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The photochemistry of metal-organic compounds in solution is determined by both intra- and inter-molecular relaxation processes after photoexcitation. Understanding its prime mechanisms is crucial to optimise the reactive paths and control their outcome. Here we investigate the photoinduced dynamics of aqueous ferrioxalate ([Fe-III(C2O4)(3)](3-)) upon 263 nm excitation using ultrafast liquid phase photoelectron spectroscopy (PES). The initial step is found to be a ligand-to-metal electron transfer, occuring on a time scale faster than our time resolution (less than or similar to 30 fs). Furthermore, we observe that about 25% of the initially formed ferrous species population are lost in similar to 2 ps. Cast in the contest of previous ultrafast infrared and X-ray spectroscopic studies, we suggest that upon prompt photoreduction of the metal centre, the excited molecules dissociate in

Nitrate contamination is a common problem in groundwater around the world. Nitrate can be cathodically reduced in bioelectrochemical systems using autotrophic denitrifiers with low energy investment and without chemical addition. Successful denitrification was demonstrated in previous studies in both microbial fuel cells and microbial electrolysis cells (MECs) with continuous current flow, whereas the impact of intermittent current supply (e.g., in a fluidized-bed system) on denitrification and particularly the electron-storing capacity of the denitrifying electroactive biofilms (EABs) on the cathodes have not been studied in depth. In this study, two continuously fed MECs were operated in parallel under continuous and periodic polarization modes over 280 days, respectively. Under continuous polarization, the maximum denitrification rate reached 233 g NO3--N/m(3)/d with 98% nitrate removal (0.6 mg NO3--N/L in the effluent) with negligible intermediate production, while under a 30 s open-circuit/30 s polarization mode, 86% of nitrate was removed at a maximum rate of 205 g NO3--N/m(3)/d (4.5 mg NO3--N/L in the effluent) with higher N2O production (6.6-9.3 mg N/L in the effluent). Conversely, periodic polarization could be an interesting approach in other bioelectrochemical processes if the generation of chemical intermediates (partially reduced or oxidized) should be favored. Similar microbial communities dominated byGallionellaceaewere found in both MECs; however, swapping the polarization modes and the electrochemical analyses suggested that the periodically polarized EABs probably developed a higher ability for electron storage and transfer, which supported the direct electron transfer pathway in discontinuous operation or fluidized biocathodes.

A set of three new Ru(ii) polypyridyl complexes decorated with 5-aryl tetrazolato ligands (R-CN4)-, (D series, namely D1, D3 and D4), is presented herein. Whereas complex D1 represents the pyrazinyl tetrazolato analogue of a previously reported Ru(ii) complex (D2) with the general formula cis-[(dcbpy)2Ru(N^N)]+, in which dcbpy is 2,2′-bipyridine-4,4′-dicarboxylic acid and N^N is the chelating 2-pyridyl tetrazolato anion, the design of the unprecedented Ru(ii) species D3 and D4 relied upon a completely different architecture. More specifically, the molecular structure of thiocyanate-based species cis-[(dcbpy)2Ru(NCS)2], that is typically found in benchmark Ru(ii) dyes for dye sensitized solar cell (DSSCs), was modified with the replacement of two of the -NCS ligands in favour of the introduction of 5-aryl tetrazolato anions, such as the deprotonated form of 5-(4-bromophenyl)-1H-tetrazole, for complex D3 and 5-(4-cyanophenyl)-1H-tetrazole in the case of complex D4. To streamline the behavior of the D series of Ru(ii) complexes as photosensitizers for DSSCs, an in-depth analysis of the excited state properties of D1, D3 and D4 was performed through TDDFT calculations and TDAS (nanosecond transient difference absorption spectroscopy). The obtained results highlight a trend that was confirmed once D1, D3 and D4 were tested as photosensitizers for DSSC under different conditions. Along the series of the Ru(ii) complexes, the neutrally charged species D3 and D4 displayed the best photovoltaic performances. This journal is

Arthropod herbivores cause dramatic crop losses, and frequent pesticide use has led to widespread resistance in numerous species. One such species, the two-spotted spider mite, Tetranychus urticae, is an extreme generalist herbivore and a major worldwide crop pest with a history of rapidly developing resistance to acaricides. Mitochondrial Electron Transport Inhibitors of complex I (METI-Is) have been used extensively in the last 25 years to control T. urticae around the globe, and widespread resistance to each has been documented. METI-I resistance mechanisms in T. urticae are likely complex, as increased metabolism by cytochrome P450 monooxygenases as well as a target-site mutation have been linked with resistance. To identify loci underlying resistance to the METI-I acaricides fenpyroximate, pyridaben and tebufenpyrad without prior hypotheses, we crossed a highly METI-I-resistant strain of T. urticae to a susceptible one, propagated many replicated populations over multiple generations with and without selection by each compound, and performed bulked segregant analysis genetic mapping. Our results showed that while the known H92R target-site mutation was associated with resistance to each compound, a genomic region that included cytochrome P450-reductase (CPR) was associated with resistance to pyridaben and tebufenpyrad. Within CPR, a single nonsynonymous variant distinguished the resistant strain from the sensitive one. Furthermore, a genomic region linked with tebufenpyrad resistance harbored a non-canonical member of the nuclear hormone receptor 96 (NHR96) gene family. This NHR96 gene does not encode a DNA-binding domain (DBD), an uncommon feature in arthropods, and belongs to an expanded family of 47 NHR96 proteins lacking DBDs in T. urticae. Our findings suggest that although cross-resistance to METI-Is involves known detoxification pathways, structural differences in METI-I acaricides have also resulted in resistance mechanisms that are compound-specific.

Leaching of chemicals from adhesion promoters is, in particular, problematic for the food, water, pharmaceutical, and MedTech industries where any chemical contamination is unacceptable. A solution to this issue is to employ covalently attached nanoscale polymer brushes as adhesive layers for plastics. One of the industrially most relevant adhesion targets in that respect is poly(dimethylsiloxane) (PDMS), being used for many high-end applications such as catheters and breast implants. In this work, we have synthesized a novel surface-immobilized poly(2-hydroxyethyl methacrylate)-based brush adhesive containing reactive hydrosilane groups that can bond directly to PDMS. Two different medical grades of addition-cured PDMS were molded on top of titanium substrates already coated with the polymer brush. Titanium plates were used for the chemical analysis, and titanium rods were used for adhesion testing. Adhesion testing revealed a high adhesive force, in which cohesive failure was observed in the bulk PDMS. The necessity of the hydrosilane group in the polymer brush adhesive layer was demonstrated in comparative studies using similar brushes lacking this functionality.

