Stepwise Transfer Research Articles

Description of electron transfer in the ground and excited states of organic donor-acceptor systems by single-reference and multi-reference density functional methods.

Electron transfer in the ground and excited states of a model donor-acceptor (D-A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S0 state and a wave-like dependence of the S1 electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S0 and S1 electron transfer on the external electric field applied along the donor-acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S0 and S1 electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor-acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S0 and S1 states may interfere with the electron transfer in a weakly coupled donor-acceptor system. It is also suggested that the electronic excitation of a D(+)-A(-) system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths.

TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4′-dimethylaminoflavonol in ethanol solvent

Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4′-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF–EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3–C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

Partial hydrogenation of a tetranuclear titanium nitrido complex with ammonia borane.

The treatment of [{Ti(η(5)-C5Me5)}4(μ3-N)4] with NH3BH3 leads to the paramagnetic imidonitrido complex [{Ti(η(5)-C5Me5)}4(μ3-N)3(μ3-NH)], which can also be obtained by stepwise proton and electron transfer with HOTf and [K(C5Me5)].

Importance of Specific Interactions between Support, Metal Oxide Nanostructures and Noble Metal or Organometallic Sites in Efficient Electrocatalytic and Bioelectrocatalytic Reduction of Oxygen

Systems utilizing carbon nanostructures (e.g. nanotubes) and noble metal nanoparticles can form advanced electrocatalytic materials with well-defined composition, structure and thickness. We explore here the ability of inorganic structures to stabilize and derivatize metal (Au, Pt, Pd) and carbon nanostructures. Among inorganic systems, polyoxometallates of tungsten are attractive since they can not only adsorb irreversibly on solid surfaces but also exhibit reversible stepwise multi-electron transfer reactions. The concept of the layer-by-layer formation of hybrid inorganic assemblies composed of anionic polyoxometallate-protected carbon nanotubes (or metal nanoparticles) and ultra-thin nanostructures of positively charged metal oxide (vanadia, titania, zirconia) nanostructures (alone or in combination with tungsten oxide) will be described and discussed here. The resulting novel composite materials are characterized by fast dynamics of charge propagation. When it comes to the electrocatalytic reduction of oxygen, polyoxometallates can also be applied to stabilize and link Pt, Pd and various alloyed Pt-based catalytic nanoparticles.To produce bioelectrocatalytic materials for oxygen reduction, we explore unique properties of biofilms, i.e. polymeric aggregates of microorganisms, in which cells adhere to each other on the electrode surfaces. Such systems are characterized by extracellular electron transfers involving c-type cytochromes (heme-containing proteins). Biofilms grown on inert carbon electrode substrates tend to exhibit electrocatalytic properties towards oxygen and hydrogen peroxide reductions in neutral media. The processes have been found to be further enhanced by introduction of multi-walled carbon nanotubes (MCNTs) that are modified with ultra-thin layers of organic (e.g. 4-(pyrrole-l-yl) benzoic acid. We expect here attractive electrostatic interactions between carboxyl-group containing anionic adsorbates and positively charged domains of the biofilm with c-type cytochrome enzymatic sites. Coexistence of the above components leads to synergistic effect that is evident from positive shift of the oxygen reduction voltammetric potentials and significant increase of voltammetric currents. Most likely, the reduction of oxygen has been initiated at the molecular (e.g. intentionally added metalloporphyrin redox centers), whereas the undesirable hydrogen peroxide intermediate are further decomposed at the cytochrome sites. Acknowledgement We appreciate collaboration with Krzysztof Miecznikowski, Adam Lewera, Beata Dembinska, Jakub Sek, and Anna Dobrzeniecka from Faculty of Chemistry, University of Warsaw.

