Synthesis and Photocytotoxicity of Mono-functionalised Porphyrin with Valine Moiety

A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenyl ring was synthesized for photocytotoxicity examination in four steps, starting from regiospecific mono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Al adenocarcinona cell line was tested.     

Absorption Complex between Porphyrin and Phenothiazine in Reverse Micelles

Porphyrin derivatives attract much more interest in photodynamic therapy (PDT). Their importance as therapeutic drugs and targeting agents has been widely recognized1, and many of the efforts have been put towards crafting new porphyrin-based molecular entities to achieve enhanced tumor localization, better tissue penetration and increased singlet oxygen quantum yield2. The states of porphyrins in tissue models such as micelles, lipid bilayers are extensively investigated focusing more or l…     

Synthesis and Characterization of One-dimensional and Two-Dimensional Porphyrin Polymers (Ⅰ)

Porphyrin polymers are of interest in relation to conductive materials[1, 2], catalysts for photosynthetic charge separation[3], or the fundamental features in biological systems[4]. There have been many versatile studies about them[5.6]. The one-dimensional "Shish Kebab"porphyrin polymers synthesized with a new method different from those reported and Schiff-base porphyrin polymers with two-dimensional nano-structure have provided a new field of study. The present paper covers highly ordered…     

Spectrophotometric Study of Reaction Between Platinum and α,β,γ,δ-Tetra-(2-Chlorophenyl) Porphyrin

The present paper describes the complex reaction of α, β,γ, δ-tetra-(2-chlorophenyl} porphyrin with platinum in the presence of the mixture surfactant, sodium dodecylbenzene sulfonate and OP, and a new highly sensitive method for spectrophotometric determination of micro amounts of platinum. Beer's Law was obeyed when the concentration of platinum was in the range of 0?.2μg/25ml. The molar absorptivity was found to be 3.1×106 L mol-1 cm-1 at 417nm.     

Gold-catalyzed Synthesis of Pyridine Containing Macrocycles, Related to Porphyrin

Porphyrins are very important substances used in a wide range of model systems in many areas, such as biomimic chemistry and material science. This kind of macrocycle generally consists of 5-membered ring to form a cyclic extended aromatic network. Recently much work have been done concerning the modification of porphyrins core structures, and many kinds of analogues have been recorded. One of the important aspects was the research of the porphyrinogen ligand.These macrocycles bear functional resemblance to certain kind of polydentate ligand, and provide a variety of tri-dimensional binding cavities for metal ions. In addition, some other kinds of analogues have been recorded, involving the introduction of a CH unit to replace one of the nitrogen atoms. We also notice the fact that pyridine is a very effective ligand, and it can coordinate with many kinds of metals. Based on these observations, we would like to design and synthesize a new porphyrinogen (5) analogue containing a NNNN core, two of the N atoms from pyrrole and the other two N from pyridine. Such core modifications may alter the electronic structure of the ring and provide variable cavity for metal coordination.     

Studies on Porphyrin and Phthalocyanine Monolayers by Means of Compression－Recompression Isotherms and BAM

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Novel Mixed LB Films of Porphyrin and Phthalocyanine Based on Molecular Recognition

Phthalocyaninesaresyntheticsubstancesrelatedtothenaturallyoccurringporphyrins.Itsthermalandchemicalstabilitymakesitveryusefulinmolecularelectronicsl.TheLBfilmsofphthalocyaninehavebeenwidelystudiedinthepastdecade.ButfewreportsonthemixedLBfilmsofphthalocyanineandporphyrinhavebeenpublished"'HerewereportanovelmixedLBfilmfabricatedbydepositingporphyrinandphthalocyaineinonelayerbasedonmolecularrecognition.Figure1.ThestructureofcompoundAandBAsymmetricallysubstitutedphthalocyanineAandporphyrinBa…     

Synthesis and Study of Spectroscopic Properties of Imidazole Porphyrin and Its Zn(Ⅱ) Complex

A novel sensitizer with imidazole zinc porphyrin as electron donor has been synthesized. The structure has been characterized by UV-Vis, elemental analyses and 1 H NMR.UV-Vis and fluorescence spectra show that it has good light absorbing properties in the range of visible light and suggests that it has potential applications in dye-sensitized solar cells.     

