the lattice where the relative concentration of the vacancies, responsible for the TL response, changes with milling time. An enhancement in the TL response was recorded for nanocrystalline LiF at high‐temperature traps (after dislocations recovery starts >425 K). It is also found that vacancies are playing a major role in the dislocations recovery mechanism. Moreover, the interactions among vacancies–dislocations and/or dislocations–dislocations weaken the TL response.     

Label-free molecular analysis of live Neospora caninum tachyzoites in host cells by selective scanning Raman micro-spectroscopy

A selective scanning method was used to measure spatially resolved Raman spectra of live Neospora caninum tachyzoites colonizing human brain microvascular-endothelial cells. The technique allowed the detection of nucleic acids, lipids and proteins linked to the parasites and their cellular micro-environment at ～10× shorter acquisition time compared to raster scanning.     

Electrochemically controlled self-assembly of an organometallic block copolymer

A new means of controlling the order-disorder transition of block copolymers is presented. By applying small electrical potentials (2 V/cm) to disordered solutions of an organometallic block copolymer, oriented ordered grains were obtained near the positive electrode. After reversing the electrical bias on the system, the ordered grains disappeared, and new, oriented, ordered regions were formed at the opposite electrode. Our work establishes the concept of electrochemical self-assembly for controlling order formation in block copolymers.     

Reactions of N,N-Disubstituted 5-Arylmethylidene-2-amino-thiazol-4(5H)-ones with CH Acids

Summary.  N,N-Disubstituted 5-arylmethylidene-2-aminothiazol-4(5H)-ones reacted with diethyl malonate, ethyl benzoylacetate, acetylacetone, or cyclopentadiene in refluxing toluene and in presence of powdered sodium to give the respective 5-arylmethylidene-2′-amino-2,5′-bithiazolylidene-4,4′-dione derivatives in moderate yields. 5-Benzylidene-2-morpholin-4-yl-2-thiazol-4(5H)-one reacted with malononitrile in toluene and in presence of powdered sodium under mild conditions to afford the 1:1 adduct, benzylmalononitrile, and 2-morpholin-4-yl-2-thiazol-4(5H)-one. However, similar treatment of 5-(4-methoxyphenylmethylidene)-2-morpholin-4-yl-2-thiazol-4(5H)-one with malononitrile yielded the 2,5′-bithiazolylidene-4,4′-dione derivative together with 4-methoxyphenylmethylidene malononitrile. Treatment of 5-benzylidene- and 5-(4-methoxyphenylmethylidene)-2-morpholin-4-yl-2-thiazol-4(5H)-ones with 3-phenyl-4-oxo-2-thioxo-1,3-thiazolidine in refluxing toluene and in presence of powdered sodium produced 5-arylmethylidene-3-phenyl-4-oxo-2-thioxo-1,3-thiazolidines in good yields. The structures of all products were deduced from microanalytical and spectroscopic data, mechanistic details are discussed. Corresponding author. E-mail: kamalkandeel@hotmail.com Received November 5, 2001. Accepted (revised) December 17, 2001     

A conjugated polyazine containing diketopyrrolopyrrole for ambipolar organic thin film transistors

A π-conjugated polyazine containing diketopyrrolopyrrole (DPP) moiety, PDBTAZ, is synthesized through a simple condensation polymerization. PDBTAZ is found to be a high-performance ambipolar semiconductor in organic thin film transistors (OTFTs), showing an electron mobility of up to 0.41 cm(2) V(-1) s(-1) and a hole mobility of up to 0.36 cm(2) V(-1) s(-1).