Significance To perform their specific electron-transfer relay functions, hemes commonly adopt low spin states with fine-tuned redox potentials. Understanding molecular elements controlling these properties is crucial for the description of natural proteins and engineering redox-active systems. We describe unusual effects of mitochondrial disease-related mutation in cytochrome bc1, based on which we identify a dual role of hydrogen bonding to the propionate group of heme bH. We observe that stabilization of the hydrogen bond in mutant enhances the redox potential but destabilizes the low spin state of oxidized heme. This demonstrates a critical role of the hydrogen bonding, and heme-protein interactions in general, to secure a suitable redox potential and spin state, a notion that might be universal for other heme proteins., Hemes are common elements of biological redox cofactor chains involved in rapid electron transfer. While the redox properties of hemes and the stability of the spin state are recognized as key determinants of their function, understanding the molecular basis of control of these properties is challenging. Here, benefiting from the effects of one mitochondrial disease–related point mutation in cytochrome b, we identify a dual role of hydrogen bonding (H-bond) to the propionate group of heme bH of cytochrome bc1, a common component of energy-conserving systems. We found that replacing conserved glycine with serine in the vicinity of heme bH caused stabilization of this bond, which not only increased the redox potential of the heme but also induced structural and energetic changes in interactions between Fe ion and axial histidine ligands. The latter led to a reversible spin conversion of the oxidized Fe from 1/2 to 5/2, an effect that potentially reduces the electron transfer rate between the heme and its redox partners. We thus propose that H-bond to the propionate group and heme-protein packing contribute to the fine-tuning of the redox potential of heme and maintaining its proper spin state. A subtle balance is needed between these two contributions: While increasing the H-bond stability raises the heme potential, the extent of increase must be limited to maintain the low spin and diamagnetic form of heme. This principle might apply to other native heme proteins and can be exploited in engineering of artificial heme-containing protein maquettes.

The vast compositional space of Prussian blue analogues (PBAs), formula A(x)M[M'(CN)(6)](y)center dot nH(2)O, allows for a diverse range of functionality. Yet, the interplay between composition and physical properties-e.g., flexibility and propensity for phase transitions-is still largely unknown, despite its fundamental and industrial relevance. Here we use variable-pressure X-ray and neutron diffraction to explore how key structural features, i.e., defects, hydration, and composition, influence the compressibility and phase behavior of PBAs. Defects enhance the flexibility, manifesting as a remarkably low bulk modulus (B-0 approximate to 6 GPa) for defective PBAs. Interstitial water increases B-0 and enables a pressure-induced phase transition in defective systems. Conversely, hydration does not alter the compressibility of stoichiometric MnPt(CN)(6), but changes the high-pressure phase transitions, suggesting an interplay between low-energy distortions. AMnCo(CN)(6) (A(I) = Rb, Cs) transition from F (4) over bar 3m to P (4) over bar n2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb0.87Mn[Co(CN)(6)](0.91) is further lowered to the polar space group Pn by an improper ferroelectric mechanism. These fundamental insights aim to facilitate the rational design of PBAs for applications within a wide range of fields.

Synthetic methodologies involving the formation of carbon–carbon bonds from carbon–hydrogen bonds are of significant synthetic interest, both for efficiency in terms of atom economy and for their undeniable usefulness in late-stage functionalization approaches. Combining these aspects with being metal-free, the radical C–H intermolecular arylation procedures covered by this review represent both powerful and green methods for the synthesis of (hetero)biaryl systems.1 Introduction2 Arylation with Arenediazonium Salts and Related Derivatives2.1 Ascorbic Acid as the Reductant2.2 Hydrazines as Reductants2.3 Gallic Acid as the Reductant2.4. Polyanilines as Reductants2.5 Chlorpromazine Hydrochloride as the Reductant2.6 Phenalenyl-Based Radicals as Reductants2.7 Electrolytic Reduction of Diazonium Salts2.8 Visible-Light-Mediated Arylation3 Arylation with Arylhydrazines: Generation of Aryl Radicals Using an Oxidant4 Arylation with Diaryliodonium Salts5 Arylation with Aryl Halides6 Conclusions

Different perylene-3,4:9,10-bis(dicarboximide) (abbreviated as perylenebisimides, or simply PBI) compounds (MT-PBI, DT-PBI, MP-PBI and DP-PBI) with thienyl and phenyl substituents at the bay position were prepared to study the effect of substitution on the photophysical properties, especially the intersystem crossing (ISC) efficacy. We found that the derivative with a monothienyl substituent (MT-PBI) shows efficient ISC (singlet oxygen quantum yield ΦΔ = 72%) and longer triplet state lifetime (τT = 64.4 μs) as compared to reference compounds (derivative with monophenyl substituent at bay position, MP-PBI, ΦΔ = 23% and τT = 48.5 μs). Theoretical computations reveal that the ISC efficiency is dependent on the magnitude of the spin orbit couplings (SOC) between the singlet and triplet excited states, and the SOC matrix element is up to 2 cm−1 for compound showing the highest ISC efficiency. Femtosecond transient absorption spectra show the ISC rate constant of 8 × 109 s−1 for MT-PBI, and no charge transfer exists. Photo-driven electron transfer was observed with the PBI derivatives in the presence of sacrificial electron donor triethanolamine (TEOA), and reversible formation of PBI radical anion (PBI−•) was observed, which shows absorption in the range of 600 nm–800 nm and 900 nm–1000 nm. Delayed fluorescence (P-type) in MT-PBI was also observed (τT = 31.0 μs). These finding are useful for the design of PBI-derived heavy atom-free compounds to be used as triplet photosensitizers.

[EN] Pterin (Ptr) is a model photosensitizer that acts mainly through type I mechanism and is able to photoinduce the one-electron oxidation of purine and pyrimidine nucleobases. However, under anaerobic conditions Ptr reacts with thymine (T) to form photoadducts (Ptr-T) but does not lead to the photodegradation of guanine (G), which is the nucleobase with the lowest ionization potential. Accordingly, G is thermodynamically able to reduce the radicals of the other nucleobases and has been described in this sense as the "hole sink" of the DNA double helix. Here we analyze by steady-state and time-resolved studies the effect of G in the anaerobic photosensitization of T by Ptr, using nucleotides and oligonucleotides of different sequences. We demonstrated that G is able to reduce T radicals but does not prevent the formation of Ptr-T adducts. Our results suggest that after the encounter between the excited Ptr and T, and completion of the electron transfer step, part of the radicals escape from the solvent cage, to further react with other species. However, a proportion of radicals do not escape and evolve to photoadducts before separation. We provide new evidence that contributes to understand the photosensitizing properties of Ptr in the absence of O-2, the mechanism of formation of photoadducts in the DNA and the protective role of G towards the photodamage in other nucleobases., The present work was partially supported by Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET-Grant P-UE 2017 22920170100100CO) , Agencia de Promocion Cientifica y Tecnologica (ANPCyT-Grant PICT 2015-1988, and PICT 2017-0925) , Universidad Nacional de La Plata (UNLP-Grant 11/X840) . Funding from the Program CSIC de Cooperacion Cientifica para el Desarrollo (iCOOP-Light project ref 20105CD0017) and Spanish Government (PGC2018-096684-B-I00) are gratefully acknowledged. S.E.R. and J.R.N.R. thanks ANPCyT and CONICET for doctoral research fellowships. A.M.R. thanks Universidad de Antioquia (Colombia) for research fellowship. C.L. and A.H.T. are research members of CONICET. V.L.V. is research member of CSIC.

