Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton-Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF₄)₂. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF₄)₂ by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF₄) regenerates protonated complex [ 1 ](BF₄)₂. In presence of acetic acid in acetonitrile solvent [ 1 ](BF₄)₂ shows electrocatalytic proton reduction with a k_obs of ≈200 s⁻¹ at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a Co^II−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.     

An efficient route to regioselective opening of N-tosylaziridines with zinc(II) halides

An efficient route for the regio- and stereoselective ring opening of N-tosylaziridines with zinc dihalides (ZnX₂, X = Cl, Br, I) is described. Depending on the solvent and Zn(II) halide, β-halo amines or imidazolines are obtained selectively in good to excellent yields.     

Biyclo[2.2.1]heptane as cyclopentane precursor. Part 4 Stereocontrolled syhthesis of a potential intermediate to chromophycane dolastane and clavularane

The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively.     

Do nonplanar distortions of porphyrins bring about strongly red-shifted electronic spectra? Controversy,consensus, new developments,and relevance to chelatases

TDDFT calculations confirm a controversial proposal by DiMagno and co-workers that ruffling distortions, by themselves, do not bring about sizable red shifts in the electronic absorption spectra of "simple" nontransition-metal porphyrins. We now report that the same also holds for saddling distortions. The situation is more complex for transition metal porphyrins. For example, ruffling does bring about strong red shifts in the electronic spectra of nickel porphyrins because of a specific metal(d)-porphyrin(pi) orbital interaction.     

Doubly excited3Se,3De and3Ge states of two-electron atomic systems

Summary Time-dependent perturbation theory has been applied to calculate the doubly excited triplet statesNsns:³S^e,Npnp:³D^e andNdnd:³G^e (N=2, 3, 4,n=N+1, ... ,5) for He, Li⁺, Be²⁺ and B³⁺. A time-dependent harmonic perturbation causes simulataneous excitation of both the electrons with a change of spin state. The doubly excited energy levels have been identified as the poles of an appropriately constructed linearized variational functional with respect to the driving frequency. In addition to the transition energies, effective quantum numbers of these doubly excited states have been calculated and analytic representations of their wave functions are obtained. These are utilized to estimate the Coulomb repulsion term for these states which checks the consistency of the wave functions. These wave functions may also be used for calculating other physical properties of the systems.     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.     

Effect of pyridine on the kinetics of polymerization of methyl methacrylate initiated by benzoyl peroxide and azobisisobutyronitrile at 60°C

Solution polymerization of MMA, with pyridine as the solvent and BZ₂O₂ and AIBN as thermal initiators, was studied kinetically at 60°C. The monomer exponent varied from 0.45 to 0.91 as [BZ₂O₂] was increased from 1 × 10^?2 to 30 × 10^?2 mole/liter in a concentration range of 8.3-4.6 mole/liter for MMA. For AIBN-initiated polymerization the monomer exponent remained constant at 0.69 as [AIBN] varied from 0.4 × 10^?2 to 1.0 × 10^?2 mole/liter in the same concentration range for MMA. The k²_p/k_t Value increased in both cases with an increase in pyridine concentration in the system. This was explained in terms of an increase in the k_p value, which was due presumably to the increased reactivity of the chain radicals by donor-acceptor interaction between the molecules of solvent pyridine and propagating PMMA radicals and in terms of lowering the k_t value for the diffusion-controlled termination reaction due to an increase in the medium viscosity and pyridine content.     

Liesegang rings — Part I

Summary The conditions for the formation of revert type ofLiesegang rings have been studied here. Various systems of rhythmic precipitations of silver chromate are produced in a mixtures of agar and gelatin gels under different environmental conditions. Ring systems of silver, copper and other ferricyanides have also been studied in gelatin gel. The observations show that the cause of the revert systems ofLiesegang rings is the high peptizability of the precipitating matter in the media containing gel and the unreacted ions.

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Zusammenfassung Die Bedingungen der Bildung des „umgekehrten“ Types vonLiesegang-Ringen wurden untersucht. Verschiedene Systeme rhythmischer F?llung von Silberchromat wurden in einer Mischung von Agar und Gelatinegelen unter verschiedenen Umgebungsbedingungen erzeugt. Ringsysteme von Kupfer, Silber und anderen Ferricyaniden in Gelatine wurden untersucht. Die Beobachtungen zeigen, da? die Ursache für die „umgekehrten“Liesegang-Ringe in der hohen Peptisierbarkeit der Füllsubstanz im gelhaltigen Medium und den noch nicht reagierten Ionen liegt.

     

Über die Eigenschaften hydratisierten Chromoxydes. Teil V

Ohne ZusammenfassungÜbersetzt von Dr. K. Jäckel, Marburg/L.Wir danken Herrn Prof. N. R. Dhar D.Sc. (London und Paris), F.R.I.C., F.N.I., I.E.S. (Eetd) Direktor Shila Dhar Institut für Bodenkunde und Vorstand der Chemischen Abteilung, Universität Allahabad, für sein lebhaftes Interesse und seine Ratschläge für die Arbeit.     

Synthesis and antispasmodic activity evaluation of bis-(papaverine) analogues

A new series of N-substituted bis-(tetrahydropapaverine) ring systems have been synthesised in expectation of better antispasmodic activity in comparison with papaverine. The synthesis of the targeted heterocycles is described along with a discussion of their structure activity relationship. The general synthetic methods of bis-(tetrahydropapaverine) analogues involve tetrahydropapaverine, various piperazines, diisocyanates and diisothiocyanates as starting materials. Pharmacological evaluation involves the in vitro antispasmodic activity on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, N,N'-bis-[2-carbamoyl-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolinyl]piperazine (22), was found to be the most potent muscle relaxant (IC(50): 0.31 microM).