Excitation energy migration processes in various multi-porphyrin assemblies

The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (Z(N)) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (T(N)) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZ(N)) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps(-1), respectively. With increasing the size of C(N)ZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps(-1), respectively. The EET rates of porphyrin boxes consisting of alkynylene-bridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.     

( Ti| Me) ( C,N) / Ni 的润湿性及其价电子结构

运用座滴法研究了( Ti , Me) (C , N) / Ni 体系的润湿性;运用经验电子理论( EET 理论) 计算了多元陶瓷相的价电子结构(VES) , 建立了陶瓷相化学成分与价电子结构的关系, 并建立了价电子结构与接触角的回归关系式。结果表明, 提高温度、延长保温时间均使体系接触角减小; 碳化物的添加使体系接触角进一步减小,碳化物改善润湿性能力的大小依次为: Mo₂C > TaC > WC > VC > NbC。不同碳化物的添加均能导致最强键上共价电子数n_A 增加, 其中添加VC 的影响最为明显, 依次为VC > Mo₂C > NbC > WC > TaC。      

Guest-Stimulated Nonplanar Porphyrins in Flexible Metal−Organic Frameworks

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal−organic frameworks (MOFs) is reported that exhibit guest-stimulated breathing behavior. X-Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co-porphyrin exhibits active properties in catalyzing CO₂/propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.     

Modelling photosystem I as a complex interacting network

In this paper, we model the excitation energy transfer (EET) of photosystem I (PSI) of the common pea plant Pisum sativum as a complex interacting network. The magnitude of the link energy transfer between nodes/chromophores is computed by Forster resonant energy transfer (FRET) using the pairwise physical distances between chromophores from the PDB 5L8R (Protein Data Bank). We measure the global PSI network EET efficiency adopting well-known network theory indicators: the network efficiency (Eff) and the largest connected component (LCC). We also account the number of connected nodes/chromophores to P700 (CN), a new ad hoc measure we introduce here to indicate how many nodes in the network can actually transfer energy to the P700 reaction centre. We find that when progressively removing the weak links of lower EET, the Eff decreases, while the EET paths integrity (LCC and CN) is still preserved. This finding would show that the PSI is a resilient system owning a large window of functioning feasibility and it is completely impaired only when removing most of the network links. From the study of different types of chromophore, we propose different primary functions within the PSI system: chlorophyll a (CLA) molecules are the central nodes in the EET process, while other chromophore types have different primary functions. Furthermore, we perform nodes removal simulations to understand how the nodes/chromophores malfunctioning may affect PSI functioning. We discover that the removal of the CLA triggers the fastest decrease in the Eff, confirming that CAL is the main contributors to the high EET efficiency. Our outcomes open new perspectives of research, such comparing the PSI energy transfer efficiency of different natural and agricultural plant species and investigating the light-harvesting mechanisms of artificial photosynthesis both in plant agriculture and in the field of solar energy applications.     

Porphyrin colorimetric indicators in molecular and nano-architectures

One of the most important outcomes of organic nanotechnologies could be development of well-integrated systems for sensing of particular chemical species. Use of color indicators is an attractive approach to guest reporting. Of the known chromophores, porphyrin and its derivatives are the most widely studied functional chromophores in a diverse range of research fields. In this review, recent developments in colorimetric indicator functions of porphyrin derivatives and related compounds in their molecular and nano-architectures are reviewed according to the classification: (i) rather simple porphyrin derivatives, (ii) porphyrin conjugates, (iii) porphyrins embedded in bulk materials, and (iv) porphyrins in organized films. Porphyrin derivatives with unusual structures, such as expanded and N-confused ones have been used for color indicators in specific cases. Electron and energy transfers in porphyrins conjugated with other functional moieties resulted in dynamic sensing systems including switch-on and switch-off actions. Immobilization of porphyrin color indicators in appropriate matrices is important for practical applications. Use of supramolecular films such as self-assembled monolayers, Langmuir-Blodgett films, and layer-by-layer assemblies as porphyrin nanoarchitectures often offers opportunities for colorimetric outputs based on control of their aggregate structures.     