The structure-function relationship is at the heart of biology, and major protein deformations are correlated to specific functions. For ferrous heme proteins, doming is associated with the respiratory function in hemoglobin and myoglobins. Cytochrome c (Cyt c) has evolved to become an important electron-transfer protein in humans. In its ferrous form, it undergoes ligand release and doming upon photoexcitation, but its ferric form does not release the distal ligand, while the return to the ground state has been attributed to thermal relaxation. Here, by combining femtosecond Fe K-alpha and K-beta X-ray emission spectroscopy (XES) with Fe K-edge X-ray absorption near-edge structure (XANES), we demonstrate that the photocycle of ferric Cyt c is entirely due to a cascade among excited spin states of the iron ion, causing the ferric heme to undergo doming, which we identify. We also argue that this pattern is common to a wide diversity of ferric heme proteins, raising the question of the biological relevance of doming in such proteins.

This research aimed to prepare a recoverable sonophotocatalyst, in which microfibrillated carboxymethyl cellulose (MFC) acted as the Zn-Cu-Mg-mixed metal hydroxide/graphitic carbon nitride (MMH/g-C3N4) carrier. The characteristics of bare and composite sonophotocatalysts were analyzed by the XRD, FT-IR, BET, DRS, PL and FE-SEM equipped with the EDX mapping. The performance of prepared composites (MMH/g-C3N4@MFC) with various weight ratios of the MMH/g-C3N4 was studied for the sonophotocatalytic degradation of sulfadiazine (SDZ) as the model emerging contaminant. 93% of SDZ was degraded using the most effective catalyst (MMH/gC(3)N(4)@MFC3) with 15% weight ratio of the MMH/g-C3N4 under the desired operating conditions including solution pH of 6.5, SDZ concentration of 0.15 mM and ultrasonic power of 300 W. The MMH addition to the gC(3)N(4) structure increased the separation of charge carriers generated via the visible light or ultrasound irradiations. Moreover, the MMH/g-C3N4 was dispersed uniformly on the MFC and consequently, more active sites were available to form reactive oxygen species (ROS), compared to powder form. Hydroxyl radicals ((OH)-O-center dot) were determined as the main ROS in the SDZ degradation by performing a series of scavenging experiments. Less than 10% decrease in the degradation efficiency of SDZ was observed during five subsequent experiments, which indicated the proper retention of the MMH/g-C3N4 particles in the MFC. The adequate mineralization of SDZ (83% decrease in chemical oxygen demand (COD)) was obtained after 200 min of treatment. Eventually, ten degradation intermediates were identified by the GC-MS analysis and a plausible degradation mechanism for the contaminant was proposed.

Certain pairs of paramagnetic species generated under conservation of total spin angular momentum are known to undergo magnetosensitive processes. Two prominent examples of systems exhibiting these so-called magnetic field effects (MFEs) are photogenerated radical pairs created from either singlet or triplet molecular precursors, and pairs of triplet states generated by singlet fission. Here, we showcase confocal microscopy as a powerful technique for the investigation of such phenomena. We first characterise the instrument by studying the field-sensitive chemistry of two systems in solution: radical pairs formed in a cryptochrome protein and the flavin mononucleotide/hen egg-white lysozyme model system. We then extend these studies to single crystals. Firstly, we report temporally and spatially resolved MFEs in flavin-doped lysozyme single crystals. Anisotropic magnetic field effects are then reported in tetracene single crystals. Finally, we discuss the future applications of confocal microscopy for the study of magnetosensitive processes with a particular focus on the cryptochrome-based chemical compass believed to lie at the heart of animal magnetoreception., Confocal microscopy is showcased as a powerful technique for the measurement of spatiotemporally-resolved magnetic field effects in both solutions and single crystals.

Redox reactions between polyoxometalates (POMs) and biologically relevant molecules have been virtually unexplored but are important, considering the growing interest in the biological applications of POMs. In this work we give a detailed account on the redox behavior of CeIV-substituted polyoxometalates (CeIV-POMs) toward a range of amino acids and peptides. CeIV-POMs have been shown to act as artificial proteases that promote the selective hydrolysis of peptide bonds. In presence of a protein, a concomitant reduction of CeIV to CeIII ion is frequently observed, leading us to examine the origins of this redox reaction by first using amino acid building blocks as simple models. Among all of the examined amino acids, cysteine (Cys) showed the highest activity in reducing CeIV-POMs to CeIII-POMs, followed by the aromatic amino acids tryptophan (Trp), tyrosine (Tyr), histidine (His), and phenylalanine (Phe). While the redox reaction with Cys afforded the well-defined product cystine, no oxidation products were detected for the Trp, His, Tyr, and Phe amino acids after their reaction with CeIV-POMs, suggesting a radical pathway in which the solvent likely regenerates the amino acid. In general, the rate of redox reactions increased upon increasing the pD, temperature, and ionic strength of the reaction. Moreover, the redox reaction is highly sensitive to the type of polyoxometalate scaffold, as complexation of CeIV to a Keggin (K) or Wells-Dawson (WD) polyoxotungstate anion resulted in a large difference in the rate of redox reaction for both Cys and aromatic amino acids. The reduction of CeIVK was at least 1 order of magnitude faster in comparison to CeIVWD, in accordance with the higher redox potential of CeIVK in comparison to CeIVWD. The reaction of CeIVPOMs with a range of peptides containing redox-active amino acids revealed that the redox reaction is influenced by their coordination mode with CeIV ion, but in all examined peptides the redox reaction is favored in comparison to the hydrolytic cleavage of the peptide bond. ispartof: INORGANIC CHEMISTRY vol:59 issue:15 pages:10569-10577 ispartof: location:United States status: published

The biological role of non-symbiotic plant hemoglobins (Hbs) is not well understood. It may involve sensing and signaling of reactive nitrogen and oxygen species–a property that can be used in electrochemical sensing. Here, we electrochemically studied two novel non-symbiotic Beta vulgaris Hbs: BvHb1.2 and BvHb2 expressed in E. coli. At pH 7, we observed close potentials of their Fe2+/3+ hemes, −349 mV for BvHb1.2 and −345/−457 mV vs. Ag/AgCl for the “open” penta-/“closed” hexa-coordinated states of BvHb2. BvHbs bound and bioelectrocatalytically reduced O2 and H2O2 at potentials significantly exceeding their Fe2+/3+ heme potentials. BvHb2, with the onset of H2O2 reduction at 370 mV, enabled O2-interference-free 10 μM H2O2 detection at 0 mV, with a 87 nA μM−1 cm−2 sensitivity comparable to some peroxidases. The results underpin broad electrochemical applications of BvHbs in the electroanalysis of reactive species and in electrochemical biotransformations.

