DeltaE Degrees Research Articles

ChemInform Abstract: From Homoleptic to Heteroleptic Double Stranded Copper(I) Helicates: The Role of Self-Recognition in Self-Assembly Processes.

The ligands 2,9-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6' ',6' -bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl)]-2' ',2' -bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl]-2, 2'-bithiophene (7), and 6,6'-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-2,2'-biphenyl (8) and their respective homo- and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu(3)](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu(3)](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu(2)](2+) complexes. The potential shift, DeltaE degrees (,) of the Cu(+)/Cu(2+) redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu(+) as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cu(+). Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.

Anthracene-Bridged Binuclear Ruthenium Complexes: Electrochemical and Spectroscopic Evidence of Electronic Communication Through the π System

Six dinuclear cyclometalated ruthenium complexes, 1-6, based on diphenylanthracene (DPA) and anthracene (AN) as bridging ligands have been synthesized and fully characterized electrochemically and spectroscopically. The anodic electrochemistry of the homobinuclear ruthenium complexes, 1-6, has been examined in three different nonaqueous solvents (ACN, DMF, and CH(2)Cl(2)). The ability of the anthracene derivatives to transmit electronic effects between the two redox units has been demonstrated by the observed splitting of the voltammetric signals ascribed to the metal centers. The electronic communication has also been evidenced by the presence of intervalence charge transfer transition bands in the near-infrared region of the spectrum due to an intramolecular electron transfer process mediated by the bridge when the mixed valence species (Ru(II)/Ru(III)) are electrochemically generated. Cyclic voltammetric measurements have been carried out under different conditions of solvent and supporting electrolyte. Differences in DeltaE degrees', the potential separation of the formal potentials of the metal-based anodic processes, have been observed and found to depend on the medium employed. These differences have been ascribed to different degrees of ion pairing. Such effects can be, in turn, modulated as a function of not only the polarity and donor strength of the solvent but also of the coordinating capacity of the anion employed as a supporting electrolyte.

Correlation of exhaled breath temperature with bronchial blood flow in asthma

In asthma elevated rates of exhaled breath temperature changes (Δe°T) and bronchial blood flow (Qaw) may be due to increased vascularity of the airway mucosa as a result of inflammation.We investigated the relationship of Δe°T with Qaw and airway inflammation as assessed by exhaled nitric oxide (NO). We also studied the anti-inflammatory and vasoactive effects of inhaled corticosteroid and β2-agonist.Δe°T was confirmed to be elevated (7.27 ± 0.6 Δ°C/s) in 19 asthmatic subjects (mean age ± SEM, 40 ± 6 yr; 6 male, FEV1 74 ± 6 % predicted) compared to 16 normal volunteers (4.23 ± 0.41 Δ°C/s, p < 0.01) (30 ± 2 yr) and was significantly increased after salbutamol inhalation in normal subjects (7.8 ± 0.6 Δ°C/ s, p < 0.05) but not in asthmatic patients. Qaw, measured using an acetylene dilution method was also elevated in patients with asthma compared to normal subjects (49.47 ± 2.06 and 31.56 ± 1.6 μl/ml/min p < 0.01) and correlated with exhaled NO (r = 0.57, p < 0.05) and Δe°T (r = 0.525, p < 0.05). In asthma patients, Qaw was reduced 30 minutes after the inhalation of budesonide 400 μg (21.0 ± 2.3 μl/ml/min, p < 0.05) but was not affected by salbutamol.Δe°T correlates with Qaw and exhaled NO in asthmatic patients and therefore may reflect airway inflammation, as confirmed by the rapid response to steroids.

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeIIcomplexes

The effects of pressure and temperature on the energy (Eop) of the metal-to-metal charge transfer (MMCT, FeII-->CoIII) transition of the cyano-bridged complexes trans-[L14CoNCFe(CN)5]- and cis-[L14CoNCFe(CN)5]- (where L14=6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus-Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in Eop due to both pressure and temperature were found to be less than the shifts in the energy difference (DeltaE degrees]) between the CoIII-FeII and CoII-FeIII redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of CoII, are discussed in order to account for this trend. To study the effect of pressure on CoIII electronic absorption bands, a new cyano-bridged complex, trans-[L14CoNCCo(CN)5], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans-[L14CoNCFe(CN)5].5H2O.

Intramolecular charge transfer and biomimetic reaction kinetics in galactose oxidase model complexes.

One-electron oxidation of two structurally similar CuII-diphenolate complexes, 1 and 2, creates EPR-silent CuII-phenoxyl complexes [1]+ and [2]+ that mimic the oxidized form of the enzyme galactose oxidase (GOase). Both model complexes display novel NIR absorptions assigned to phenolate-phenoxyl charge transfer that resemble a tyrosinate-tyrosyl charge-transfer band observed in the enzymatic system. [1]+ and [2]+ react with benzyl alcohol to form 0.5 equivs of benzaldehyde per complex; biomimetic reduction to CuI-phenol complexes is not observed, but such species may exist transiently. Initial kinetic studies show that [2]+ reacts faster with benzyl alcohol than does [1]+, despite being a significantly weaker oxidant (DeltaE degrees = 370 mV). This acceleration is ascribed to mechanistic differences: [2]+ appears to bind substrate prior to the rate-determining step. Large, nonclassical kinetic isotope effects confirm C-H bond cleavage as the rate-determining step in the reactions of both [1]+ and [2]+ with benzyl alcohol, as is the case for GOase.