A model of valence electron structure for embrittlement of TiAl

In this paper, the valence electron structure and embrittlement of TiAl are studied theoretically based on the empirical electron theory (EET). From the viewpoint of the EET, a model for the space topographic distribution of valence electron structure is proposed. This model can be used to simply explain the embrittlement of TiAl and could be extended to other intermetallic compounds.     

Ultrafast Photocatalytic Detoxification of Mustard Gas Simulants by a Mesoporous Metal–Organic Framework with Dangling Porphyrin Molecules

Developing effective catalysts to degrade chemical warfare agents is of great significance. Herein, a mesoporous MIL-101(Cr) composite material dangled with porphyrin molecules (denote as TCPP@MIL-101(Cr), TCPP = tetra(4-carboxyphenyl)porphyrin) is reported, which can be used as a heterogeneous photocatalyst for detoxification of mustard gas simulants 2-chloroethyl ethyl sulfide (CEES) to 2-chloroethyl ethyl sulfoxide (CEESO) with a half-life of 1 min. The catalytic performance of TCPP@MIL-101(Cr) is comparable to that of homogeneous molecular porphyrin. Mechanistic studies reveal that both ¹O₂ and O₂^•− are efficiently generated and play vital roles in the oxidation reaction. Gold nanoparticles (AuNPs) are attached to the TCPP@MIL-101(Cr) to further enhance the catalytic activity with a benchmark half-life of 45 s, which is the fastest record so far. A medical mask loaded TCPP@MIL-101(Cr) is fabricated for practical applications, which can selectively photoxidize CEES to CEESO under sunlight and air atmosphere, exhibiting the best degradation performance among the reported fabric-like composite materials.     

Fluorescent sensor for imidazole derivatives based on monomer-dimer equilibrium of a zinc porphyrin complex in a polymeric film

A new zinc(II) porphyrin conjugate with an appended pyrene subunit has been synthesized and shown to exhibit significant and analytical usefulness for fluorescence sensing toward imidazole derivatives. The molecular recognition was based on the bridging interaction of the imidazole ring of analyte with the zinc(II) center of the porphyrin, while the transduction signal for the recognition process was the pyrene excimer fluorescence. The sensor was constructed and applied for fluorescence assay of histidine in aqueous solution by immobilizing the sensing material in a plasticized PVC membrane. When the membrane was bathed in an alkaline solution void of histidine, zinc(II) porphyrin was present in the monomer form, and pyrene emitted monomer fluorescence at 378 and 397 nm. With the presence of histidine in the sample solution, histidine was extracted into the membrane phase and bridged with the Zn(II) center of the porphyrin, causing the monomer porphyrin to be converted to its dimeric species. Since the formation of porphyrin dimer was accompanied by the enhancement of pyrene excimer emission at 454 nm, the chemical recognition process could be directly translated into a fluorescent signal. With the optode membrane M1 described, histidine in sample solution from 6.76 x 10(-7) to 5.01 x 10(-3) M can be determined. The limit of detection was 1.34 x 10(-7) M. The optical selectivity coefficient obtained for histidine over biologically relevant amino acids and anions met the selectivity requirements for the determination of histidine in biological samples. Serum histidine values obtained by the optode membrane fell in the normal range of the content reported in the literature and were in good agreement with those obtained by HPLC.     

Porphyrin Monolayer‐Modified Gold Clusters as Photoactive Materials

Porphyrin monolayer‐modified gold clusters (three‐dimensional system) have been prepared successfully. Their electrochemical and photophysical properties have been compared to those of the corresponding two‐dimensional system of self‐assembled monolayers (SAMs) of the porphyrin as well as the bis(porphyrin) disulfide reference in solutions. In particular, the time‐resolved single‐photon counting fluorescence studies have indicated that the undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three‐dimensional system is much suppressed, as compared to the quenching of the porphyrin SAMs on the two‐dimensional flat gold surface. Thus, the present systems have a variety of potential utility for development of the artificial photosynthetic materials, photocatalysts, and chemical and biochemical sensors using fluorescent chromophore‐monolayer modified gold clusters.     