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and isotactic polypropylene (iPP) are highly incompatible and consequently their uncompatibilized blends are quite brittle regardless of the molecular weights and ductility of the individual components. Isotactic polypropylene-polystyrene block copolymers, to be applied as compatibilizers for a broad range of PPO/iPP blend compositions, were prepared by mechanism transformation from coordination polymerization (iPP) to Activators Regenerated by Electron Transfer (ARGET) Atom Transfer Radical Polymerization of styrene. The effect of the block copolymer composition and loading on the mechanical, thermal and morphological properties of the blends was studied. The addition of compatibilizer resulted in significant decreased domain size of the dispersed phase and improved mechanical properties. An unexpected phenomenon was observed for some compatibilized iPP-rich blends with only 20% PPO, which were characterized by an even higher impact resistance than that of pure PPO. (C) 2018 Elsevier Ltd. All rights reserved.

A mechanism based on the sequential absorption of two photons by the components of a redox couple has been recently proposed for catalysis of the energetically demanding reduction of aryl halides. Here, we analyze the suggested photochemical mechanism of this reaction, which employs perylenediimide (PDI) as a photocatalyst, on the basis of spectroscopic, electrochemical and electron paramagnetic resonance data. Our results indicate that the photoexcited PDI radical anion (*PDI˙−) cannot play the role of a photosensitizer in the aforementioned process. Instead, the reduction of 4′-bromoacetophenone likely involves *PDI˙− decomposition products. The extremely short lifetime of the photoexcited transient species, as *PDI˙−, is a major general limitation for photocatalytic schemes based on sequential two-photon excitation. In order to better understand the potential of such schemes, we discuss them in the context of the Z-scheme in natural photosynthesis.

The deposition of perylene diimide-based aggregates (PDI) onto wide band gap n-type Sb-doped SnO2 (ATO) was investigated with the aim of finding efficient and versatile dye-sensitized platforms :for photoelectrochemical solar fuel generation. These ATO-PDI photoanodes displayed hydrolytic stability in a wide range of pH (from 1 to 13) and revealed superior perforthances (up to 1 mA/cm(2) net photocurrent at 1 V vs SCE) compared to both WO3-PDI and: undoped SnO2-PDI when used in a photoelectrochemical setup for HBr splitting. Although ATO, SnO2, and WO3 are endowed with similar conduction band edge energetics, in ATO the presence-of a:significant density of intrabandgap states, whose occupancy Varies with the applied potential, plays a substantial role in tuning the efficiency of photoinduced charge separation and collection. Furthermore, the investigation of the charge injection kinetics confirmed that, even in the absence of applied bias, ATO and WO3 are the best substrates for the-oxidative quenching of poorly reducing PDI excited states, with at least a fraction of them injecting within

NADPH oxidases (NOXs) are the only enzymes exclusively dedicated to reactive oxygen species (ROS) generation. Dysregulation of these polytopic membrane proteins impacts the redox signaling cascades that control cell proliferation and death. We describe the atomic crystal structures of the catalytic flavin adenine dinucleotide (FAD)and heme-binding domains of Cylindrospermum stagnale NOX5. The two domains form the core subunit that is common to all seven members of the NOX family. The domain structures were then docked in silico to provide a generic model for the NOX family. A linear arrangement of cofactors (NADPH, FAD, and two membrane-embedded heme moieties) injects electrons from the intracellular side across the membrane to a specific oxygen-binding cavity on the extracytoplasmic side. The overall spatial organization of critical interactions is revealed between the intracellular loops on the transmembrane domain and the NADPH-oxidizing dehydrogenase domain. In particular, the C terminus functions as a toggle switch, which affects access of the NADPH substrate to the enzyme. The essence of this mechanistic model is that the regulatory cues conformationally gate NADPH-binding, implicitly providing a handle for activating/deactivating the very first step in the redox chain. Such insight provides a framework to the discovery of much needed drugs that selectively target the distinct members of the NOX family and interfere with ROS signaling.

Electrocatalysis is a promising tool for utilizing carbon dioxide as a feedstock in the chemical industry. However, controlling the selectivity for different CO2 reduction products remains a major challenge. We report a series of manganese carbonyl complexes with elaborated bipyridine or phenanthroline ligands that can reduce CO2 to either formic acid, if the ligand structure contains strategically positioned tertiary amines, or CO, if the amine groups are absent in the ligand or are placed far from the metal center. The amine-modified complexes are benchmarked to be among the most active catalysts for reducing CO2 to formic acid, with a maximum turnover frequency of up to 5500 s-1 at an overpotential of 630 mV. The conversion even works at overpotentials as low as 300 mV, although through an alternative mechanism. Mechanistically, the formation of a Mn-hydride species aided by in situ protonated amine groups was determined to be a key intermediate by cyclic voltammetry, 1H NMR, DFT calculations, and infrared spectroelectrochemistry.

Time-resolved transient absorption spectroscopy and computational analysis of D-pi-A complexes comprising Fe-II donors and Ti-IV acceptors with the general formula (Cp2Ti)-Cp-R(C(2)Fc)(2) (where RCp = Cp*, Cp, and Cp-MeOOC) and (Cp2Ti)-Cp-TMS(C(2)Fc)(C2R) (where R = Ph or CF3) are reported. The transient absorption spectra are consistent with an Fe-III/Ti-III metal-to-metal charge-transfer (MMCT) excited state for all complexes. Thus, excited-state decay is assigned to back-electron transfer (BET), the lifetime of which ranges from 18.8 to 41 ps. Though spectroscopic analysis suggests BET should fall into the Marcus inverted regime, the observed kinetics are not consistent with this assertion. TDDFT calculations reveal that the singlet metal-to-metal charge-transfer ((MMCT)-M-1) excited state for the Fe-II/Ti-IV complexes is not purely MMCT in nature but is contaminated with the higher-energy (1)Fc (d-d) state. For the diferrocenyl complexes, (Cp2Ti)-Cp-R(C(2)Fc)(2), the ratio of MMCT to Fc centered character ranges from 57:43 for the Cp* complex to 85:15 for the Cp-MeOOC complex. For the diferrocenyl and monoferrocenyl complexes investigated herein, the excited-state lifetimes decrease with increased (1)Fc character. The effect of Cu-I coordination was also analyzed by time-resolved transient absorption spectroscopy and reveals the elongation of the excited-state lifetime by 3 orders of magnitude to 63 ns. The transient spectra and TDDFT analysis suggest that the long-lived excited state in Cp2Ti(C(2)Fc)(2).CuX (where X is Cl or Br) is a triplet iron species with an electron arrangement of Ti-IV-Fe-3(II)-Cu-I.