Theoretical Mechanistic Studies on Methyltrioxorhenium-Catalyzed Olefin Cyclopropanation: Stepwise Transfer of a Terminal Methylene Group

Methyltrioxorhenium (MTO)-catalyzed transfer of a methylene group to styrene has been computationally found to preferably follow a stepwise mechanism to give phenylcyclopropane via formation of a pseudo-metallacyclic intermediate and subsequent alkylative cyclization. The present result serves as the first theoretical evidence for d0 transition metal mediated transfer of methylene as a terminal form rather than a metal carbene or carbenoid fashion, accompanied by the cleavage of a H2C═O double bond. The mechanism presented here is in contrast to the carbenoid or metal carbene promoted methylene transfer and to the MTO-catalyzed isoelectronic atom (group) transfer in MeRe(O)2(η2-O–NH) or MeRe(O)2(η2-O–O). This study not only enriches the chemistry of olefin cyclopropanation and the MTO-catalyzed group (atom) transfer event but also sheds new light on the reaction chemistry of formaldehyde.

Competing benzyl cation transfers in the gas-phase fragmentation of the protonated benzyl phenylalaninates

In this study, the competing benzyl cation transfer reactions have been explored by investigating the gas phase chemistry of the protonated benzyl phenylalaninates. Protonation at the carboxylic O atom results in the breakage of the ester CO bond to afford the benzyl cation, which undergoes the competing migration to the amino N atom or the phenyl ring C atom. Both the amino and the phenyl ring hydrogen atoms can be activated to be mobile due to the electrophilic attack of the transferring benzyl cation, and migration of the activated hydrogen atom to the carboxylic hydroxyl leads to (H2O+CO) elimination of the precursor ion. Interestingly, it is much more preferred for the benzyl cation to transfer to the phenyl ring via the amino N, leading to the stepwise benzyl cation transfer, albeit the amino N atom contains more nucleophilic affinity. The mechanistic processes have been confirmed by the MS3 spectra data, along with D-labeling experiments and theoretical calculations.

Stepwise and concerted dissociative electron transfer onto a σ*-type orbital in polybrominated aromatics

Convolution analysis of voltammetric data along with DFT calculations shows that the studied pentabromophenyl ethers undergo concerted dissociative electron transfer onto a σ*CBr-type orbital. Hexabromobenzene and chloropentabromobenzene form σ* radical anions upon reduction.

Redox-Active Silica Nanoparticles. 9.1 Synthesis, Electrochemistry, and Diffusion Properties of Caged Octakis(N-ferrocenoyl-3- aminopropyl)silsesquioxane

The caged, cube-shaped silsesquioxane T8Fc8 with eight attached ferrocenoyl units has been synthesized. Its structure is supported by NMR and IR spectroscopy as well as mass spectrometry. Electrochemical results show separate signals for adsorbed and freely diffusing molecules. Estimation of the diffusion coefficient and comparison of electrochemical and PGSE NMR data lead to the conclusion that the ferrocene units undergo stepwise one-electron transfers with closely spaced formal potentials, where possibly not all electroactive moieties are oxidized.

Near-Infrared to Visible Light-Upconversion in Molecules: From Dream to Reality

Light-upconversion via stepwise energy transfer from a sensitizer to an activator exploits linear optics for converting low-energy infrared or near-infrared incident photons to higher energy emission. This approach is restricted to activators possessing intermediate long-lived excited states such as those found for trivalent lanthanide cations dispersed in solid-state matrices. When the activator is embedded in a molecular complex, efficient nonradiative relaxation processes usually reduce excited state lifetimes to such an extent that upconversion becomes too inefficient to be detected under practical excitation intensities. Theoretical considerations presented here predict that the combination of at least two millisecond time scale sensitizers with a central lanthanide activator in supramolecular complexes circumvents this bottleneck by creating a novel upconversion pathway, in which successive excitations are stored on the sensitizers prior to inducing stepwise energy transfer processes. Application of...

CATALYTIC MECHANISM OF ALL-TRANS-RETINOIC ACID 4-HYDROXYLATION MEDIATED BY CYTOCHROME P450 2C8: HOW DOES ARGININE 241 AFFECT THEC–HBOND ACTIVATION?

