Tetra 4-aminophenyl Porphyrin Research Articles

Spectroscopic Investigations of Porphyrin-TiO2 Nanoparticles Complexes

This study presents the spectral characterization of TiO2 nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin (TAPP), 5,10,15,20-(Tetra-4-methoxyphenyl) porphyrin (TMPP), and 5,10,15,20-(Tetra-4-carboxyphenyl) porphyrin (TCPP). UV-Vis absorption and Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) spectroscopic studies of these porphyrins and their complexes with TiO2 NPs were performed. In addition, the efficiency of singlet oxygen generation, the key species in photodynamic therapy, was investigated. UV-Vis absorption spectra of the NPs complexes showed the characteristic bands of porphyrins. These allowed us to determine the loaded porphyrins on TiO2 NPs functionalized with porphyrins. FTIR-ATR revealed the formation of porphyrin-TiO2 complexes, suggesting that porphyrin adsorption on TiO2 may involve the pyrroles in the porphyrin ring, or the radicals of the porphyrin derivative. The quantum yield for singlet oxygen generation by the studied porphyrin complexes with TiO2 was higher compared to bare porphyrins for TAPP and TMPP, while for the TCPP-TiO2 NPs complex, a decrease was observed, but still maintained a good efficiency. The TiO2 NPs conjugates can be promising candidates to be tested in photodynamic therapy in vitro assays.

A Porphyrin‐functionalized Graphene Oxide Nanocomposite for Simultaneous Detection of Dopamine and Uric Acid

AbstractCarbon nanomaterials combined with porphyrins having the similar electrocatalytic active center to heme protein are quite promising for high‐performance nonenzymatic electrochemical sensor. Herein, the catalytic tetra(4‐aminophenyl) porphyrin (TAPP) molecules are covalent immobilized on the conductive graphene oxide (GO) surface (TAPP@GO) by a simple one‐pot method. TAPP@GO as a novel electrochemical sensor successfully realized the sensitive detection of dopamine (DA) and uric acid (UA) in nM level with high stability and repeatability. The detection limit (LOD) for DA and UA is as low as 38 and 47 nM, and sensitivity up to 40.3 and 54.2 μA mM−1 in a wide detection range from 0.1 to 350 μM, respectively. Impressively, both DA and UA in the coexistence system can be simultaneously determined with the LOD of 51 and 64 nM for DA and UA, which is further confirmed by accurate determination of both in urine samples. This work represents not only the first example of electrochemical sensor based on organic porphyrin molecules covalent linked on GO surface, but more importantly provides an effective method for developing high‐performance sensing materials.

Pillar[5]arene-derived covalent organic materials with pre-encoded molecular recognition for targeted and synergistic cancer photo- and chemotherapy.

An efficient targeted and synergistic cancer photo- and chemotherapy platform was constructed from aldehyde-modified pillar[5]arene and tetra-(4-aminophenyl)porphyrin successfully.

Covalent functionalization of single-walled carbon nanotubes using meso-tetra(4-aminophenyl) porphyrin and its zinc complex

Covalent linking of 5,10,15,20 meso tetra(4-aminophenyl) porphyrin (TAP) and its zinc complex with single-walled carbon nanotubes (SWCNTs) (nanohybrids A and B, respectively) has been reported. Significant decrease in the intensity of D-band and higher frequency shift of G-band of SWCNT-TAP in Raman spectrum reveals the improved graphitic sp2 hybridization of SWCNT as compared to SWCNT-ZnTAP. This is due to the functionalization of free base porphyrin (electron donating group) in the nanohybrid A. Shifting of carbonyl stretching frequency from 1700 cm−1 to 1680 cm−1 and further appearance of striking bands in the X-ray photoelectron spectroscopy (XPS) and FTIR spectra of nanohybrids A and B confirm the covalent linking of porphyrin chromophores with SWCNTs. XPS reveals that the extent of functionalization of nanohybrid A is more as compared to nanohybrid B. These nanohybrids demonstrate positive solvatochromism. Upon excitation at 450 nm, the nanohybrids A and B reveal ∼76% and 65% fluorescent quenching of emission bands at 686 and 632 nm, respectively. This is due to the energy or electron transfer from porphyrins to SWCNTs.