Faster rise of exhaled breath temperature in asthma: a novel marker of airway inflammation?

In asthma there is increased vascularity of the airway mucosa, altering heat loss in the airways. We hypothesized that as a result of these inflammatory changes, asthmatic patients would have elevated rates of the exhaled air temperature increase (Deltae degrees T). We measured Deltae degrees T in 18 asthmatic subjects (mean age +/- SEM, 38 +/- 8 yr; 9 male, FEV(1) 74 +/- 10%) and 16 normal volunteers (mean age +/- SEM, 33 +/- 3 yr) and compared it with exhaled nitric oxide (NO) as a marker of inflammation. Deltae degrees T was measured during a flow- and pressure-controlled single exhalation with a fast response (1 ms) thermometer. The end-expiratory plateau temperature was similar in asthmatic compared with normal subjects (35.75 +/- 0.6 degrees C and 34.45 +/- 0.8 degrees C, p > 0.05). However, Deltae degrees T was greater in asthmatic subjects (8.17 +/- 0.83 degrees C/s and 4.12 +/- 0.41 degrees C/s, p < 0.01) and correlated with NO (r = 0.65, p = 0.034). Deltae degrees T was increased in normal subjects (from 4.28 +/- 0.8 degrees C/s to 7.60 +/- 0.5 degrees C/s, p < 0.01) but not in asthmatic patients (from 8.28 +/- 0.41 degrees C/s to 8.80 +/- 0.41 degrees C/s, p > 0.05) after the inhalation of albuterol, indicating that Deltae degrees T may reflect bronchial blood flow. Asthmatic subjects have elevated Deltae degrees T. This may represent a novel, noninvasive means of measuring airway blood flow and inflammation in asthma.

Electronic structure contributions to electron transfer in blue Cu and Cu(A).

The experimentally determined electronic structures of mononuclear blue Cu and binuclear Cu(A) centers are summarized and their relation to intra- and inter-protein electron transfer (ET) kinetics are described. Specific contributions of the electronic structures of these two broad classes of Cu ET proteins to H(AB), lambda, and deltaE degrees are discussed. Also, the role of the protein structure in determining key geometric features which define the electronic structures of the metal sites in these proteins is considered.

From homoleptic to heteroleptic double stranded Copper(I) helicates: the role of self-recognition in self-assembly processes

The ligands 2,9-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6' ',6' "-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl)]-2' ',2' "-bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl]-2, 2'-bithiophene (7), and 6,6'-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-2,2'-biphenyl (8) and their respective homo- and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu(3)](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu(3)](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu(2)](2+) complexes. The potential shift, DeltaE degrees (,) of the Cu(+)/Cu(2+) redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu(+) as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cu(+). Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.

Effects of nonspecific ion-protein interactions on the redox chemistry of cytochrome c.

The effects of the ionic atmosphere on the enthalpic and entropic contributions to the reduction potential of native (state III) beef heart cytochrome c have been determined through variable-temperature direct electrochemistry experiments. At neutral or slightly alkaline pH values, from 5 to 50 degrees C, the reduction enthalpy and entropy become less negative with decreasing ionic strength. The reduction entropy extrapolated at null ionic strength is approximately zero, indicating that, in the absence of the screening effects of the salt ions on the network of the electrostatic interactions at the protein-solvent interface, the solvation properties and the conformational flexibility of the two redox states are comparable. The moderate decrease in E degrees' observed with increasing ionic strength [DeltaE degrees'IS = (E degrees')I = 0.1 M - (E degrees')I = (0)M = -0.035 V at 25 degrees C], once the compensating enthalpic and entropic effects of the salt-induced changes in the hydrogen bonding within the hydration sphere of the molecule in the two redox states are factored out, results in being ultimately determined by the stabilizing enthalpic effect of the negatively charged ionic atmosphere on the ferri form. At pH 9, the ionic strength dependence of the reduction termodynamics of cytochrome c follows distinctive patterns, possibly as a result of specific binding of the hydroxide ion to the protein. A decrease in ionic strength at constant pH, as well as a pH increase at constant ionic strength, induces a depression of the temperature of the transition from the low-T to high-T conformer of cytochrome c, which suggests that a temperature-induced decrease in the pK(a) for a residue deprotonation is the key event of this conformational change.

Novel Cofacial Ruthenium(II) Porphyrin Dimers and Tetramers.

A series of cofacially arranged ruthenium(II) porphyrin dimers 1-5 having a variety of axial ligands such as CO, pyridine, and 4-cyanopyridine, were synthesized. Porphyrin tetramers, 6 and 7, which have pyridylporphyrin ligands at the axial positions of the parent cofacial ruthenium(II) dimers, were also prepared. These porphyrin dimers and tetramers were characterized by (1)H NMR spectroscopy, ESI (electrospray ionization)-mass spectroscopy, and elemental analysis. The ruthenium porphyrin dimers and tetramers exhibited characteristic electrochemical and spectroscopic properties caused by interactions between the porphyrin subunits. Stepwise oxidations of the porphyrin rings or the ruthenium ions in the cofacial dimer skeltons were observed in the cyclic voltammograms. The potential differences (DeltaE degrees ' mV) of the oxidation steps were larger than 260 mV for all the porphyrin oligomers. The Soret bands of the cofacial dimers were significantly broadened by excitonic interactions between the two porphyrin subunits. Furthermore, the mixed-valence states of 3-7 showed specific intervalence charge-transfer (IT) bands between the Ru(II) and Ru(III) cores in the near-IR region at around 1500 nm.