Experiments revealed that cytochrome P450 2C8 enzyme (CYP2C8) has two distinct substrate binding sites to the physiologically important molecules, retinoic acids, and the main difference between these two binding sites is whether there is a salt bridge interaction between the anionic carboxylate tail of retinoic acids and the surrounding protein environment. However, the influence of such salt bridge interaction toward catalysis is still elusive. In the present paper, density functional theory (DFT) calculations were employed to research the reaction mechanism of all-trans-retinoic acid (atRA) 4-hydroxylation mediated by CYP2C8. Our DFT calculations revealed that such salt bridge interaction has obvious effects on the reaction mechanism of atRA 4-hydroxylation. In the binding site containing a salt bridge interaction between the anionic carboxylate tail of atRA and the cationic guanidine group of Arg241, C – H bond activation proceeds via a normal hydrogen atom transfer (HAT) mechanism; in the other site without this salt bridge interaction, however, C – H bond activation is achieved via a stepwise electron transfer and hydrogen atom transfer, thus, a novel ET/HAT mechanism. These findings enrich the mechanism patterns of C – H bond activation catalyzed by metalloenzymes and their biomimetics. Meanwhile, the self-interaction error (SIE) problem encountered during our calculations in vacuum was affected and removed by the inclusion of an external electric field in the calculations.

Centenary of the Franck‐Hertz experiments

In 1925 the Nobel Prize in Physicswas awarded jointly to James Franck(1882–1964) and Gustav L. Hertz(1887–1975) “for their discovery ofthe laws governing the impact of anelectron upon an atom” [1]. Theyconducted an ingenious set of exper-iments in 1913 and 1914 in whichthey measured the ionization po-tential of different gases [2]; stud-ied collisions between gas moleculesand slow electrons [3]; developed atheory of ionization by collision [4];determined the ionization potentialof mercury vapor with the methodof electron collision [5]; and car-ried out spectroscopic experimentswith mercury vapor which yieldedthe spectral line 253.6

Organic Electron Donors as Powerful Single‐Electron Reducing Agents in Organic Synthesis

One-electron reduction is commonly used in organic chemistry for the formation of radicals by the stepwise transfer of one or two electrons from a donor to an organic substrate. Besides metallic reagents, single-electron reducers based on neutral organic molecules have emerged as an attractive novel source of reducing electrons. The past 20 years have seen the blossoming of a particular class of organic reducing agents, the electron-rich olefins, and their application in organic synthesis. This Review gives an overview of the different types of organic donors and their specific characteristics in organic transformations.

A Kinetic Model of Proton Transport in a Multi-Redox Centre Protein: Cytochrome c Oxidase

We use chemical reaction kinetics to explore the stepwise electron and proton transfer reactions of cytochrome c oxidase (C cO) from R. sphaeroides. Proton transport coupled to electron transport (ET) is investigated in terms of a sequence of protonation-dependent second-order redox reactions. Thereby, we assume fixed rather than shifting dissociation constants of the redox sites. Proton transport can thus be simulated particularly when separate proton uptake and release sites are assumed rather than the same proton pump site for every ET step. In order to test these assumptions, we make use of a model system introduced earlier, which allows us to study direct ET of redox enzymes by electrochemistry. A four-electron transfer model of C cO had been developed before, according to which electrons are transferred from the electrode to CuA. Thereafter, electrons are transferred along the sequence heme a, heme a3 and CuB. In the present investigation, we consider protonation equilibria of the oxidised and reduced species for each of the four centres. Moreover, we add oxygen/H2O as the terminal (fifth) redox couple including protonation of reduced oxygen to water. Finally we arrive at a kinetic model comprising five protonation-dependent redox couples. The results from the simulations are compared with experimental data obtained in the absence and presence of oxygen. As a result, we can show that proton transport can be modelled in terms of protonation-dependent redox kinetics.

