Impact of Group 10 Metals on the Solvent-Induced Disproportionation of o-Semiquinonato Complexes

The oxidation of [M^II(3,5-DTBCat)(DTBbpy)] (M=Ni ( [Ni] ), Pd ( [Pd] ), and Pt ( [Pt] ); 3,5-DTBCat=3,5-di-tert-butylcatecholato; DTBbpy=4,4′-di-tert-butyl-2,2′-bipyridine) afforded the dimeric {[Ni^II(3,5-DTBSQ)(DTBbpy)](PF₆)}₂ ( {[Ni](PF₆)}₂ ; 3,5-DTBSQ=3,5-di-tert-butylsemiquinonato) and monomeric semiquinonato (SQ) complexes [M^II(3,5-DTBSQ)(DTBbpy)](PF₆) (M=Pd ( [Pd](PF₆) ) and Pt ( [Pt](PF₆) )). The negative solvatochromic properties of the SQ complexes allowed us to estimate the relative order of their dipole moments: [Pd](PF₆) > [Pt](PF₆) > {[Ni](PF₆)}₂ . The complexes [Pd](PF₆) and [Pt](PF₆) adopt monomeric structures and are stable in CH₂Cl₂ and toluene, whereas they gradually disproportionate at room temperature to [M] and 3,5-di-tert-butylbenzoquinone (3,5-DTBBQ) in polar solvents such as THF, MeOH, EtOH, DMF, or DMSO. The results of spectroscopic studies suggested that the oxidized nickel complex adopts a monomeric structure ( [Ni](PF₆) ) in CH₂Cl₂, but a dimeric structure ( {[Ni](PF₆)}₂ ) in the other investigated solvents. In polar solvents, {[Ni](PF₆)}₂ may disproportionate to [Ni] and 3,5-DTBBQ at 323 K, thereby demonstrating a significant solvent- and metal-dependence in temperature. The relative activities of {[Ni](PF₆)}₂ and [M](PF₆) toward disproportionation are related to the electrochemically estimated K_dis values in CH₂Cl₂ and DMF. The present work demonstrates that solvent polarity and the dipole moments of the SQ complexes promote disproportionation, which can be controlled by a judicious choice of the metal ion, solvent, and temperature.     

Stable meso–meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′-tetramesityl-10-10′-linked 3NH-corrole dimer with DDQ gave the corresponding triply linked 2NH-corrole tape, the use of an equimolar amount of p-chloranil as a milder oxidant resulted in the formation of a 10-10′-linked neutral 2NH-corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10-10′-linked bis-pyridine-coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Transcutaneous application of carbon dioxide improves contractures after immobilization of rat knee joint

Objective: Joint contractures are a major complication following joint immobilization. However, no fully effective treatment has yet been found. Recently, carbon dioxide (CO₂) therapy was developed and verified this therapeutic application in various disorders. We aimed to verify the efficacy of transcutaneous CO₂ therapy for immobilization-induced joint contracture. Method: Twenty-two Wistar rats were randomly assigned to three groups: caged control, those untreated after joint immobilization, and those treated after joint immobilization. The rats were treated with CO₂ for 20 min once a daily either during immobilization, (prevention) or during remobilization after immobilization (treatment). Knee extension motion was measured with a goniometer, and the muscular and articular factors responsible for contractures were calculated. We evaluated muscle fibrosis, fibrosis-related genes (collagen Type 1α1 and TGF-β1) in muscles, synovial intima''s length, and fibrosis-related proteins (Type I collagen and TGF-β1) in the joint capsules. Results: CO₂ therapy for prevention and treatment improved the knee extension motion. Muscular and articular factors decreased in rats of the treatment group. The muscular fibrosis of treated rats decreased in the treatment group. Although CO₂ therapy did not repress the increased expression of collagen Type 1α1, the therapy decreased the expression of TGF-β1 in the treatment group. CO₂ therapy for treatment improved the shortening of the synovial membrane after immobilization and decreased the immunolabeling of TGF-β1 in the joint capsules. Conclusions: CO₂ therapy may prevent and treat contractures after joint immobilization, and appears to be more effective as a treatment strategy for the deterioration of contractures during remobilization.     

