Tetra Phenyl Research Articles

Highly Emissive Nanoparticles Based on AIE-Active Molecule and PAMAM Dendritic "Molecular Glue".

The highly emissive nanoparticles Gn-TCMPE (n = 0-4) were prepared by using PAMAM dendrimers as "molecular glue" to adhere an AIE-active molecule tetra(4-(carboxymethoxy)phenyl)ethylene (TCMPE). The electrostatic interaction of ammonium-carboxylate ion pairs provides a driving force between TCMPE and PAMAM dendrimers to form the nanoparticles Gn-TCMPE (n = 0-4), which is validated by the FTIR and (1)H NMR spectra. The formation of nanoparticles dramatically blocks the nonradiative pathway and enhances the fluorescence of TCMPE. The quantum yields of Gn-TCMPE gradually boost at first and then reach to a plateau with increasing the generation of PAMAM dendrimers, and the highest absolute quantum yields are obtained to be 0.42 and 0.64 for Gn-TCMPE (n = 2-4) in methanol dispersion and solid phases, respectively. The fluorescence of the nanoparticles can be tuned by addition of trifluoroacetic acid (TFA). Furthermore, the G4-TCMPE has been successfully applied to selectively image cytoplasm of Hela cells with excellent photostability and low cytotoxicity. This study provides a novel noncovalent strategy for developing highly emissive and robust organic materials fitting for cell fluorescence imaging.

Effects of different light irradiations on structure and optical properties of methoxy-substituted tetraphenylporphyrins

UV lamp, filtered halogen lamp (at 425 nm) and Green laser (532 nm) experiments on a series of meso-substituted tetra phenyl porphyrin, TPP, bearing methoxy peripheral groups together with a metal derivate of 3,4 dimethoxy TPP were lead to different protonation and aggregation structures. Properties of irradiated porphyrins were investigated using their absorption and emission spectra in dichloromethane solution. The results show that the optical properties of the TPP derivates depend on light irradiation source, which shows the tuning of the absorption and emission spectra of the TPP derivates. From the dynamic light scattering measurements, the size distribution of samples was estimated about 5–15 nm in solvent after irradiation. Atomic force microscopy images of deposited porphyrins on the glass surface were shown average particle size between 10 and 30 nm. Particularly, self-assembly of the porphyrin derivates was also observed when green laser was used. We suggest that the irradiation source plays an important role in the controlling of size and morphology of products, and we propose a self-organization model to explain the formation of the porphyrin nanostructures.

Anion conductive aromatic membrane of poly(tetra phenyl ether sulfone) containing hexa-imidazolium hydroxides for alkaline fuel cell application

Abstract Anion exchange membranes of poly(tetra phenyl ether sulfone) containing hexa-imidazolium hydroxides on the hydrophilic segment of a polymer unit were synthesized by sequential polycondensation, chloromethylation, substitution with 1-methylimidazolium and ion exchange. They showed elevated molecular weight, high solubility in polar aprotic solvents and strong chemical and thermal stabilities in comparison to alkyl quaternary ammonium-functionalized polymers. Different levels of substitution and ion exchange were tested; the resulting ionomer membranes showed high ion exchange capacities (IECs) of up to 2.41 mmol g− 1. The imidazolium-functionalized copolymer membranes showed lower water affinity and high durability in alkaline condition. They exhibited hydroxide conductivity above 10− 2 S cm− 1 at room temperature and good chemical stability for up to 7 days without significant losses of ion conductivity.

Disproportionation of O‐Benzylhydroxylamine Catalyzed by a Ferric Bis‐Picket Fence Porphyrin Complex

AbstractHydroxylamine (NH2OH) is an important molecule in biology that serves as an intermediate in the nitrogen cycle, and that can also be utilized as a nitric oxide donor in mammals under certain conditions. In light of this, the interaction of NH2OH with hemes in proteins and model systems has gained much attention recently. In this study, we use the more stable, oxygen substituted O‐benzylhydroxylamine (NH2OBn) as a model for NH2OH. Here, the reactivity of the ferric bis‐picket fence porphyrin complexes [Fe(3, 5‐Me‐BAFP)(ClO4)] (1) and [Fe(3, 5‐Me‐BAFP)(PF6)] (2) (3,5‐Me‐BAFP2– = dianion of tetra(2, 6‐bis(3,5‐dimethylphenoxy)phenyl)porphyrin)) with NH2OBn is investigated. The product of these reactions is characterized by UV/Vis and EPR spectroscopy and X‐ray crystallography. We found that addition of excess NH2OBn to our ferric porphyrin complexes results in reduction of the heme to the ferrous oxidation state. This is followed by disproportionation of additional NH2OBn to yield the ferrous complex [Fe(3,5‐Me‐BAFP)(NH3)2] (3) as the final product. The crystal structure of (3) constitutes the first structural characterization of a bis‐ammonia complex of a ferrous heme. The stability of this complex may be facilitated by the picket fences of the porphyrin ligand used here.