Reactions between the π-acidic cyclic trimetallic coinage metal(I) complexes {[Cu(μ-3,5-(CF3)2pz)]3, {[Ag(μ-3,5-(CF3)2pz)]3, and {[Au(μ-3,5-(CF3)2pz)]3 with TTF, DBTTF and BEDT-TTF give rise to a series of coinage metal(I)-based new binary donor-acceptor adducts {[Cu(μ-3,5-(CF3)2pz)]3DBTTF} (1), {[Ag(μ-3,5-(CF3)2pz)]3DBTTF} (2), {[Au(μ-3,5-(CF3)2pz)]3DBTTF} (3), {[Cu(μ-3,5-(CF3)2pz)]3TTF} (4), {[Ag(μ-3,5-(CF3)2pz)]3TTF} (5), {[Au(μ-3,5-(CF3)2pz)]3TTF} (6), {[Cu(μ-3,5-(CF3)2pz)]3BEDT-TTF} (7), {[Ag(μ-3,5-(CF3)2pz)]3BEDT-TTF} (8), and {[Au(μ-3,5-(CF3)2pz)]3BEDT-TTF} (9), where pz = pyrazolate, TTF = tetrathiafulvalene, DBTTF = dibenzotetrathiafulvalene, and BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene. This series of binary donor-acceptor adducts has been found to exhibit remarkable supramolecular structures in both the solid state and solution, whereby they exhibit supramolecular stacked chains and oligomers, respectively. The supramolecular solid-state and solution binary donor-acceptor adducts also exhibit superior shelf stability under ambient laboratory storage conditions. Structural and other electronic properties of solids and solutions of these adducts have been characterized by single-crystal X-ray diffraction (XRD) structural analysis, 1H and 19F NMR, UV-vis-near-IR spectroscopy, Fourier transform infrared, and computational investigations. The combined results of XRD structural data analysis, spectroscopic measurements, and theoretical studies suggest sustenance of the donor-acceptor stacked structure and electronic communication in both the solid state and solution. These properties are discussed in terms of potential applications for this new class of supramolecular binary donor-acceptor adducts in molecular electronic devices, including solar cells, magnetic switching devices, and field-effect transistors.

A pentapeptide sequence was functionalized with an asymmetric arylated methyl-viologen (AVI3D2) and through controllable β-sheet self-assembly, conductive nanofibers were formed. Using a combination of spectroscopic techniques and conductive atomic force microscopy, we investigated the molecular conformation of the resultant AVI3D2 fibers and how their conductivity is affected by β-sheet self-assembly. These conductive nanofibers have potential for future exploration as molecular wires in optoelectronic applications. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:51 pages:7354-7357 ispartof: location:England status: published

Charge-transfer complexes involving tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) derivatives are engineered in a 2D arrangement onto a carbon surface through the exposure of immobilized TTF units to TCNQ compounds. TTF molecules were immobilized as robust monolayers on carbon surfaces using the electrografting method followed by a click chemistry coupling. When the TTF monolayer is exposed to TCNQ, TCNQF2 (2,5-difluoro-TCNQ), and TCNQF4 (2,3,5,6-tetrafluoro-TCNQ), strong donor–acceptor complexes are formed onto the surface. A considerable decrease of the electrochemical response accompanies the formation of the charge-transfer complex. This observation is rationalized by the analysis of original crystal samples using an ultramicroelectrode cavity, confirming that charge-transfer complexes are electrochemically silent. A fine control of the degree of charge transfer with the judicious choice of different acceptors is evidenced through electrochemical and X-ray photoelectron spectroscopy (XP...

A donor acceptor dyad composed of a BF2-chelated dipyrromethene (BODIPY) and a C-60 fullerene has been newly synthesized and characterized. The two moieties are linked by direct addition of an azido substituted BODIPY on the C-60, producing an imino fullerene BODIPY adduct. The photoinduced charge transfer process in this system was studied by ultrafast transient absorption spectroscopy. Electron transfer toward the fullerene was found to occur selectively exciting both the BODIPY chromophore at 475 nm and the C-60 unit at 266 nm on a time scale of a few picoseconds, but the dynamics of charge separation was different in the two cases. Eletrochemical studies provided information on the redox potentials of the involved species and spectroelectrochemical measurements allowed to unambiguously assign the absorption band of the oxidized BODIPY moiety, which helped in the interpretation of the transient absorption spectra. The experimental studies were complemented by a theoretical analysis based on DFT computations of the excited state energies of the two components and their electronic couplings, which allowed identification of the charge transfer mechanism and rationalization of the different kinetic behavior observed by changing the excitation conditions.

Oxidative transformations utilizing molecular oxygen (O2 ) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O2 are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O2 as the "primary" oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium-catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen- or electron-transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including (18) O labeling established the in situ formation of an oxo-ruthenium intermediate as the active catalytic species in the cycle and involvement of a two-electron hydride transfer in the rate-limiting step.

International audience; Nitric oxide (NO) synthases (NOSs) catalyze the formation of NO from L-arginine. We have shown previously that the NOS enzyme catalytic cycle involves a large number of reactions, but can be characterized by a global model with three main rate-limiting steps. These are the rate of heme reduction by the flavin domain (kr); of dissociation of NO from the ferric heme‒NO complex (kd) and of oxidation of the ferrous heme‒NO complex (kox). The reaction of oxygen with the ferrous heme‒NO species is part of a futile cycle that does not directly contribute to NO synthesis, but allows a population of inactive enzyme molecules to return to the catalytic cycle, and thus enables a steady-state NO synthesis rate. Previously, we have reported that this reaction does involve the reaction of oxygen with NO-bound ferrous heme complex, but the mechanistic details of the reaction, that could proceed via either an inner-sphere or an outer-sphere mechanism, remains unclear. Here we present additional experiments with neuronal NOS (nNOS) and inducible NOS (iNOS) variants (nNOS W409F and iNOS K82A and V346I) and computational methods to study how changes in heme access and electronics affect the reaction. Our results support an inner-sphere mechanism and indicate that the particular heme-thiolate environment of the NOS enzymes can stabilize an N-bound FeIII-N(O)OO- intermediate species and thereby catalyze this reaction, which otherwise is not observed or favorable in proteins like globins that contain a histidine-coordinated heme.

The addition of a compact titanium dioxide (TiO2) layer between the fluorine-doped tin oxide (FTO) coated glass substrate and the mesoporous TiO2 layer in the dye-sensitized solar cell (DSC) based on the iodide/triiodide redox couple (I-/I-3(-)) is known to improve its current-voltage characteristics. The compact layer decreases the recombination of electrons extracted through the FTO layer with I-3(-) around the maximum power point. Furthermore, the short-circuit photocurrent was improved, which previously has been attributed to the improved light transmittance and/or better contact between TiO2 and FTO. Here, we demonstrate that the compact TiO2 layer has another beneficial effect: it blocks the reaction between charge carriers in the FTO and photogenerated diiodide radical species (I-2(-center dot)). Using photomodulated voltammetry, it is demonstrated that the cathodic photocurrent found at bare FTO electrodes is blocked by the addition of a compact TiO2 layer, while the anodic photocurrent due to reaction with I-2(-center dot) is maintained. (C)The Author(s) 2019. Published by ECS.