Stepwise versus pseudo-concerted two-electron-transfer in a triarylamine–iridium dipyrrin–naphthalene diimide triad

A triad based on triarylamine donors, an iridium dipyrrin sensitiser and a naphthalene diimide acceptor is investigated using fs-pump-probe spectroscopy at two different pump wavelengths. Excitation of the naphthalene diimide induces a stepwise electron transfer process that yields within ca. 100 ps a charge separated state with 50-60% quantum yield in which one triarylamine is oxidised and the imide is reduced. Although being in the Marcus normal region, this state has a lifetime of 580 ns in MeCN. Excitation at the dipyrrin ligand centred absorption directly produces the charge separated state within ca. 1 ns however without formation of an intermediate. This pseudo-concerted two-electron transfer step was analysed with the help of a model dyad and a modified triad and is interpreted to be caused by inverted electron transfer rates. Although being much slower the latter process has a quantum yield of practically 100%.

Double-Proton-Transfer Reaction in Guanine-Cytosine Base Pair Embedded in B-Form DNA

The double-proton-transfer reaction of the isolated guanine-cytosine (GC) base pair and four DNA trimers with different nucleobase sequences (dATGCAT, dGCGCGC, dTAGCTA, and dCGGCCG) are studied by quantum mechanical calculations using ONIOM(M06-2X/6-31G*:PM3). Proton-transfer patterns, energy and structural properties are analyzed to gain insight into the double-proton-transfer mechanism with consideration to environmental factors. In the gas phase, a stepwise mechanism is found for the dCGGCCG trimer, and a concerted mechanism is found in the other four models. The computational results demonstrate that electrostatic interaction of the peripheral and middle base pairs have a pronounced effect on double-proton-transfer pattern of GC base pairs. The structures with dATGCAT and dGCGCGC sequences facilitate H4a proton transfer and those with dTAGCTA and dCGGCCG sequence facilitate H1 proton transfer. The high proton affinity of cytosine at N3 facilitates H1 proton transfer. In aqueous solution, electrostatic interactions are reduced and the products of single-proton-transfer in the stepwise mechanism are stabilized. This results in a stepwise transfer pattern becoming favorable. Solvent effects favor the single-proton-transfer reaction more than gas phase conditions, but increase the reaction energy of double-proton-transfer. 1233 Acta Phys. ⁃Chim. Sin. 2013 Vol.29

Computer modeling on the tautomerization of sulbactam intermediate in SHV-1 β-lactamases: E166A mutant vs. wild type

We present a theoretical study for the tautomerization of sulbactam intermediates in different SHV-1 β-lactamases: E166A and wild-type (WT). Molecular dynamics (MD) simulations were employed and hydrogen bonds network around active site was found different between the WT and E166A acyl-enzymes. In E166A, Asn170 restricts the C5C6 bond rotation, thus stabilizes the dihedral angle N4C5C6C7 of imine to a trans conformation. The DFT calculations (B3LYP/6-31+G* and B3LYP/6-31++G**) were performed on tautomerization reactions. Two mechanisms including direct and stepwise proton transfer reactions were proposed based on the MD results. In E166A, the substrate carboxyl group acts as a relay station which assists the proton transfer with a very low energy barrier. However, in WT, such stepwise mechanism is difficult to proceed because of the large separation between C6 and substrate carboxyl group. Our results explain why E166A SHV-1 β-lactamases forms greater population of trans-enamine than WT.

Proton/Hydrogen Transfer Mechanisms in the Guanine-Cytosine Base Pair: Photostability and Tautomerism.