Preparation and properties of phosphoric acid doped sulfonated poly(tetra phenyl phthalazine ether sulfone) copolymers for high temperature proton exchange membrane application

Phosphoric acid-doped sulfonated poly(tetra phenyl phthalazine ether sulfone) (PA-SPTPPES) copolymers were successfully synthesized by the 4,4′-dihydroxydiphenylsulfone with 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenylbenzene (BFBTPB) and 4,4′-difluorodiphenylsulfone in sulfolane. Poly(tetra phenyl phthalazine ether sulfone)s (PTPPESs) were prepared via an intramolecular ring-closure reaction of dibenzoylbenzene of precursor and hydrazine. The sulfonated poly(tetra phenyl phthalazine ether sulfone) (SPTPPES) membranes were obtained by sulfonation under concentrated sulfuric acid, and followed phosphoric acid-doped by immersion in phosphoric acid. Different contents of doped and sulfonated unit of PA-SPTPPES (10, 15, 20 mol% of BFBTPB) were studied by FT-IR, 1H NMR spectroscopy, and thermo gravimetric analysis (TGA). The ion exchange capacity (IEC) and proton conductivity of SPTPPESs and PA-SPTPPESs were evaluated with increase of degree of sulfonation and doping level. The PA-SPTPPESs membranes exhibit proton conductivities (80 °C, relative humidity 30%) of 41.3 ∼ 74.1 mS/cm and the maximum power densities of PA-SPTPPES 10, 15, and 20 were about 294, 350, and 403 mW/cm2.

Phosphoric acid doped sulfonated poly(tetra phenyl isoquinoline ether sulfone) copolymers for high temperature proton exchange membrane potential application

Phosphoric acid-doped sulfonated poly(tetra phenyl isoquinoline ether sulfone)s (PA-SPTPIESs) were successfully synthesized for high temperature proton exchange membrane. Poly(tetra phenyl ether ketone sulfone)s (PTPEKS) were prepared from 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenyl benzene (BFBTPB) and bis(4-fluorohenyl) sulfone with bis(4-hydroxyphenyl) sulfone. The synthesis of the poly(tetra phenyl isoquinoline ether sulfone)s (PTPIESs), was carried out via an intramolecular ring-closure reaction of dibenzoylbenzene of PTPEKS with benzylamine. The sulfonated poly(tetra phenyl isoquinoline ether sulfone)s (SPTPIESs) were obtained by following sulfonation with concentrated sulfuric acid and doped by phosphoric acid. Different contents of sulfonated unit on PTPIESs (8, 12, 16 mol% of BFBTPB) and PA-SPTPIESs were studied by FT-IR, 1H NMR spectroscopy, and thermogravimetric analysis (TGA). Strong acid–base interaction effect between poly benzisoquinoline (PBI) and sulfonic acid groups formed ionic crosslinking network between polymer chains. The ion exchange capacity (IEC) and proton conductivity of PA-SPTPIESs were evaluated with degree of sulfonation and doping of phosphoric acid.

Synthesis and characteristics of multi-aryl substituted molecular glasses bearing biphenyl core

Two novel compounds based on biphenyl structure, 2,2′-di(3,5-di(tert-butylcarbonate)phenyl)-4,4′-di(tert-butylcarbonate)biphenyl (A) and 2,2′,4,4′-tetra(3,5-di(tert-butylcarbonate)phenyl)biphenyl (B) were synthesized by commercially available materials. The products were fully characterized by FTIR, NMR and elemental analysis. The thermal stability and the phase transition of these compounds had been studied by TGA and DSC techniques. For compound A, thermal decomposition temperature was of 176°C and glass transition temperature (Tg) was of 105°C. While for compound B, the thermal decomposition occurred at 186°C and Tg was of 122°C. The synthesized compounds were found to be amorphous materials by XRD analysis and good film-forming ability by AFM analysis. These results indicated that the synthetic molecular glasses would be suitable for low molecular weight photo resists in EUV lithography.