Neutron-absorption deformable boron-rich ferrous alloys

The structure of the eutectic-type iron-boron alloys (up to 3.5 wt% B) crystallized at various velocities has been studied. It was established that due to temperature increase a coarse structure of the eutectic Fe+Fe₂B transforms into a fine dendritic structure. High-temperature annealing leads to the destruction of columnar construction of the eutectic phase and boride dendrites subsequently transform into the inclusions of spherical shape. These processes are more active at high velocities leading to decrease of strength properties and increase of elasticity of the alloys. Such treatment makes possible hot repartition of the ingots from the alloys Fe+3%B through their forging so that the ingots can be rolled into 3-5 mm thick platelets. The obtained product may serve as a material applicable for the preparation of neutron-absorption protective constructions.     

Complete thermal-unfolding profiles of oxidized and reduced cytochromes C

The complete thermal-unfolding profiles of both oxidized and reduced forms of cytochrome c551 (PA) from mesophilic Pseudomonas aeruginosa and cytochrome c552 (HT) from thermophilic Hydrogenobacter thermophilus were obtained by the newly developed pressure-proof cell compartment installed in a circular dichroic spectrometer, which facilitates protein thermal-unfolding experiments up to 180 degrees C. The thermodynamic cycle, which relates protein stability and redox function, indicated that the redox potentials of PA and HT in the native state are regulated by the stability of the oxidized proteins rather than by that of the reduced ones.     

Cleavage of a P=P Double Bond Mediated by N-Heterocyclic Carbenes

The reaction of the bulky diphosphenes (Rind)P=P(Rind) ( 1 ; Rind=1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl) with two molecules of N-heterocyclic carbene (NHC; 1,3,4,5-tetramethylimidazol-2-ylidene) resulted in the quantitative formation of the NHC-bound phosphinidenes NHC→P(Rind) ( 2 ), along with the cleavage of the P=P double bond. The reaction times are dependent on the steric size of the Rind groups (11 days for 2 a (R=Et) and 2 h for 2 b (R=Et, Me) at room temperature). The mechanism for the double bond-breaking is proposed to proceed via the formation of the NHC-coordinated, highly polarized diphospehenes 3 as an intermediate. Approach of a second NHC to 3 induces P−P bond cleavage and P−C bond formation, which proceeds through a transition state with a large negative Gibbs energy change to afford the two molecules of 2 , thus being the rate-determining step of the overall reaction with the activation barriers of 80.4 for 2 a and 29.1 kJ mol⁻¹ for 2 b .     

Trajectory of the spectral/structural rearrangements for photo-oxidative reaction of neat ketoprofen and its cyclodextrin complex

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Ketoprofen is a nonsteroidal anti-inflammatory drug used as mohrus tape which causes unwanted photosensitivity due to UV irradiation. In...     

Selective fabrication of n‐ and p‐type SnO films without doping

Undoped n‐ and p‐type tin monoxide (SnO) films have been selectively fabricated by pulsed laser deposition with a Sn target and careful control of oxygen partial pressure. The films are epitaxially grown in optimal growth conditions on yttria‐stabilized zirconia (YSZ) substrates with out‐of‐plane and in‐plane orientation relationships of (001)_SnO//(001)_YSZ and [110]_SnO//[100]_YSZ, respectively. Both Seebeck and Hall measurements show consistent results on the carrier types of the films. The electron Hall mobility is approximately 11 cm²/Vs at room temperature and the carrier activation energy is 0.14 eV for the n‐type film. The growth at increased oxygen partial pressure yields p‐type films, demonstrating the selective fabrication of both n‐ and p‐type SnO films without doping. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Chosen ciphertext secure keyed-homomorphic public-key cryptosystems

In homomorphic encryption schemes, anyone can perform homomorphic operations, and therefore, it is difficult to manage when, where and by whom they are performed. In addition, the property that anyone can “freely” perform the operation inevitably means that ciphertexts are malleable, and it is well-known that adaptive chosen ciphertext (CCA) security and the homomorphic property can never be achieved simultaneously. In this paper, we show that CCA security and the homomorphic property can be simultaneously handled in situations that the user(s) who can perform homomorphic operations on encrypted data should be controlled/limited, and propose a new concept of homomorphic public-key encryption, which we call keyed-homomorphic public-key encryption (KH-PKE). By introducing a secret key for homomorphic operations, we can control who is allowed to perform the homomorphic operation. To construct KH-PKE schemes, we introduce a new concept, transitional universal property, and present a practical KH-PKE scheme with multiplicative homomorphic operations from the decisional Diffie-Hellman (DDH) assumption. For \(\ell \)-bit security, our DDH-based KH-PKE scheme yields only \(\ell \)-bit longer ciphertext size than that of the Cramer–Shoup PKE scheme. Finally, we consider an identity-based analogue of KH-PKE, called keyed-homomorphic identity-based encryption and give its concrete construction from the Gentry IBE scheme.