T → S Energy Transfer in Some Molecular Complexes

Calculations on the bimolecular complexes of acetophenone or benzophenone with anthracene and its substituted derivatives were carried out using a standard quantum-chemical approach to molecular systems. The deactivation pathways for lower triplet excited states of acetophenone and benzophenone were established. The probability of energy transfer from the energy donor to acceptor in the complexes was considered. The analysis of calculation results showed that the T S transfer of electronic excitation energy in these complexes is feasible only in the case of a small distance between the molecules, and the efficiency of this transfer is higher in the acetophenone rather than benzophenone complexes.     

Accessing Lanthanide-to-Lanthanide Energy Transfer in a Family of Site-Resolved [LnIIILnIII′] Heterodimetallic Complexes

The ligand H₃L (6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploited to engender and study energy transfer (ET) in two dinuclear [Ln^IIILn^III′] analogues of interest, [EuYb] and [NdYb]. Their structural and physical properties have been compared with newly synthesised analogues featuring no possible ET ([EuLu], [NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and [NdNd] analogues, which have been previously reported. Photophysical data suggest that ET between Eu^III and Yb^III does not occur to a significant extent, whereas emission from Yb^III originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring between the two Nd^III centres in [NdNd], as well as in [NdYb], in which Yb^III luminescence is thus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-to-lanthanide ET phenomena in defined molecular systems.     

Ligand Reprogramming in Dinuclear Helicate Complexes: A Consequence of Allosteric or Electrostatic Effects?

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.     

Nucleophilic Substitution Reaction of p-Dinitrobenzene by a Carbanion: Evidence for Electron Transfer Mechanism

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Phosphate Diester Hydrolysis by Dinuclear Tb(III) Complexes with BDBPH in Second-order Dependence

In the past decade, many lanthanide metal complexes with polyazamacrocycle, Schiff base, and glycol ligands have been shown to enhance the rate of DNA-phosphate hydrolysis by seven orders of magnitude1-3. This efficiency results from the conjunction of hi…     

Non-Classical Synthons: Supramolecular Recognition by S⋅⋅⋅O Chalcogen Bonding in Molecular Complexes of Riluzole

Classical examples of supramolecular recognition units or synthons are the ones formed by hydrogen bonds. Here, we report the ubiquity of a S⋅⋅⋅O chalcogen bonded synthon observed in a series of supramolecular complexes of the amyotrophic lateral sclerosis drug riluzole. Although the potential of higher chalcogens such as Se and Te to form robust and directional chalcogen bonded motifs is known, intermolecular sulfur chalcogen bonding is considered to be weak owing to the lower polarizability of S atoms. Here, the robustness and electronic nature of a S⋅⋅⋅O chalcogen bonding non-classical synthon, and the origin of its exceptional directionality have been explored. Bond orders of the drug–coformer chalcogen bonding are found to be as high as one third of a single bond, and they are largely ionic in nature. The contribution of the S⋅⋅⋅O chalcogen bonded motifs to the lattice energies of a series of crystals from the Cambridge Structural Database has been analyzed, showing they can be indeed significant, especially in molecules devoid of strong hydrogen bond donor groups.     

Evidence for a Proton-Coupled Electron Transfer Mechanism in a Biomimetic System for Monoamine Oxidase B Catalysis

Mechanistic studies with 5-ethyl-3-methyllumiflavinium (Fl⁺) perchlorate, a biomimetic model for flavoenzyme monoamine oxidase B (MAO-B) catalysis, and the tertiary, allyl amine 1-methyl-4-(1-methyl-1 H-pyrrol-2-yl)-1,2,3,6-tetrahydropyridine (MMTP) reveal that proton-coupled electron transfer (PCET) may be an important pathway for MAO catalysis. The first step involves a single-electron transfer (SET) leading to the free radicals Fl^. and MMTP^., the latter produced by deprotonation of the initially formed and highly acidic MMTP^.+. Molecular oxygen (O₂) is found to play a hitherto unrecognized role in the early steps of the oxidation. MMTP and several structurally similar tertiary amines are the only tertiary amines oxidized by MAO, and their structural/electronic properties provide the key to understanding this behavior. A general hypothesis about the role of SET in MAO catalysis, and the recognition that PCET occurs with appropriately substituted substrates is presented.     

A 1010 Rate Enhancement of Phosphodiester Hydrolysis by a Dinuclear Aminopeptidase—Transition-State Analogues as Substrates?