Proton/hydrogen-transfer processes have been broadly studied in the past 50 years to explain the photostability and the spontaneous tautomerism in the DNA base pairs. In the present study, the CASSCF/CASPT2 methodology is used to map the two-dimensional potential energy surfaces along the stretched NH reaction coordinates of the guanine-cytosine (GC) base pair. Concerted and stepwise pathways are explored initially in vacuo, and three mechanisms are studied: the stepwise double proton transfer, the stepwise double hydrogen transfer, and the concerted double proton transfer. The results are consistent with previous findings related to the photostability of the GC base pair, and a new contribution to tautomerism is provided. The C-based imino-oxo and imino-enol GC tautomers, which can be generated during the UV irradiation of the Watson-Crick base pair, have analogous radiationless energy-decay channels to those of the canonical base pair. In addition, the C-based imino-enol GC tautomer is thermally less stable. A study of the GC base pair is carried out subsequently taking into account the DNA surroundings in the biological environment. The most important stationary points are computed using the quantum mechanics/molecular mechanics (QM/MM) approach, suggesting a similar scenario for the proton/hydrogen-transfer phenomena in vacuo and in DNA. Finally, the static model is complemented by ab initio dynamic simulations, which show that vibrations at the hydrogen bonds can indeed originate hydrogen-transfer processes in the GC base pair. The relevance of the present findings for the rationalization of the preservation of the genetic code and mutagenesis is discussed.

Synthesis, self-assembly, and pH-responsive behavior of (photo-crosslinked) star amphiphilic triblock copolymer

Conventional polymeric micelles employed as drug carriers suffer from the drawback of disaggregation when diluted into body fluids, giving rise to premature release of drugs. In this work, cinnamate was chosen as a crosslinker to overcome this issue and regulate pH response. A series of photo-crosslinkable star amphiphilic triblock copolymers, star poly(ε-caprolactone)-b-poly(2-cinnamoyloxyethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (SPCL-b-PCEMA-b-PDMAEMA), were prepared by combination of stepwise reversible addition-fragment chain transfer (RAFT) polymerization and carbodiimide-mediated coupling reaction. These star amphiphilic copolymers could self-assemble into core–shell-corona micelles. Facile photo crosslinking of the micelles was carried out via UV irradiation. The crosslinked micelles showed an improved stability determined by critical micelle concentration (CMC). The degree of photo crosslinking was easily regulated by tuning UV irradiation time, and the hydrodynamic diameters (Dh) decreased with increasing degree of photo crosslinking. The pH responses of micelles were investigated by dynamic light scattering (DLS), indicating pH-induced swelling-shrinking behavior. For photo-crosslinked micelle, its capability of swelling-shrinking weakened with increasing crosslinking degree, suggesting that pH response was controlled by crosslinking density. This novel photo-crosslinked micelle system with adjustable pH response was expected to have potential as drug carriers for controlled release.

Rare-earth doped optical spectral conversion materials with their applications

Based on the research work carried out in our laboratory in recent years, we focus on three categories of rare-earth doped spectral conversion materials, i.e., red phosphor for white-LED lighting, near-infrared downconversion materials and upconversion nanosized biological fluorescent labeling materials. Our work on the red phosphor for white-LED has been mainly focused on Eu3+ doped materials, and the energy transfer from sensitizers to Eu3+ ions is investigated in order to enhance the efficiency under the excitation of near-ultraviolet light. For the purpose of enhancing the efficiency of silicon-based solar cells, we have carried out the studies on near-infrared downconversion materials based on stepwise and cooperative energy transfer mechanisms and have clarified the downconversion mechanisms in NaYF4:Ho3+, Yb3+ and YVO4:Yb3+ materials. Biological fluorescent labeling is another important application of luminescent materials, which has some stringent requirements on the materials, such as the nanoparticle size, water-solubility, non-toxicity and luminescent efficiency. In our recent work, core/shell NaYF4:Yb3+, Er3+(Tm3+)/NaYF4 UCNPs have been successfully synthesized and transferred to aqueous phase by coating a cross-linked PMAO polymer. The cross-linked core/shell nanoparticles are very stable for several days, and are successfully internalized into human prostate cancer cells, which substantiates the utility of these nanoparticles in biolabeling applications. To sum up, due to significant existing and potential applications in biological and chemical sensing, new energy resources, energy saving and environmental protection, rare-earth doped spectral conversion materials have been attracting extensive attention. The future of rare-earth doped optical spectral conversion materials would be bright.

ChemInform Abstract: The Chemical Problem of Energy Change: Multi‐Electron Processes

AbstractReview: 59 refs.