Potentiometric Membrane Sensors for Determination of Memantine Hydrochloride and Pramipexole Dihydrochloride Monohydrate

Five solid membrane sensors responsive to memantine hydrochloride (MEM) and pramipexole dihydrochloride monohydrate (PXL) are described for simple and fast determination of these drugs in pharmaceutical preparation and human plasma. The first and the second sensors are based on the formation of an ion association complex between MEM as a cationic drug with Na tetra phenyl borate and ammonium reineckate (as anionic exchanger), respectively. The third sensor is based on the formation of an ion association complex between PXL with ammonium reineckate. The produced electroactive material is dispersed in PVC matrix. While the other fourth and fifth sensors are based on using functionalized lipophilic cyclodextrin derivative (2-hydroxypropyl-�-cyclodextrin) as sensor ionophore for the determination of MEM and PXL. The performance characteristics of these sensors-evaluated according to IUPAC recommendations-reveal fast, stable and near Nernstian response for 1x10 -4 -1x10 -1 M and 1x10 -6 -1x10 -2 M for (MEM) and (PXL), respectively. Many inorganic and organic substances such as drug excipients and diluents normally used in drug formulations do not interfere with drugs response. Statistical comparison between the results obtained by applying the proposed potentiometric method for the determination of the (MEM) and (PXL) in their pure powder forms and those obtained by applying the reported methods was done and no significant difference was found at p =0.05. Validation of the method according to ICH guidelines shows the suitability of the sensors for quality control analysis of the cited drugs in pharmaceutical formulations and human plasma. The proposed sensors can also be used as a detector for HPLC.

Preparation and characterization of sulfonated poly(tetra phenyl ether ketone sulfone)s for proton exchange membrane fuel cell

Sulfonated poly(tetra phenyl ether ketone sulfone)s SPTPEKS were successfully synthesized for proton exchange membrane. Poly(tetra phenyl ether ketone sulfone)s PTPEKS were prepared by the 4,4′-dihydroxydiphenylsulfone with 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenylbenzene (BFBTPB) and 4,4′-difluorodiphenylsulfone, respectively, at 210 °C using potassium carbonate in sulfolane. PTPEKS were followed by sulfonation using chlorosulfonic acid and concentrated sulfuric acid at two stage reactions. Different contents of sulfonated unit of SPTPEKS (17, 20, 23 mol% of BFBTPB) were studied by FT-IR, 1H NMR spectroscopy, and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water. The ion exchange capacity (IEC) and proton conductivity of SPTPEKS were evaluated with increase of degree of sulfonation. The water uptake of synthesized SPTPEKS membranes exhibit 25–61% compared with 28% of Nafion 211®. The SPTPEKS membranes exhibit proton conductivities (25 °C) of 11.7–25.3 × 10−3 S/cm compared with 33.7 × 10−3 S/cm of Nafion 211®.

Effect of hydrogen bonding on catalytic activity of some manganese porphyrins in epoxidation reactions

Mn (III)-tetra phenyl porphyrin-acetate (MnTPPOAc) and some kinds of meso-phenyl substituted porphyrins by hydroxyl groups and their Mn (III) complexes were synthesized. These Mn -porphyrins were used as catalyst in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n- Bu4NHSO5 ) as oxidant and tetra-n-butylammonium acetate (n- Bu4NOAc ) as the axial ligand. The following order of catalytic activity was observed for cyclooctene: T(2,3-OHP)PMnOAc ≫ T(2,4,6-OHP)PMnOAc ≥ T(4-OHP)PMnOAc ≥ T(2,6-OHP)PMnOAc ≥ TPPMnOAc and T(2,3-OHP)PMnOAc ≫ TPPMnOAc > T(4-OHP)PMnOAc > T(2,4,6-OHP)PMnOAc > T(2,6-OHP)PMnOAc for other alkenes. Different activity and stability of the catalysts were interpreted based on the hydrogen bonding between hydroxyl groups with appropriate orientation on the meso-position of the phenyl groups and axial bases or oxidant. T(2,3-OHP)PMnOAc catalyst has shown optimal condition for effective hydrogen bonding. In the case of other catalysts, electronic and steric factors overcome the hydrogen bonding effect.