Carbon nanotube films as a platform to transduce molecular recognition events in metalloporphyrins

Porphyrins have been widely used for many years as functional materials for chemical sensors. Their outstanding chemical features are balanced by some restrictions in terms of transduction techniques. In particular, porphyrin layers are barely conductive, with the consequence that the fabrication of porphyrin based chemiresistors is not possible, except in few rare cases. On the other hand, carbon nanotubes (CNTs) have superior electric properties ranging from metallic to semiconductor in character. Although the conductivity of CNTs is very sensitive to adsorbed molecules, it should be considered that the adsorption onto carbon structures is also scarcely selective and cannot be modified unless other molecular recognition systems are coupled with the CNTs. Following this approach, in this paper we investigated the sensing properties of hybrid CNT-porphyrin films to explore the possibility of transducing the adsorption events occurring in a porphyrin layer into resistance changes of the CNT layers. The results obtained indicate that the presence of the porphyrin films increases the sensitivity of the electric resistance of the CNTs to the concentration of volatile compounds. This enhancement is probably due to the catalytic effect of the metalloporphyrin in conveying the charge transfer from the adsorbate molecule to the CNTs substrate. This property of metalloporphyrins may introduce a further differentiation between porphyrin based sensors that could be positively utilized in sensor array configurations.     

Formation of Extended Covalently Bonded Ni Porphyrin Networks on the Au（lll） Surface

The growth and ordering of {5,10,15,20-tetrakis(4-bromophenyl)porphyrinato}nickel(II) (NiTBrPP) molecules on the Au(111) surface have been investigated using scanning tunnelling microscopy, X-ray absorption, core-level photoemission, and microbeam low-energy electron diffraction. When deposited onto the substrate at room temperature, the NiTBrPP forms a well-ordered close-packed molecular layer in which the molecules have a flat orientation with the porphyrin macrocycle plane lying parallel to the substrate. Annealing of the NiTBrPP layer on the Au(111) surface at 525 K leads to dissociation of bromine from the porphyrin followed by the formation of covalent bonds between the phenyl substituents of the porphyrin. This results in the formation of continuous covalently bonded porphyrin networks, which are stable up to 800 K and can be recovered after exposure to ambient conditions. By controlling the experimental conditions, a robust, extended porphyrin network can be prepared on the Au(111) surface that has many potential applications such as protective coatings, in sensing or as a host structure for molecules and clusters.     

Capillary electrophoresis of cytochrome P-450 epoxygenase metabolites of arachidonic acid. 1. Resolution of regioisomers

The essential fatty acid arachidonate is oxidized by cytochrome P-450 epoxygenases to four epoxyeicosatrienoic acids (EETs): 14,15-, 11,12-, 8,9-, and 5,6-EETs. Each of the four EET regioisomers and their hydrolysis products (DHETs) has multiple paracrine and autocrine functions and may also potently dilate blood vessels and activate potassium channels. The present work describes a method to resolve EETs and DHETs by capillary electrophoresis (CE) using trimethyl-beta-cyclodextrin and CH3CN as buffer additives. While stored at 25 degrees C, most of the EET and DHET regioisomers remained intact when suspended in alkaline vehicle. However, under these same conditions, 5,6-EET rapidly broke down to a lactone and was slowly converted to 5,6-DHET. When subjected to CE, the EET and DHET regioisomers were baseline resolved (R > or = 1.3); 10 pg of an EET or a DHET regioisomer was readily detectable at 194 nm. In addition, the UV spectra were regiospecific and identical to those obtained during HPLC except that an additional, weak absorption occurred at 235 nm. Together, the high-sensitivity, high-resolution, and differential UV spectra permitted the identification and quantification of EETs in phospholipids isolated from murine liver. Thus, CE was successfully used for the trace analysis of eicosanoids.     

Real-time single-molecule imaging of oxidation catalysis at a liquid-solid interface

Many chemical reactions are catalysed by metal complexes, and insight into their mechanisms is essential for the design of future catalysts. A variety of conventional spectroscopic techniques are available for the study of reaction mechanisms at the ensemble level, and, only recently, fluorescence microscopy techniques have been applied to monitor single chemical reactions carried out on crystal faces and by enzymes. With scanning tunnelling microscopy (STM) it has become possible to obtain, during chemical reactions, spatial information at the atomic level. The majority of these STM studies have been carried out under ultrahigh vacuum, far removed from conditions encountered in laboratory processes. Here we report the single-molecule imaging of oxidation catalysis by monitoring, with STM, individual manganese porphyrin catalysts, in real time, at a liquid-solid interface. It is found that the oxygen atoms from an O2 molecule are bound to adjacent porphyrin catalysts on the surface before their incorporation into an alkene substrate.     