Investigation of Light-harvest Material： Synthesis and Characterization of Nanometer Porphyrin Trimer

ω-Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linkedreagent and 5- (4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H2MHTPP) as the matrix reacts with 5, 15-di(4- hydroxyphenyl)-10, 20-diphenyl porphyrin(trans-H2DHDPP) to give the title nanometer porphyrintrimer. The characterization was carried out by means of elemental analyses, UV-Vis, IR, ^1H NMR andXRD.     

On-Surface Synthesis and Characterization of Triply Fused Porphyrin–Graphene Nanoribbon Hybrids

On-surface synthesis offers a versatile approach to prepare novel carbon-based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine-tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non-benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on-surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond-resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc-AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV.     

Dynamic Assemblies and Photophysical Changes of Zinc Porphyrin Dimer Regulated by N-Containing Ligands

Zinc porphyrin dimer （1） has been designed and synthesized as a novel host of N-containing ligands. The assembly behavior and photophysical changes of its host-guest complexes were evaluated by IH NMR, fluorescence, and UV-visible titrations, and the processes reveal that the host-guest assembly first creates a stable sandwich complex, then an axial coordination equilibrium appears between the sandwich complex and free ligand. The changes of absorption spectra of the assembly processes rely on the stabilities of the complexes, and fluorescence quenching depends on the axial coordination equilibrium, which indicates that the axial ligation/de-ligation dynamics is indeed a pathway from the excited state to the ground state for metalloporphyrin complexes.     

Optical and Electronic Properties of Different Kinds of Water‐Soluble Porphyrin Films

Water‐soluble porphyrin‐porphyrin and porphyrin‐CdSe nanoparticle monolayer films were self‐assembled on different substrates. The influence of substrates, types of films, and heat treatment temperature on fluorescence of different kinds of porphyrin films was investigated. The SEM images showed the formation of monolayer films on porous alumina foil. The films assembled on porous alumina foil possessed higher fluorescence intensity and thermal stability. The result of conductance measurement indicated that the interaction of trimethylamidophenylporphyrin iodide (TAPPI) molecules with hydroxyl groups on porous alumina foil was weakened after CdSe nanoparticles assembled with TAPPI.     

Synthesis and Langmuir-Blodgett Film Analysis of Atropisomers of “Picket Fence” Porphyrin

Four "picket fence" porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra(o-aminophenyl)porphyrin that had been chromatographed on a column eluted with petro-leum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 °C. They were characterized by 1 H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett(LB) film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1 H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.     

Electrochemical Behavior of meso-Tetra (4-Sulfonatophenyl) Porphyrin and Its Copper Complex

The complex of Cu-TPPS was formed directly by mixing equal-molar concentrations of Cu~(2+) and meso-tetra(4-sulfonatophenyl) porphyrin(TPPS)in an acetate buffer solution at pH 4-6, and its electrochemical behavior was studied by the techniques of polarography, cyclic voltammetry and spectroelectrochemistry. Three different methods were applied to accelerating the formation of Cu-TPPS in aqueous solution, i.e. heating of solution,using vitamin C as a catalyst and preadsorbing TPPS on a hanging mercury electrode. The voltammetric reductions have shown 2e~- for the first step of TPPS and 4e~- for Cu-TPPS with a peak potential at -1.04V. By applying the method of spectroelectrochemistry using a selfdesigned long-optical-path cell with Hg working electrode, the amount of saturated adsorption of TPPS and Cu-TPPS on mercury surface is found to be the same. Hence, the area of the adsorbed molecule calculated by measuring the area (i×t) under the voltammetric peak is also the same as 395 (?)~2.     

Synthesis and Spectroscopic Properties of a Covalently Linked Porphyrin–Fullerene C60 Dyad

A covalently linked porphyrin–fullerene C₆₀ dyad 6 was conveniently synthesized by 1,3‐dipolar cycloaddition using 5‐(4‐carbonylphenyl)‐10,15,20‐tris(4‐methoxylphenyl)porphyrin 5, N‐methylglycine and fullerene C₆₀. Spectroscopic studies show that dyad 6 is a promising architecture with potential application as photoactive organic material.     

