Sensing Of Aqueous Phosphates By Polymers With Dual Modes Of Signal Transduction

A new approach to sensing of aqueous phosphate-related anions based on chromogenic conductive polymers is demonstrated. This method utilizes synergy between low-level p-doping in a polythiophene polymer and hydrogen bonding to increase anion-sensor affinity. These chromogenic conductive polymers show anion-specific changes both in color and in conductivity upon increasing concentration of anions, thus providing two independent modes of signal transduction

Interaction Of Porphyrins With A Dendrimer Template: Self-aggregation Controlled By Ph

The interaction between self-aggregated porphyrins such as 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and 5,10,15,20-tetrakis(4-phosphonatophenyl)porphyrin (TPPP), and a generation 5 (G5) PAMAM dendrimer template is governed by minute differences of porphyrin acido-basic properties. While at neutral pH both monomeric TPPS and TPPP form complexes with G5, decreasing pH did not lead to porphyrin ring protonation (pK(a) approximate to 5) but rather to the preferential formation of H-aggregates (probably H-dimers), most likely due to protonation of the G5. Upon further acidification of the solution, this face-to-face orientation of the porphyrin units is being converted to edge-to-edge aligned J-aggregates with a tightly defined structure. This process starts by protonation of the porphyrin ring at pH below 2.3 and 2.8 for TPPS and TPPP, respectively. The AFM imaging of porphyrin/G5 nanostructures obtained at pH 0.7 shows the formation of long nanorods of TPPS with partially aggregated G5 and small aggregates of TPPP connected to individual G5 molecules

Emission Color Tuning In Alq(3) Complexes With Extended Conjugated Chromophores

GraphicsA new method for the synthesis of 5-arylethynyl-8-hydroxyquinoline ligands using Sonogashira-Hagihara coupling was developed. The electronic nature of arylethynyl substituents affects the emission color and quantum yield of the resulting Al(III) complex. Photophysical properties of the metallocomplexes correspond to the electron-withdrawing/-donating character of the arylethynyl substituents. Optical properties of such AI(Ill) complexes correlate with the Hammett constant values of the respective substituents. This strategy offers a powerful tool for the preparation of electroluminophores with predictable photophysical properties

1,3-indane-based Chromogenic Calixpyrroles With Push-pull Chromophores: Synthesis And Anion Sensing

Knoevenagel condensation of 2-formyl-octamethylcalix[4]pyrrole with selected 1,3-indanedione derivatives yields calix[4]pyrrole anion sensors with push-pull chromophores displaying strong intramolecular charge transfer. The push-pull feature results in augmented signal output as well as in dramatic changes in anion selectivity exemplified by a 50-fold increase in acetate vs chloride selectivity compared to the parent calix[4]pyrrole

Sensing Of Antipyretic Carboxylates By Simple Chromogenic Calix[4]pyrroles

We present a simple, two- or three-step method for the synthesis of chromogenic octamethylcalix[4]pyrrole-based (OMCP) sensors for anions. Electrophilic aromatic substitution allows for converting the pyrrole moieties of OMCP into a dye. The formation of a sensor-anion complex results in partial charge transfer and a dramatic change in color. The absorption (UV-vis) and NMR titration experiments show that the chromogenic OMCPs sense anions administered as aqueous solutions, even at high ionic strength ( approximately 0.1 M NaCl), while displaying selectivity for pyrophosphate and carboxylate anions. The experiments with polyurethane sensor films show a strong response for aqueous carboxylates, such as antipyretics naproxen approximately ibuprofen \u3e salicylate, without being biased by bicarbonate or carboxy termini of blood plasma proteins

Self-aggregates Of Cationic Meso-tetratolylporphyrins In Aqueous Solutions

Aggregation properties of meso-tetratolylporphyrins bearing cationic substituents of a lipophilic nature such as ammonium, pyridinium, phosphonium, sulfonium, and isothiouronium were studied by UV/vis and resonance light scattering spectroscopy. The exciton point-dipole approximation was used to predict the structural alignment of the porphyrin units within the aggregate. The contribution of various types of aggregates depends on the porphyrin substitution, ionic strength, and temperature of aqueous solution of the porphyrin. In general, the preferred structure of an aggregate formed by temperature-induced aggregation is the J-aggregate exhibiting the characteristically narrow, red-shifted Soret band indicating a parallel side-by-side arrangement of the porphyrin units. The formation of aggregates of cationic tetratolylporphyrins is controlled by both electrostatic and hydrophobic interactions, Observed aggregation properties of porphyrin derivatives bearing trimethylammonium, trimethylphosphonium, pyridinium, dimethylphenylphosphonium, and triphenylphosphonium substituents are in very good agreement with a theoretical model based solely on electrostatic interactions