Streptomyces dizinc aminopeptidase (sAP) shows a specific activity of 33.7 nmol min⁻¹ mg⁻¹ toward the hydrolysis of the transition-state analogue bis-p-nitrophenylphosphate with a rate constant of k_cat/K_m=100 M ⁻¹ s⁻¹ and a first-order rate enhancement of about 10¹⁰, which is much superior to several Zn chemical models and comparable to some phosphodiesterases. This study suggests that sAP can serve as a novel dinuclear model system to provide further insight into dinuclear hydrolysis.     

One-Photon Excitation Followed by a Three-Step Sequential Energy–Energy–Electron Transfer Leading to a Charge-Separated State in a Supramolecular Tetrad Featuring Benzothiazole–Boron-Dipyrromethene–Zinc Porphyrin–C60

A panchromatic triad, consisting of benzothiazole (BTZ) and BF₂-chelated boron-dipyrromethene (BODIPY) moieties covalently linked to a zinc porphyrin (ZnP) core, has been synthesized and systematically characterized by using ¹H NMR spectroscopy, ESI-MS, UV-visible, steady-state fluorescence, electrochemical, and femtosecond transient absorption techniques. The absorption band of the triad, BTZ-BODIPY-ZnP, and dyads, BTZ-BODIPY and BODIPY-ZnP, along with the reference compounds BTZ-OMe, BODIPY-OMe, and ZnP-OMe exhibited characteristic bands corresponding to individual chromophores. Electrochemical measurements on BTZ-BODIPY-ZnP exhibited redox behavior similar to that of the reference compounds. Upon selective excitation of BTZ (≈290 nm) in the BTZ-BODIPY-ZnP triad, the fluorescence of the BTZ moiety is quenched, due to photoinduced energy transfer (PEnT) from ¹BTZ^* to the BODIPY moiety, followed by quenching of the BODIPY emission due to sequential PEnT from the ¹BODIPY* moiety to ZnP, resulting in the appearance of the ZnP emission, indicating the occurrence of a two-step singlet–singlet energy transfer. Further, a supramolecular tetrad, BTZ-BODIPY-ZnP:ImC₆₀, was formed by axially coordinating the triad with imidazole-appended fulleropyrrolidine (ImC₆₀), and parallel steady-state measurements displayed the diminished emission of ZnP, which clearly indicated the occurrence of photoinduced electron transfer (PET) from ¹ZnP* to ImC₆₀. Finally, femtosecond transient absorption spectral studies provided evidence for the sequential occurrence of PEnT and PET events, namely, ¹BTZ^*-BODIPY-ZnP:ImC₆₀→BTZ-¹BODIPY^*-ZnP:ImC₆₀→BTZ-BODIPY-¹ZnP^*:ImC₆₀→BTZ-BODIPY-ZnP^.+:ImC₆₀^.− in the supramolecular tetrad. The evaluated rate of energy transfer, k_EnT, was found to be 3–5×10¹⁰ s⁻¹, which was slightly faster than that observed in the case of BODIPY-ZnP and BTZ-BODIPY-ZnP, lacking the coordinated ImC₆₀. The rate constants for charge separation and recombination, k_CS and k_CR, respectively, calculated by monitoring the rise and decay of C₆₀^.− were found to be 5.5×10¹⁰ and 4.4×10⁸ s⁻¹, respectively, for the BODIPY-ZnP:ImC₆₀ triad, and 3.1×10¹⁰ and 4.9×10⁸ s⁻¹, respectively, for the BTZ-BODIPY-ZnP:ImC₆₀ tetrad. Initial excitation of the tetrad, promoting two-step energy transfer and a final electron-transfer event, has been successfully demonstrated in the present study.     