Preparation and preliminary evaluation of [67Ga]-tetra phenyl porphyrin complexes as possible imaging agents

[67Ga]labeled tetraphenyl porphyrin ([67Ga]-TPP) was prepared using freshly prepared [67Ga]GaCl3 and tetraphenyl porphyrin (TPPH2) for 30–60 min at 25 °C (radiochemical purity: >97 ± 1% ITLC, >98 ± 0.5% HPLC, specific activity: 13–14 GBq/mmol). Stability of the complex was checked in final formulation and human serum for 24 h. The partition coefficient was calculated for the compound (log P 1.89). The biodistribution of the labeled compound in vital organs of wild-type rats was studied using scarification studies and SPECT imaging up to 24 h. A detailed comparative pharmacokinetic study performed for 67Ga cation and [67Ga]-TPP. The complex is mostly washed out from the circulation through kidneys and can be an interesting tumor imaging/targeting agent due to low liver uptake and rapid excretion through the urinary tract.

Optical investigations of interaction between zinc tetra phenyl porphyrin and CdSe nanoparticles

Interactions between nanoparticles of zinc tetra phenyl porphyrin (ZnTPP) with CdSe nanoparticles in dimethyl sulphoxide solvent have been investigated. A ZnTPP–CdSe complex was formed which showed substantial changes in the UV–Vis absorption spectra in the presence of CdSe. Fluorescence measurements showed an interesting behavior at low as well as high concentrations of CdSe. When low concentrations of CdSe nanoparticles were added to the ZnTPP nanoparticles solution, besides two fluorescence bands due to ZnTPP nanoparticles, an intense new band appeared. On the other hand at high concentrations of CdSe one of the fluorescence band of ZnTPP at ∼604 nm increased.

U (2) algebraic model applied to vibrational spectra of Nickel Metalloporphyrins

In this paper the highly excited stretching and bending vibrational energy levels of some Nickel Metalloporphyrin molecules are studied by U (2) algebraic model. Its application to Nickel Octaethyl Porphyrin, Nickel Tetra Phenyl Porphyrin and Nickel Porphyrin are presented with fewer algebraic fitting parameters. The highly excited stretching and bending vibrational energy levels of these molecules are showing the energy clustering spectrum.

Comparative studies of ONNO-based ligands as ionophores for palladium ion-selective membrane sensors

Palladium sensors based on two neutral ionophores, N, N′-bis(acetylacetone) cyclohexanediamine ( L 1 ) and N, N′-bis( o-hydroxyacetophenone)-1,2-cyclohexanediamine ( L 2 ) for quantification of palladium ions are described. Effect of various plasticizers ( o-NPOE, DBP, DEP, DOP, TBP, and CN) and anion excluder, sodium tetra phenyl borate (NaTPB) has been studied. The best performance is obtained with a membrane composition of PVC: o-NPOE:ionophore ( L 1 ):NaTPB of 150:300:5:5 (%, w/w). The sensor exhibits significantly enhanced selectivity towards palladium ion over the concentration range 1.0 × 10 −8 to 1.0 × 10 −1 M with a lower detection limit of 4.0 × 10 −9 M and a Nernstian compliance (29.1 ± 0.3 mV decade −1 of activity) within pH range 2.0–6.0 and fast response time of 10 s. Influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability of the sensor are demonstrated. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 4 months. Selectivity coefficients determined with fixed interference method (FIM) indicate high selectivity for palladium. The proposed electrode shows fairly good discrimination of palladium from other cations. The application of prepared sensor has been demonstrated in determination of palladium ions in spiked water sample.

Meso-tetraarylporphyrin catalyzed highly regioselective ring opening of epoxides with acetic acid

Abstract Highly regioselective ring opening of styrene oxide with acetic acid in the presence of catalytic amounts of meso -tetra(4-CH 3 )phenyl- or meso -tetraphenylporphyrin at room temperature is reported. Under the same reaction conditions, cyclohexene oxide is more reactive than styrene oxide and gives the trans -isomer as the sole product.

Development of Nalbuphine‐Selective Membrane Electrode and Its Applications in Pharmaceutical Analysis

A nalbuphine ion‐selective PVC membrane electrode based on ion‐pair complex of nalbuphine with tetra phenyl borate was prepared with di‐butyl sebacate as a plasticizer. The electrode exhibits a linear response with a Nernstain slope 59.6 mV decate−1 at 25°C with the concentration range of 1×10−6−1×10−2 M nalbuphine. The electrode response was not sensitive to pH changes from 3.5–7 and not affected by possible interfering species such as common inorganic cations, sugars and amino‐acids. The electrode shows good stability, reproducibility and fast response. These characteristics of the electrode enable it to be used successfully for the determination of nalbuphine hydrochloride in pure form and in pharmaceutical preparations.