Heterogenization of RuL3 complexes on a support with proper anchor points provides a route toward design of green catalysts. In this paper, Ru(II) polypyridyl complexes are investigated with the aim to unravel the influence on the photocatalytic properties of varying nitrogen content in the ligands and of embedding the complex in a triazine-based covalent organic framework. To provide fundamental insight into the electronic mechanisms underlying this behavior, a computational study is performed. Both the ground and excited state properties of isolated and anchored ruthenium complexes are theoretically investigated by means of density functional theory and time-dependent density functional theory. Varying the ligands among 2,2′-bipyridine, 2,2′-bipyrimidine, and 2,2′-bipyrazine allows us to tune to a certain extent the optical gaps and the metal to ligand charge transfer excitations. Heterogenization of the complex within a CTF support has a significant effect on the nature and energy of the electronic transitions. The allowed transitions are significantly red-shifted toward the near IR region and involve transitions from states localized on the CTF toward ligands attached to the ruthenium. The study shows how variations in ligands and anchoring on proper supports allows us to increase the range of wavelengths that may be exploited for photocatalysis.

Cascade polyene cyclization reactions are highly efficient and elegant bioinspired transformations that involve simultaneous multiple bond constructions to rapidly generate complex polycyclic molecules. This review summarizes the most prominent work on a variety of cationic and radical cascade cyclizations and their applications in natural product synthesis published between 2014 and 2018.1 Introduction2 Cationic Polyene Cyclizations2.1 Lewis Acid Mediated Polyene Cyclizations2.2 Brønsted Acid Mediated Polyene Cyclizations2.3 Halogen Electrophile Initiated Polyene Cyclizations2.4 Sulfur Electrophile Initiated Polyene Cyclizations2.5 Transition-Metal-Mediated Cationic Polyene Cyclizations3 Radical Polyene Cyclizations3.1 Transition-Metal-Mediated Radical Polyene Cyclizations3.2 Photocatalyst-Mediated Polyene Cyclizations4 Origin of Stereocontrol in Polyene Cyclizations5 Conclusion

The oxidation of the C-H and C=C bonds of hydrocarbons with H2O2 catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive Fe-IV=O species such as [(N4Py)Fe-IV=O](2+) formed by homolytic cleavage of the O-O bond of an Fe-III-OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine). We show here that at low H2O2 concentrations the Fe-IV=O species formed is detectable in methanol. Furthermore, we show that the decomposition of H2O2 to water and O-2 is an important competing pathway that limits efficiency in the terminal oxidant and indeed dominates reactivity except where only sub-/near-stoichiometric amounts of H2O2 are present. Although independently prepared [(N4Py)Fe-IV=O](2+) oxidizes stoichiometric H2O2 rapidly, the rate of formation of Fe-IV=O from the Fe-III-OOH intermediate is too low to account for the rate of H2O2 decomposition observed under catalytic conditions. Indeed, with excess H2O2, disproportionation to O-2 and H2O is due to reaction with the Fe-III-OOH intermediate and thereby prevents formation of the Fe-IV=O species. These data rationalize that the activity of these catalysts with respect to hydrocarbon/alkene oxidation is maximized by maintaining sub-/near-stoichiometric steady-state concentrations of H2O2, which ensure that the rate of the H2O2 oxidation by the Fe-III-OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the Fe-IV=O species with a substrate.

Anaerobic oxidation of methane provides a globally important, yet poorly constrained barrier for the vast amounts of methane produced in the subseafloor. Here we provide a global map and budget of the methane flux and degradation in diffusion-controlled marine sediments in relation to the depth of the methane oxidation barrier. Our new budget suggests that 45-61 Tg of methane are oxidized with sulfate annually, with approximately 80% of this oxidation occurring in continental shelf sediments (

Reactive oxygen species (ROS) oxidize guanosines in DNA to form 8-oxo-7,8-dihydro-2-deoxyguanosine (8-oxodG), a biomarker for oxidative stress. Herein we describe a novel 64-microwell electrochemiluminescent (ECL) array enabling sensitive multiplexed detection of 8-oxodG in dsDNA without hydrolysis. Films of Nafion and reduced graphene oxide containing ECL dye [Os(bpy)(2)(phen-benz-COOH)](2+) (OsNG, {bpy= 2,2'-bipyridine and phen-benz-COOH = (4-(1,10-phenanthrolin-6-yl)benzoic acid)}) were assembled into microwells on a pyrolytic graphite wafer to detect 8-oxodG in oligonucleotides by electrochemiluminescence (ECL). DNA oxidation by Fenton's reagent or by ROS formation during redox cycles involving NADPH, Cu-II, and model metabolites was monitored. UPLC-MS/MS of oxidized DNA samples were used for calibration. Detection limit for the fluidic arrays was one 8-oxodG per 670 intact nucleobases, or 0.15%. The method is sensitive enough to evaluate DNA oxidation from biologically relevant ROS-generating reactions of Cull, NADPH, and model metabolites.

The addition of graphene nanoplatelets (GNP) to TiO2 nanoparticles (NPs) has been recently considered as a method to improve the photocatalytic efficiency of TiO2 by favoring charge carrier separation. Here, we show that it is possible to improve the efficiency of GNP-TiO2 composites by controlling the shape, stability, and facets of TiO2 NPs grown on GNP functionalized with either COOH or NH2 groups, while adding ethylendiamine (EDA) and oleic acid (OA) during a hydrothermal synthesis. We studied the photocatalytic activity of all synthesized materials under UV-A light using phenol as a target molecule. GNP-TiO2 composites synthesized on COOH-functionalized GNP, exposing {101} facets, were more efficient at abating phenol than those synthesized on NH2-functionalized GNP, exposing {101} and {100} facets. However, neither of these composites was stable under irradiation. The addition of both OA and EDA stabilized the materials under irradiation; however, only the composite prepared on COOH-functionalized GNP in the presence of EDA showed a significant increase in phenol degradation rate, leading to results that were better than those obtained with TiO2 alone. This result can be attributed to Ti-OH complexation by EDA, which protects GNP from oxidation. The orientation of the most reducing {101} facets toward GNP and the most oxidizing {100} facets toward the solution induces faster phenol degradation owing to a better separation of the charge carriers.