Highly sensitive optical waveguide sensor for SO2 and H2S detection in the parts-per-trillion regime using tetraaminophenyl porphyrin

ABSTRACTOptical waveguide (OWG) sensors present great potential for detecting trace levels of harmful gases because of their high sensitivity and anti-electromagnetic interference. However, OWG-based SO2 and H2S-detecting sensors in the parts-per-trillion (ppt) range are still lacking. We fabricated 5,10,15,20-(tetra-4-aminophenyl) porphyrin (TAPP) thin film-based OWG sensor devices (TAPP-OWG) to detect SO2 and H2S gases, in which TAPP thin film was immobilized over the surface of a potassium ion exchange glass OWG. These sensors successfully measure extremely low concentrations of SO2 and H2S (detection limit = 1 ppt), providing good repeatability for SO2 (10 ppt) and H2S (10 ppt) gases, with relative standard deviations of 1.67% and 3.68%, respectively. With fast response (t1) and recovery (t2) times for SO2 (t1=4 s, t2=157 s) and H2S (t1=2 s, t2=117 s) at room temperature, TAPP thin film enhances the potential of OWGs for use in high-sensitivity trace-level gas detection.

Function of Tetra (4-Aminophenyl) Porphyrin in Altering the Electronic Performances of Reduced Graphene Oxide-Based Field Effect Transistor.

Porphyrin functionalized reduced graphene oxide (rGO) is attractive for multi-disciplinary research studies, and its improvements for an rGO-based field effect transistor (rGO-FET) were exploited to realize ultrasensitive biochemical and clinical assay. Although it was believed that the hybrids of porphyrin and rGO can make positive impacts on the rGO-FET’s electronic performances, the understandings of its functions are still piecemeal. Herein, the reduced mixtures of tetra (4-aminophenyl) porphyrin (TAP), GO (TAP-rGO), and the FET channeled by them are examined to throw a light on the possible approaches through which TAP affects rGO’s quality and its carrier mobilities. A TAP-caused game relationship is established by deliberating about the results of the intentionally altered experimental conditions, including TAP contents and the overmixing pretreatment. The p-type doping deduction for the right-shifted ambipolar transfer characteristic curves is evidenced by X-ray photoelectron spectroscopy (XPS). The problems posed by the TAP-induced FET features’ improvement, regression, and deterioration are clarified by the integrated proofs from Raman fingerprints, the amide and carboxyl groups’ changing trajectory found by C1s XPS core spectra, and the enlarged few-layer graphene morphology from atomic force microscope and transmission electron microscope. We hope that this effort will provide some constructive recommendations for producing low-cost graphene derivatives and promoting their applications in FET-like electronic components.

Mechanical behavior of crystalline ionic porphyrins

Mechanical properties of six different binary ionic porphyrin crystals with variable morphologies were measured and correlated with their structural properties. These solids were formed from stoichiometric combinations of negatively charged tectons, meso-tetra(4-sulfonatophenyl)porphyrin (TSPP), Cu(II) meso-tetra(4-sulfonatophenyl)porphyrin (CuTSPP), Ni(II) meso-tetra (4-sulfonatophenyl)porphyrin (NiTSPP), and four different cationic tectons, namely, meso-tetra (4-pyridyl)porphyrin (TPyP), tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (TMPyP), Cu(II) meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (CuTMPyP), Ni(II) meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (NiTMPyP), and tetra(4-aminophenyl)porphyrin (TAPP). Crystal structures were determined from single crystal and powder X-ray diffraction patterns. Scanning electron and atomic force microscopes (SEM and AFM) provided topographical information. The common arrangement of the porphyrin tectons within the crystals is consistent with alternating face-to-face molecular arrangement forming coherent columns along the fast-growing long axis which are held together by electrostatic and [Formula: see text]–[Formula: see text] interactions as well as hydrogen bonding. In acquiring the indentation data of the porphyrin crystals using AFM, stress was applied perpendicular to the direction where ionic and [Formula: see text]–[Formula: see text] bonds dominate the packing. At indent loads [Formula: see text]50 nN/nm2, all the porphyrin structures deformed elastically. Young’s modulus ([Formula: see text] values for the different crystals range from 6 to 28 GPa. In a broader perspective, this study highlights the extraordinary mechanical behavior of porphyrin assemblies formed by ionic self-assembly. Judicious selection of charged porphyrin synthons can yield crystalline materials with mechanical properties that combine the elastic characteristics of ‘soft’ polymers with the stiffness of composite materials. Such high-performance materials are excellent candidates for deformable optoelectronic devices.