经验电子理论在纳米晶软磁材料中的应用及展望

概述了固体与分子经验电子理论（简称EET理论）在一般材料和纳米晶软磁材料中的应用现状,提出了EET理论在纳米晶软磁材料应用中尚存在的问题,并给出了一些解决方案,最后展望了EET理论在纳米晶软磁材料中的应用前景。     

An optical fiber chemical sensor for mercury ions based on a porphyrin dimer

The synthesis of a novel fluoroionophore, 5-p-[[4-(10',15',20'-triphenyl-5'-porphinato) phenyloxyl]-1-butyloxyl]phenyl-10,15,20-triphenylporphine (DTPP), and its application for preparation of a Hg(II)-sensitive optical fiber chemical sensor are described. The response of the sensor is based on the fluorescence quenching of DTPP by coordination with Hg(II). The porphyrin dimer-based sensor shows a linear response toward Hg(II) in the concentration range 5.2 x 10(-7)-3.1 x 10(-4) mol x L(-1), with a working pH range from 2.4 to 8.0. The sensor shows excellent selectivity for Hg(II) over transition metal cations including Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II), and Fe(III). As a sensing agent, the porphyrin dimer shows obviously better fluorescence response characteristics toward Hg(II) compared to porphyrin monomer or metalloporphyrin. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for determination of Hg(II) in water samples.     

A significant promotion of the iron tetra(p-methoxylphenyl) porphyrin catalysis for the aerobic oxidation of cyclohexane using boehmite

An important issue for the application of metalloporphyrins in the chemical industry is the preparation of a reusable and active supported catalyst. In this work, a new nanocatalyst material consisting of boehmite and a second-generation iron tetraphenylporphyrin with electron-donating groups (methoxyl) has been prepared and characterised using UV-Vis and FT-IR spectroscopy, X-ray powder diffraction, scanning electron microscopy and thermal analysis. The reusability of the boehmite-supported iron tetra (p-methoxylphenyl) porphyrin catalyst for the aerobic oxidation of cyclohexane was investigated. The supported catalyst material containing only 1?mg of iron tetra (p-methoxylphenyl) porphyrin per 1?g of boehmite could be recovered easily and reused effectively for at least 10 times for the oxidation of cyclohexane. The oxidative results gave, on average, 5.1% cyclohexane conversion, 91.2% selectivity (ketone?+?alcohol) and a catalyst turnover number of 7.91?×?10⁴ over several cycles using moderate reaction conditions. The special character of the catalyst material is related to the structure of the combined boehmite and iron porphyrin.     

Nicotine, cotinine, and myosmine determination using polymer films of tailor-designed zinc porphyrins as recognition units for piezoelectric microgravimetry chemosensors

Two electropolymerizable zinc porphyrins with receptor sites tailor-designed for selective recognition of the nicotine, cotinine, or myosmine alkaloids were synthesized. These were 5-(2-phenoxyacetamide)-10,15,20-tris(triphenylamino)porphyrinato zinc(II) 1 and 5-(2,5-phenylene-bis(oxy)diacetamide)-10,15,20-tris(triphenylamino)porphyrinato zinc(II) 2 featuring one and two pendant amide side "pincers", respectively, and three triphenylamine substituents at the meso positions of the porphyrin macrocycles capable of electrochemical polymerization. Thin polymerfilms of these porphyrins served for recognition and the piezoelectric microgravimetry (PM) for analytical signal transduction of a new chemical sensor devised for determination of these alkaloids. The films were deposited by potentiodynamic electropolymerization on the 10 MHz quartz resonators of the electrochemical quartz crystal microbalance (EQCM) without affecting the electronic structure of the porphyrin macrocycles. Under favorable flow injection analysis (FIA) conditions, the alkaloid analytes were determined at the concentration level of 0.1 mM with high sensitivity and selectivity. Affinity toward the analytes of the polymer of 2 was higher than that of 1 due to the higher binding ability offered by two pendant pincers of the former. Because of the selective receptors and PM applied under FIA conditions, the developed procedure offered an alternative to the time-consuming and relatively expensive high-performance liquid chromatography (HPLC), capillary electrophoresis (CE), and gas chromatography mass spectrometry (GC-MS) methods of detection and quantification of these alkaloids.     