The quinone-dependent alcohol dehydrogenase (PQQ-ADH, E.C. 1.1.5.2) from the Gram-negative bacterium Pseudogluconobacter saccharoketogenes IFO 14464 oxidizes primary alcohols (e.g. ethanol, butanol), secondary alcohols (monosaccharides), as well as aldehydes, polysaccharides, and cyclodextrins. The recombinant protein, expressed in Pichia pastoris, was crystallized, and three-dimensional (3D) structures of the native form, with PQQ and a Ca2+ ion, and of the enzyme in complex with a Zn2+ ion and a bound substrate mimic were determined at 1.72 angstrom and 1.84 angstrom resolution, respectively. PQQ-ADH displays an eight-bladed beta-propeller fold, characteristic of Type I quinone-dependent methanol dehydrogenases. However, three of the four ligands of the Ca2+ ion differ from those of related dehydrogenases and they come from different parts of the polypeptide chain. These differences result in a more open, easily accessible active site, which explains why PQQ-ADH can oxidize a broad range of substrates. The bound substrate mimic suggests Asp333 as the catalytic base. Remarkably, no vicinal disulfide bridge is present near the PQQ, which in other PQQ-dependent alcohol dehydrogenases has been proposed to be necessary for electron transfer. Instead an associated cytochrome c can approach the PQQ for direct electron transfer.

The design and synthesis of a set of supported azolium salt pre-catalysts is presented along with their utilization in the production of monoesters of glycerol and solketal by oxidative N-heterocyclic carbene (NHC)-catalysis through batch and continuous-flow approaches. After a propaedeutic study with soluble NHCs, the heterogeneous analogues (silica and polystyrene supports) were tested in a model monoesterification of glycerol using either the Kharasch oxidant or air (in the presence of electron transfer mediators) as the terminal oxidants. The best performing polystyrene-supported triazolium salt pre-catalyst afforded monoacylglycerols (MAGs) in high yields (up to 95%) and almost complete selectivity (monoester/diester >95 : 5) using air and the green solvent Me-THF. The synthesis of fully bio-based MAGs from furfural, 5-hydroxymethylfurfural (HMF), citronellal, and vanillin is also reported. Continuous-flow experiments have been finally performed by fabricating the corresponding packed-bed microreactor, which could be operated for ca. 120 hours with maintenance of conversion efficiency and selectivity.

The role of relative concentrations of energy donors (fluorescein, D), acceptors (rhodamine, A) and silica on Forster resonance energy transfer (FRET) efficiency and dynamics in dye silica conjugates has been studied, as a part of our initial attempts to ascertain the potential of dye-silica nanoconjugates as light harvesting nanoantennae. Two types of dye-silica nanoconjugates, prepared by the co-condensation method, have been examined. The first is based on silica nanoshells (SNS-dye) while the second is based on silica nanoparticles (SNP-dye). Both these nanostructures have a diameter of approximately 25 nm. Efficient energy transfer (91% and 97%, respectively) has been observed in both, for total fluorophore concentration upto 5-6 mmol, irrespective of the D : A ratio. The lower efficiency at dye concentrations greater than these has been rationalized by the competitive self-quenching of D. A risetime of approximately 500 fs is observed in the A emission in SNS-dye, but there is no such feature in SNP-dye. The shape and size dependence of the FRET efficiency and dynamics has been rationalized as follows: the initial step of dye rich core formation in nanoparticles results in high proximity of dye molecules to each other, leading to highly efficient FRET than in nanoshells. In larger SNP-dye nanoconjugates of 65 nm in diameter, the FRET efficiency decreases to 85%, while a risetime in D emission emerges. This provides support to the proposed correlation between efficiency and packing. Hence, it is inferred that total fluorophore concentration, rather than D : A ratios, governs the FRET dynamics and efficiency in these systems.

Small push pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs.

The reduction of an aryl iodide is generally believed to involve a clean-cut two-electron: reduction to produce an aryl anion and iodide. This is in contradiction to what is observed if a highly efficient grafting agent, such as an aryldiazonium salt, is employed. The difference in behavior is explained by the much more extreme potentials required for reducing an aryl iodide; which facilitates the further reduction of the aryl radical formed as an intermediate. However, in this study we disclose that electrografting of aryl iodides is indeed possible upon extended voltammetric cycling. This implies that even if the number of aryl radicals left unreduced at the electrode surface is exceedingly small, a functionalization of the surface may still be promoted. In fact,, the grafting efficiency is found to increase during the grafting process, which may be explained by the inhibiting effect the growing film exerts on the competing reduction of the aryl radical. The, slow buildup of the organic film results in a well-ordered structure as shown by the well-defined electrochemical response frond a grafted film containing ferrocenylmethyl groups. Hence, the reduction of aryl Iodides allows a precisely controlled, albeit slow, growth of thin organic films.

The reaction of 2,2'-bipyridine-3,3'-diol (H2L) and cis-Os-II(bpy)(2)Cl-2 (bpy = 2,2'-bipyridine) results in isomeric forms of [Os-II(bpy)(2)(HL-)]ClO4, [1]ClO4 and [2]ClO4, because of the varying binding modes of partially deprotonated HL-. The identities of isomeric [1]ClO4 and [2]ClO4 have been authenticated by their single crystal X-ray structures. The ambidentate HL- in [2]ClO4 develops the usual N,N bonded five-membered chelate with a strong O-H center dot center dot center dot O hydrogen bonded situation (O-H center dot center dot center dot O angle: 160.78 degrees) at its back face. The isomer [1]ClO4 however represents the monoanionic O-,N coordinating mode of HL-, leading to a six-membered chelate with the moderately strong O-H center dot center dot center dot N hydrogen bonding interaction (O-H center dot center dot center dot N angle: 148.87 degrees) at its backbone. The isomeric [1]ClO4 and [2]ClO4 also exhibit distinctive spectral, electrochemical, electronic structural, and hydrogen bonding features. The pK(a) values for [1]ClO4 and [2]ClO4 have been estimated to be 0.73 and 50 degrees) in paramagnetic [Os-III(bpy)(2)(L'(2-))]ClO4 ([4]ClO4). The electronic structural aspects of the complexes reveal the noninnocent potential of the coordinated HL-, L2-, and L'(2-). The K-c value of 49 for 3(3+) reveals a class I mixed-valent (OsOsIII)-Os-II state.

Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor–acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor–acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor–acceptor graphene-based hybrids, will be discussed.

The rates of hole transfer between guanine and adenine in single strand DNA have been evaluated by using Fermi’s golden rule and Kubo’s generating function approach for the Franck–Condon weighted density of states. The whole sets of the normal modes and vibrational frequencies of the two nucleobases, obtained at DFT/B3LYP level of calculation, have been considered in computations. The results show that in single strand the pyramidalization/planarization mode of the amino groups of both nucleobases plays the major role. At room temperature, the Franck–Condon density of states extends over a wide range of hole site energy difference, 0–1 eV, giving some hints about the design of oligonucleotides of potential technological interest.

Three porphyrin-cobaloxime dyads, suitable for application in photoinduced hydrogen generation with sacrificial donors, are characterized by ultrafast spectroscopy in order to clarify the primary photochemical events.