Preprogramming Of Porphyrin-nucleic Acid Assemblies Via Variation Of The Alkyl/aryl Substituents Of Phosphonium Tetratolylporphyrins

Cationic alkyl/arylphosphonium meso-tetratolylporphyrins aggregate in an aqueous solution to form H-aggregates, J-aggregates, and long-range assemblies. The ratio between the monomer and various types of aggregates can be controlled by the substitution in the phosphonium units and by the ionic strength. A trimethylphosphonium derivative is predominantly monomeric, dimethylphenylphosphonium forms monomers as well as low-molecular-weight H- and J-aggregates, triphenylphosphonium forms mainly H- and J-aggregates, and tri(n-butyl)phosphonium forms mainly long-range assemblies. Porphyrin monomers associate with calf thymus DNA (binding constant Kb approximate to 10(7) M-1) and oligonucleotides (K-b approximate to 10(5-)10(6) M-1). The large size of the meso-substituents prevents the intercalation between base pairs. All phosphonium porphyrins described in this study were found to bind to the phosphate backbone of a nucleic acid with a significant preference for A-T base pair sequences. Porphyrin aggregates formed in the solution deposit readily on the surface of the DNA and oligonucleotides without changing their structure and size. Porphyrin monomers bound to DNA and nucleotides have photophysical properties (higher quantum yield of triplet states and singlet oxygen) different from those of porphyrin aggregates

Simple Electrooptical Sensors For Inorganic Anions

Electrooptical sensors consisting of a conjugated chromophore undergoing a change in color and a redox-active moiety such as quinone fused to the chromophore were synthesized. Strong changes in colorimetric and electrochemical properties were observed in the presence of inorganic anions. A unique anion-specific response was observed for fluoride, pyrophosphate, and acetate. DFT (B3LYP/6-31G*) calculations performed for both on/off states of a sensor-fluoride model are in good agreement with the observed electrochemical and spectroscopic data

Minipig cytochrome P450 3A, 2A and 2C enzymes have similar properties to human analogs

BACKGROUND: The search for an optimal experimental model in pharmacology is recently focused on (mini)pigs as they seem not only to be an alternative source of cells and tissues for xenotherapy but also an alternative species for studies on drug metabolism in man due to similarities between (mini) pig and human drug metabolizing systems. The purpose of this work is to characterize minipig liver microsomal cytochromes P450 (CYPs) by comparing their N-terminal sequences with corresponding human orthologs. RESULTS: The microsomal CYPs exhibit similar activities to their human orthologous enzymes (CYP3A4, nifedipine oxidation; 2A6, coumarin 7-hydroxylation; 2D6, bufuralol 1'-hydroxylation; 2E1, p-nitrophenol hydroxylation; and 2C9, tolbutamide hydroxylation). Specific minipig CYP (2A, 2C and 3A) enzymes were partially purified and proteins identified by immunostaining (using antibodies against the respective human CYPs) were used for N-terminal amino acid sequencing. From comparisons, it can be concluded that the sequence of the first 20 amino acids at the N-terminus of minipig CYP2A is highly similar to human CYP2A6 (70% identity). The N-terminal sequence of CYP2C shared about 50% similarity with human 2C9. The results on the minipig liver microsomal CYP3A yielded identical data with those obtained for amino acid sequences of the pig CYP3A29 showing 60% identity with human CYP3A4. CONCLUSIONS: Thus, our results further support the view that minipigs may serve as model animals in pharmacological/toxicological studies with substrates of human CYP enzymes, namely, of the CYP3A and CYP2A forms

Green Synthesis Of Polycyclic Benzimidazole Derivatives And Organic Semiconductors

Polycyclic benzimidazole derivatives, an important class of compounds in organic electronics and photovoltaics, were prepared using a solvent-free green process based on heating carboxylic acid anhydrides and arylene diamines in the presence of zinc acetate in the solid state. Products were isolated and purified directly by train sublimation of the crude reaction mixtures. The reaction conditions were optimized using various carboxylic acid anhydrides. Optical and electrochemical properties of these materials are also described