5,10,15,20-Tetrakis （p-4-fluorobenzoyloxy） phenyl Porphyrin and Its Transition Metal Complexes

The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10,15,20-tetrakis(p-4-fluorobenzoyloxy) phenyl porphyrin(TFBOPPH2) and its transition metal complexes {TFBOPPM [M=Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ)]} were synthesized and characterized by means of UV-Vis, IR photoacoustic spectrometry, 1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrin molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balanceable anion in Fe(Ⅲ) and Mn(Ⅲ) complexes.     

Dicyano and pyridine derivatives of β-carotene: synthesis and vibronic, electronic, and photophysical properties

Density functional theory and time-dependent density functional theory calculations provide pictures of the molecular orbitals involved in the ground and excited states of two cyano derivatives of 8'-apo-β-caroten-8'-al synthesized via an acid-base-catalyzed Knoevenagel condensation reaction. Population analysis shows that the symmetry-allowed transition, S(0) ((1)A(g)) → S(2) ((1)B(u)) based on the C(2h) symmetry is a HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) π → π* transition with electron densities located mostly on the polyene chain. Calculated and actual steady-state absorption spectra show similar features with low-energy peak maxima between 550 and 600 nm.     

Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis,structure, magnetic properties,and Mössbauer spectra

Russian Chemical Bulletin - Crystalline compounds (H3O)2(phz)3M2(C6O4Cl2)3·(CH3COCH3) n ·(H2O) n (n = 0?2, M = Mn (1), Fe (3)) were obtained in an acetone-water-tetrahydrofuran...     

Complexes H2CO:PXH2 and HCO2H : PXH2 for X=NC,F, Cl,CN, OH,CCH, CH3, and H: Pnicogen Bonds and Hydrogen Bonds

Ab initio MP2/aug’-cc-pVTZ calculations have been carried out to investigate H₂CO : PXH₂ pnicogen-bonded complexes and HCO₂H : PXH₂ complexes that are stabilized by pnicogen bonds and hydrogen bonds, with X=NC, F, Cl, CN, OH, CCH, CH₃, and H. The binding energies of these complexes exhibit a second-order dependence on the O−P distance. DFT-SAPT binding energies correlate linearly with MP2 binding energies. The HCO₂H : PXH₂ complexes are stabilized by both a pnicogen bond and a hydrogen bond, resulting in greater binding energies for the HCO₂H : PXH₂ complexes compared to H₂CO : PXH₂. Neither the O−P distance across the pnicogen bond nor the O−P distance across the hydrogen bond correlates with the binding energies of these complexes. The nonlinearity of the hydrogen bonds suggests that they are relatively weak bonds, except for complexes in which the substituent X is either CH₃ or H. The pnicogen bond is the more important stabilizing interaction in the HCO₂H : PXH₂ complexes except when the substituent X is a more electropositive group. EOM-CCSD spin-spin coupling constants ^1pJ(O−P) across pnicogen bonds in H₂CO:PXH₂ and HCO₂H : PXH₂ complexes increase as the O−P distance decreases, and exhibit a second order dependence on that distance. There is no correlation between ^2hJ(O−P) and the O−P distance across the hydrogen bond in the HCO₂H : PXH₂ complexes. ^2hJ(O−P) coupling constants for complexes with X=CH₃ and H have much greater absolute values than anticipated from their O−P distances.     

Metal-Backboned Polymer:Conception,Design and Synthesis

The backbones of polymers are generally composed of non-metal elements such as C, N, O and Si. Here we propose and synthesize a new class of polymers whose backbones are completely made from metal atoms connected by chemical bonds, and they are thus named metalbackboned polymers. As a demonstration, nickel is selected as the metal to construct the nickel-backboned polymers with varied lengths, which are verified by mass spectrometry and studied by ultraviolet-visible spectroscopy. These metal-bo...