A metal organic framework (MOF) based on the [Cu(4)I(4)DABCO(2)] cluster (DABCO = 1,4-diazabicyclo[2.2.2]octane), MOF 1, shows bright emission with a maximum at 556 nm and an emission quantum yield of 0.53 in the solid state. When the large cavities of the MOF are loaded during the synthesis with different amounts of ferrocene {FeCp2, [((5)-C5H5)(2)Fe-II]}, the luminescence of MOF 1 decreases with the increase in the ferrocene content, reaching an almost complete quenching for 3.5 wt.-% of cage loading, corresponding to the complete filling of the MOF cavities. When an electric potential is applied to the FeCp2@MOF 1 deposited onto an ITO glass, the (FeCp2)-Cp-II is oxidised to (FeCp2+)-Cp-III, and the MOF 1 emission is partially switched on again, indicating that a photoinduced electron-transfer reaction is contributing to the quenching process.

The electrochemical and spectroelectrochemical properties of a bis-pyrid-4-yl functionalised vinylenedithio-TFF derivative, 1, in solution are reported. The compound was immobilised on a Pt electrode and the resulting layers formed were investigated using electrochemical techniques. Two oxidation processes were observed for 1, typical of TTF derivatives. A solvent dependence study revealed that the stabilisation of the radical cation intermediate, 1(center dot+), towards further oxidation is achieved in solvents with a low Gutmann donor number such as dichloromethane. Analysis of 1(2+) in solution under aerobic and anaerobic conditions reveal that its stability is compromised in the presence of oxygen and therefore the stability of monolayers of 1 is greatly enhanced under anaerobic conditions. Time dependent OFT calculations of the compound in several oxidation states are discussed to obtain information on the location of the various redox processes. (C) 2013 Elsevier Ltd. All rights reserved.

A mononuclear hexa-coordinated iron carbonyl complex [Fe(mu-bdt)(CO)(2)(PTA)(2)](1) (bdt = 1,2-benzenedithiolate; PTA = 1,3,5-triaza-7-phosphaadamantane) with two bulky phosphine ligands in the trans position was synthesized and characterized by X-ray structural analysis coulometry data, FTIR, electrochemistry and electronic structure calculations. The complex undergoes a facilitated two-electron reduction 1/1(2-) and shows an inverted one-electron reduction for 1/1(-) at higher potentials. Electrochemical investigations of 1 are compared to the closely related [Fe(bdt)(CO)(2)(PMe3)(2)] compound. A mechanistic suggestion for the hydrogen evolution reaction upon proton reduction from acid media is derived. The stability of 1 in both weak and strong acids is monitored by cyclic voltammetry.

New hybrid nanomaterials, with improved photocatalytic performance in pollutants removal, were obtained through the modification of titanate nanotubes (TNT) with a cobalt porphyrin, the cyanocobalamin, also knowing as vitamin B12 (812). The nanocrystalline TNT were produced by hydrothermal treatment and after treated with cobalamin to produce B12-TNT materials. The characterization of the new hybrid material was performed by XRD, FTIR, TEM-EDS, DRS, XPS and ICP. The results show that the immobilization of the cobalt containing specie is dependent on the point of zero charge of the TNT and no modifications on the structure and morphology were observed. No significant changes in the optical band gap were observed after B12 incorporation, but an increasing in the visible light absorption, which arises from charge transfer and d-d transitions of the cobalt, was visualized. The samples photocatalytic performance was studied for the hydroxyl radical production and the highest catalytic ability was achieved by the B12-HTNT sample. The catalytic ability of these new hybrid nanomaterials for two model pollutants photodegradation, phenol and rhodamine B (RhB) was investigated. For both pollutants, the best results were achieved using B12-HTNT with a removal of 94% of a 10 ppm RhB and 87% of a 20 ppm phenol solution in 90 min of irradiation (150 mL, 0.2 g catalyst/L). (C) 2016 Elsevier Masson SAS. All rights reserved. Fundacao para a Ciencia e a Tecnologia [PTDC/CTM-NAN/113021/2009, DID/MULTI/ 00612/2013, IF/01210/2014] info:eu-repo/semantics/publishedVersion

The azaBODIPYs containing one and two formyl functional groups on the 1,7-aryl groups present at the azaBODIPY core were synthesized over sequence of steps and characterized by mass, NMR, absorption, and electro-chemical techniques. The monoformylated and diformylated azaBODIPYs are very useful synthons to prepare a wide variety of new fluorescent compounds. The mono- and diformylated azaBODIPYs were treated with pyrrole under mild acidic conditions followed by column chromatographic purification to afford azaBODIPYs appended with one and two dipyrromethanyl groups. The dipyrramethanyl groups of azaBODIPYs were oxidized with DDQand complexed with BF3-Et2O to obtain covalently linked azaBODIPY-BODIPY dyads and azaBODIPY-(BODIPY)(2) triads. The dyads and triads were characterized in detail by HR-MS, 1D and 2D NMR, absorption, fluorescence, and electrochemical techniques and the structure of one of the triads was deduced by X-ray crystallography. The crystal structure of azaBODIPY-(BODIPY)2 triad revealed that the two BODIPY units were in perpendicular orientation with azaBODIPY unit. The absorption and electrochemical studies indicated a weak interaction among the BODIPY and azaBODIPY moieties and the moieties retain their independent characteristic features in dyads and triads. The preliminary fluorescence studies supported an efficient energy transfer from BODIPY unit(s) to azaBODIPY unit in dyads and triads.

International audience; Electrochemical and photophysical analysis of new donoracceptor systems 2 and 3, in which a benzothiadiazole (BTD) unit is covalently linked to a tetrathiafulvalene (TTF) core, have verified that the lowest excited state can be ascribed to an intramolecular-charge-transfer (ICT) (TTF)(benzothiadiazole) transition. Owing to better overlap of the HOMO and LUMO in the fused scaffold of compound 3, the intensity of the 1ICT band is substantially higher compared to that in compound 2. The corresponding CT fluorescence is also observed in both cases. The radical cation TTF+. is easily observed through chemical and electrochemical oxidation by performing steady-state absorption experiments. Interestingly, compound 2 is photo-oxidized under aerobic conditions.

Cyclotriphosphazene and cyclotetraphosphazene appended with six and eight covalently linked porphyrin-ferrocene conjugates respectively were synthesized by treating N3P3Cl6 and N4P4Cl8 with appropriate equivalents of ferrocene linked porphyrin containing meso-hydroxyphenyl group in THF in the presence of Cs2CO3 followed by column chromatographic purification. NMR and absorption studies indicated a weak interaction between adjacent porphyrin-ferrocene conjugates. Electrochemical studies supported electrochemical equivalence of ferrocenyl and porphyrinyl moieties in these multiporphyrin-ferrocene conjugate assemblies. The fluorescence studies showed significant quenching of porphyrin fluorescence due to photo-induced electron transfer from ferrocene to singlet state of porphyrin unit in these assemblies. (C) 2012 Elsevier B. V. All rights reserved.