Porphyrin assembly on beta-cyclodextrin for selective sensing and detection of a zinc ion based on the dual emission fluorescence ratio

In the present paper, a new cyclodextrin/porphyrin supramolecular sensitizer for zinc ion has been proposed based on the porphyrin dual fluorescence emission ratio. In aqueous solution, meso-tetraphenylporphyrin shows weak fluorescence, while in the presence of alkylated beta-cyclodextrin, it exhibits significant fluorescence enhancement by forming a cyclodextrin/porphyrin inclusion complex. Furthermore, the formation of a supramolecular complex causes a remarkable increase of the porphyrin metalation rate following the porphyrin fluorescence emission changes at two different emission wavelengths. The fluorescence emission of tetraphenylporphyrin at 656-nm bands decreases while that at 606 nm increases upon zinc ion interaction. Thus, the inclusion complex can behave as a ratiometric fluorescent sensor. Theoretically derivative equations for fluorescent ratiometry have been proposed for the first time. The feasibility of the proposed method is demonstrated by the performance of fluorometric detection of zinc ion. With the optimum conditions described, zinc ion in aqueous solution can be determined from 5.0 x 10(-7) to 2.5 x 10(-4) M. As the porphyrin electronic absorption and fluorescence emission are located in the visible range, and the fluorescence changes upon zinc ion interaction show high selectivity over biologically relevant cations, the inclusion complex could be used for biomedical application.     

On-line LC-MS analysis of urinary porphyrins

A reversed-phase high-performance liquid chromatography-mass spectrometry (LC-MS) method is described for the separation and simultaneous analysis of porphyrins related to disorders of heme biosynthesis (uro-, heptacarboxylic, hexacarboxylic, pentacarboxylic, and coproporphyrins). The method involves initial porphyrin esterification and extraction from urine. Detection and quantification is performed from the extracts by separation with a Hypersil BDS column and on-line detection by MS through coupling with an atmospheric pressure chemical ionization interface. The porphyrin esters are detected as protonated molecules [M + H]+. Their mass spectra also exhibit an [M + Na]+ fragment of lower intensity. The analytical performance of this method is compared with those of LC with UV and fluorescence detection. LC-MS used in selective [M + H]+ ion monitoring provides the lowest detection and quantitation limits. In scan mode, this LC-MS method affords, without further isolation or concentration steps, the measurement of mass spectra of unknown compounds present in the urine of patients with altered porphyrin excretion.     

Self-assembly into temperature dependent micro-/nano-aggregates of 5,10,15,20-tetrakis(4-carboxyl phenyl)-porphyrin

Various nanostructures of 5,10,15,20-tetrakis(4-carboxyl phenyl)-porphyrin (H₂TCPP) can be easily synthesized by a surfactant-assisted self-assembly (SAS) method at different temperatures. When the DMF solution of porphyrin monomer was injected into cetyltimethylammonium bromide (CTAB) aqueous solution by a syringe, diverse H₂TCPP nanostructures dependent on the different temperatures, including hollow nanospheres, solid nanospheres and nanospheres with holes, were successfully obtained. As a result, the suitable concentration of the CTAB aqueous solution used to form nanostructues of porphyrin ranges from 0.15 to 0.2 mM. The various morphologies of porphyrin nanostructures were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). UV–vis adsorption spectra showed that the micro-/nano-aggregate properties of porphyrin transformed from H-aggretates to J-aggregates during the process of self-assembly of porphyrin at different temperatures. Fluorescence spectra revealed a greater fluorescence quenching of various micro-/nano-aggregatess of porphyrin formed at different temperatures in aqueous solution, compared to the DMF solution of porphyrin monomer.