A New Product Channel in the Energy Transfer of CO（ a，v'）+ NO（X）

Under single-collision conditions,a beam of metastable molecules CO（ a,v'）generated by DC discharge was allowed to collide with a beam of NO（X）at a fixed angle of 90o . The collision-induced emission from the interaction region was collected at right angles to the beam plane by a lens set and dispersed by a 1 m monochromator where a cooled photomultiplier tube was mounted on the exit slit. The signal from the PMT was transmitted via a discriminator,a photon counter and a boxcar integrator into a computer for storing and processing. Two broadband emissions were observed around the wavelengths of 780 and 860 nm,which can be assigned to NO（b-a） Ogawa bands Δv = + 4 and + 3 sequences,respectively,and referred to the spectroscopic data given by Huber. At the collision energy of 0. 05 eV in the present experimental conditions,the electronic energy of CO（ a,v' = 0）（6. 01 eV）was not enough to excite NO（X）to NO（b,v' = 4,5）（ΔE > 6. 11 eV）. So,what was in act in the energy transfer was the vibrational excitation of CO（a,v' > 0）,and the higher the vibrational excitation of CO（a,v'） was,the stronger the emission intensity of NO（ b-a）could be obtained. It is thought that electron exchange between CO（a）and NO（X）may be operative through the formation of a complex OCNO. The newly discovered formation of NO（ b）channel could be well explained considering the energy conservation,spin conservation and electron exchange mechanism.     

Directional Preference of DNA‐Mediated Electron Transfer in Gold‐Tethered DNA Duplexes: Is DNA a Molecular Rectifier?

Electrical properties of self‐assembling DNA nanostructures underlie the paradigm of nanoscale bioelectronics, and as such require clear understanding. DNA‐mediated electron transfer (ET) from a gold electrode to DNA‐bound Methylene Blue (MB) shows directional preference, and it is sequence‐specific. During the electrocatalytic reduction of [Fe(CN)₆]^3? catalyzed by DNA‐bound MB, the ET rate constant for DNA‐mediated reduction of MB reaches (1.32±0.2)10³ and (7.09±0.4)10³ s^?1 for (dGdC)₂₀ and (dAdT)₂₅ duplexes. The backward oxidation process is less efficient, making the DNA duplex a molecular rectifier. Lower rates of ET via (dGdC)₂₀ agree well with its disturbed π‐stacked sub‐molecular structure. Such direction‐ and sequence‐specific ET may be implicated in DNA oxidative damage and repair, and be relevant to other polarized surfaces, such as cell membranes and biomolecular interfaces.     

Does Fibronect in Influence the Determination of Circulating Immune Complexes by Means of a Clq-Enzyme Immunoassay?

Abstract

Fibronect in was shown to bind to solid-phase C1q and to inhibit the binding of aggregated lgG in an C1q-solid-phase enzyme immunoassay in the absence of human serum. In the presence of human serum the determination of aggregated lgG and circulating immune complexes is not influenced by fibronectin in this assay. Therefore, we suggest that fibronectin does not affect the determination of immune complexes in serum specimens by C1q binding assays.     

Molecular Tethering or Aggregation: Is the Existence of Charge‐Transfer Bands Indicative of the Formation of Blue‐Box/Tetrathiafulvalene Inclusion Complexes?

The interaction between tetrathiafulvalene and tetracation cyclobis(paraquat‐p‐phenylene) fragments—the key elements of many rotaxane systems—was investigated theoretically by using ab‐initio second‐order perturbation methods. In addition to the inclusion complex observed in the solid state, a thermodynamically stable “exterior” complex was identified. Calculation of the UV/Vis spectra for the inclusion and the exterior complexes indicated that the charge‐transfer band that is often used to predict the formation of the inclusion complexes in solution is, in reality, due to the exterior mode of complexation. These results suggest that UV/Vis spectroscopy is not a reliable method for assigning the complexation modes in TTF:BB⁴⁺ rotaxanes and related systems.     

Mechanism of Mukaiyama-Michael Reaction of Ketene Silyl Acetal: Electron Transfer or Nucleophilic Addition?

Mechanism of Mukaiyama-Michael reaction of ketene silyl acetal has been discussed. The competition reaction employing various types of ketene silyl acetals reveals that those bearing more substituents at the beta-position react preferentially over less substituted ones. However, when ketene silyl acetals involve bulky siloxy and/or alkoxy group(s), less substituted compounds react preferentially. The Lewis acids play an important role in these reactions. Enhanced preference for the more sterically demanding Michael adducts is obtained with Bu(2)Sn(OTf)(2), SnCl(4), and Et(3)SiClO(4) in the former reaction while TiCl(4) gives the highest selectivity for the less sterically demanding products in the latter case. These results are interpreted in terms of alternative reaction mechanisms. The reaction of less bulky ketene silyl acetals are initiated by electron transfer from these compounds to a Lewis acid. On the other hand, bulkier ketene silyl acetals undergo a ubiquitous nucleophilic reaction. Such a mechanistic change is discussed based on a variety of experimental results as well as the semiempirical PM3 MO calculations.