A Novel Holmium(III) Membrane Sensor Based on N‐(1‐Thien‐2‐Ylmethylene)‐1,3‐Benzothiazol‐2‐Amine

A novel plasticized membrane sensor for Ho(III) ions based on N‐(1‐thien‐2‐ylmethylene)‐1,3‐benzothiazol‐2‐amine (TBA) as a neutral carrier was prepared. The best performance was obtained with a membrane composition of 31% PVC, 61% benzyle acetate, 2% sodium tetra phenyl borate and 6% carrier. The electrode exhibits a Nernstian response for Ho(III) ions over a particular concentration range (1.0×10−5−1.0×10−2 M) with a slope of 19.7±0.2 mV decade−1. The limit of the detection is 7.0×10−6 M. The sensor has a response time of <15 s and a useful working pH range of 4.0–9.5. The proposed sensor discriminates relatively well towards Ho(III) ions with regard to common alkali, alkaline earth, and specially lanthanide ions. It was successfully applied as an indicator electrode in a potentiometric titration of Ho(III) ions with EDTA. It was also applied in determination of fluoride ions in a mouth wash preparation. The proposed sensor was applied for the determination of Ho(III) ion concentration in binary mixtures.

Synthesis, characterization and crystal structure of copper(I) tetra(phenyl thiourea) chloride

The title compound C28H32N8S4ClCu has been synthesized, crystallized and characterized by density measurement, element analysis and IR spectra. Its crystal structure has been determined by X-ray diffraction methods. The most interesting structure feature of the complex is that the dihedral angle between the thiourea framework and the benzene ring is 52.03(22)°, the minimal value in the literature. All four bonds around Cu(I) are equivalent, but the six S–Cu–S angles are non-equivalent.

Nonlinear optical properties of a porphyrin derivative incorporated in Nafion polymer

A solid state nonlinear optical medium is obtained by the incorporation of the metalloporphyrin, Zinc Tetra Phenyl Porphyrin (ZnTPP) in Nafion polymer membrane. The nonlinear refractive index of this membrane is measured at 632.8 nm by the z-scan technique and found to be on par with that exhibited by ZnTPP in the solution form. Photodegradation effects seen in the porphyrin solution appear to be inhibited due to its incorporation in the membrane. The material is found to exhibit optical limiting effects based on nonlinear refraction and its behaviour is investigated in comparison with that of ZnTPP in solution form. The nonlinearity appears to be of thermal origin.

A Porphyrin Based Potentiometric Sensor for Zn2+ Determination

PVC based membranes of disodium salt of porphyrin 3,7,12,17-tetramethyl-8, 13-divinyl 2,18-porphine dipropionic acid (I) as ionophore with sodium tetra phenyl borate (NaTPB) as anion excluder and dibutyl phthalate (DBP), dioctyl phthalate (DOP), dibutyl butyl phosphonate (DBBP), tris(2- ethyl hexyl)phosphate (TEP), tri-n-butylphosphate (TBP) and 1- chloronaphthalene (CN) as plasticizing solvent mediators were prepared and constructed for determination of Zn(II). The PVC based membrane of (I) with DBBP as plasticizer and having anion excluder, NaTPB in the ratio PVC: I: NaTPB: DBBP (150: 10: 2: 200) gave the best results in terms of working concentration range (1.3×10-5-1.0 ×10-1M) with a Nernstian slope (30.0 mV/decade of activity). The useful pH range of the sensor is 3.0 –7.4, beyond which a drift in potential was observed. The response time of the sensor is 10s and the lifetime was about 2 months during which it could be used without any measurable divergence. It had good stability and reproducibility. The membrane worked satisfactorily in non-aqueous medium up to 40% (v/v) non-aqueous content. The selectivity coefficient values indicate that the electrode is highly selective for Zn2+ over a number of other cations except Na+ and Cd2+. Although Na+ and Cd2+ are likely to cause some interference, they would not interfere if present at the concentrations &lt; 1 ×10-5 and &lt; 5 ×10-5 M, respectively. The electrode has been used as an indicator electrode to determine the end point in the potentiometric titration of Zn2+ with EDTA.