Electronic structure of tetra(4-aminophenyl)porphyrin studied by photoemission, UV–Vis spectroscopy and density functional theory

The valence and conduction bands of a thin film of tetra(4-aminophenyl)porphyrin (TAPP) are investigated by direct and inverse photoemission as well as by comparison to density functional theory (DFT) calculations. By projecting the electronic eigenfunctions onto the molecular framework it was possible to interpret the origin of each spectroscopic feature. Although the majority of the photoemission spectrum is attributed to the unsubstituted tetraphenylporphyrin (TPP) parent molecule, several features are clearly due to the amino substitution. Substitution also has important consequences for the energy positions of the frontier orbitals and therefore on the low-energy electronic excitations. The measured electronic transport energy gap (Eg=1.85eV) between the highest occupied molecular orbital (HOMO) and lowest unoccupied (LUMO) in TAPP is found to be significantly reduced with respect to TPP. Moreover, an increased energy separation between the two highest occupied states (HOMO and HOMO−1) is found both experimentally and by DFT calculations. Such evidence is attributed to an increased HOMO orbital destabilization due to an enhanced electron-donor character of the phenyl substituents upon amino functionalization. Finally, the above findings together with further time-dependent DFT calculations are used to interpret the effect of the amino groups on the UV–Vis absorption spectrum, namely an overall red-shift of the spectrum and remarkable intensity changes within the Q band.

Photoinduced energy and electron transfer in rubrene–benzoquinone and rubrene–porphyrin systems

Excited-state electron and energy transfer from singlet excited rubrene (Ru) to benzoquinone (BQ) and tetra-(4-aminophenyl) porphyrin (TAPP) were investigated by steady-state absorption and emission, time-resolved transient absorption, and femtosecond (fs)–nanosecond (ns) fluorescence spectroscopy. The low reduction potential of BQ provides the high probability of electron transfer from the excited Ru to BQ. Steady-state and time-resolved results confirm such an excited electron transfer scenario. On the other hand, strong spectral overlap between the emission of Ru and absorption of TAPP suggests that energy transfer is a possible deactivation pathway of the Ru excited state.

Charge-Transfer Complexation and Excited-State Interactions in Porphyrin-Silver Nanoparticle Hybrid Structures

Highly photoactive porphyrin is shown to form charge-transfer complex with silver nanoparticles. Complexation of tetra(4-aminophenyl) porphyrin (TAPP) with Ag nanoparticles is confirmed by ground-state absorption and Raman spectroscopy. Strong Raman enhancement indicates both electromagnetic and chemical enhancement. Evidence of chemical enhancement includes a selective enhancement of porphyrin Raman bands. Fast charge separation in the complex is indicated by ultrafast transient absorption and fluorescence upconversion measurements. The charge-separated state is shown to have a lifetime of 116 ± 6 ps. Porphyrin substituents are shown to play a role in the formation of charge-transfer complex.

Study on the Determination of Heavy-Metal Ions in Tobacco and Tobacco Additives by Microwave Digestion and HPLC with PAD Detection

A new method for the simultaneous determination of heavy-metal ions in tobacco and tobacco additive by microwave digestion and reversed-phase high-performance liquid chromatography (RP-HPLC) was developed. The tobacco and tobacco additive samples were digested by microwave digestion. The lead, cadmium, mercury, nickel, copper, and tin ions in the digested samples were precolumn derivated with tetra-(4-aminophenyl)-porphyrin (T4-APP) to form color chelates; the Hg-T4-APP, Cd-T4-APP, Pb-T4-APP, Ni-T4-APP, Cu-T4-APP, and Sn-T4-APP chelates were then enriched by solid-phase extraction with C18 disks and the retained chelates were eluted from the disks using tetrahydrofuran (THF). The chelates were separated on a Waters Xterra™ RP18 column by gradient using methanol (containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH 10.0) and acetone (containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH 10.0) as a mobile phase at a flow rate of 0.5 mL/min and detected with a photodiode array detector in the range 350–600 nm. The detection limits of lead, cadmium, mercury, nickel, copper, and tin were 5, 4, 2.5, 5, 8, and 4 ng/L, respectively, in the original samples. The method was applied to the determination of lead, cadmium, mercury, nickel, copper, and tin in tobacco and tobacco additive with good results.