Chemistry of a novel zerovalent ruthenium π-acidic alkene complex,Ru (η6-1,3,5-cyclooctatriene)(η2-dimethyl fumarate)2

A novel zerovalent ruthenium complex with a π-acidic ligand, Ru(η⁶-cyclooctatriene)(η²-dimethyl fumarate)₂ (1), was prepared from Ru(η⁴-cyclooctadiene)(η⁶-cyclooctatriene) [Ru(cod)(cot)]. Complex 1 or Ru(cod)(cot) catalyzes various new carbon-carbon bond-forming reactions that include the [2 + 2] cycloaddition of alkenes and alkynes via ruthenacycles, the creation of a new hydrocarbon, pentacyclo[6.6.0.0^2,6.0^3,13.0^10,14]tetradeca-4,11-diene [PCTD], by dimerization of 2,5-norbornadiene via C-C bond cleavage, and the codimerization of alkynes and/or alkenes. Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes. Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands. The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a ‘chiral water’ ligand were prepared and fully characterized.     

The diamond principle for the uniformity of the meager ideal implies the existence of a destructible gap

We prove the theorem from the title which answers a question addressed in the paper of Moore-Hrusak-Dzamonja [3].Supported by JSPS Research Fellowshipsfor Young Scientists.Supported by Grants-in-Aid for JSPS Fellow, No. 16.3977, Ministry of Education, Culture, Sports, Science and Technology.     

Genetic engineering of the heme pocket in human serum albumin: modulation of O2 binding of iron protoporphyrin IX by variation of distal amino acids

Complexing an iron protoporphyrin IX into a genetically engineered heme pocket of recombinant human serum albumin (rHSA) generates an artificial hemoprotein, which can bind O2 in much the same way as hemoglobin (Hb). We previously demonstrated a pair of mutations that are required to enable the prosthetic heme group to bind O2 reversibly: (i) Ile-142-->His, which is axially coordinated to the central Fe2+ ion of the heme, and (ii) Tyr-161-->Phe or Leu, which makes the sixth coordinate position available for ligand interactions [I142H/Y161F (HF) or I142H/Y161L (HL)]. Here we describe additional new mutations designed to manipulate the architecture of the heme pocket in rHSA-heme complexes by specifically altering distal amino acids. We show that introduction of a third mutation on the distal side of the heme (at position Leu-185, Leu-182, or Arg-186) can modulate the O2 binding equilibrium. The coordination structures and ligand (O2 and CO) binding properties of nine rHSA(triple mutant)-heme complexes have been physicochemically and kinetically characterized. Several substitutions were severely detrimental to O2 binding: for example, Gln-185, His-185, and His-182 all generated a weak six-coordinate heme, while the rHSA(HF/R186H)-heme complex possessed a typical bis-histidyl hemochrome that was immediately autoxidized by O2. In marked contrast, HSA(HL/L185N)-heme showed very high O2 binding affinity (P1/2O2 1 Torr, 22 degrees C), which is 18-fold greater than that of the original double mutant rHSA(HL)-heme and very close to the affinities exhibited by myoglobin and the high-affinity form of Hb. Introduction of Asn at position 185 enhances O2 binding primarily by reducing the O2 dissociation rate constant. Replacement of polar Arg-186 with Leu or Phe increased the hydrophobicity of the distal environment, yielded a complex with reduced O2 binding affinity (P1/2O2 9-10 Torr, 22 degrees C), which nevertheless is almost the same as that of human red blood cells and therefore better tuned to a role in O2 transport.     

Relationship between the bubble temperature and main oxidant created inside an air bubble under ultrasound

Numerical simulations of nonequilibrium chemical reactions in a pulsating air bubble have been performed for various ultrasonic frequencies (20 kHz, 100 kHz, 300 kHz, and 1 MHz) and pressure amplitudes (up to 10 bars). The results of the numerical simulations have indicated that the main oxidant is OH radical inside a nearly vaporous or vaporous bubble which is defined as a bubble with higher molar fraction of water vapor than 0.5 at the end of the bubble collapse. Inside a gaseous bubble which is defined as a bubble with much lower vapor fraction than 0.5, the main oxidant is H2O2 when the bubble temperature at the end of the bubble collapse is in the range of 4000-6500 K and O atom when it is above 6500 K. From the interior of a gaseous bubble, an appreciable amount of OH radical also dissolves into the liquid. When the bubble temperature at the end of the bubble collapse is higher than 7000 K, oxidants are strongly consumed inside a bubble by oxidizing nitrogen and the main chemical products inside a bubble are HNO2, NO, and HNO3.     

Suppression of sonochemiluminescence reduction at high acoustic amplitudes by the addition of particles

The effect of particle addition to a liquid or liquid surface on the sonochemiluminescence (SCL) was investigated using a luminol aqueous solution under ultrasonic treatment at 154 kHz. The acoustic-amplitude dependence of the SCL intensity was measured, in addition to capturing images of luminescent spatial patterns. At higher acoustic amplitudes, the cavitation efficiency dramatically reduces. This behavior is suppressed in the presence of particles. Particle addition provides nucleation sites for cavitation bubbles, lowering the cavitation threshold, and weakening the liquid surface vibration as the pressure amplitude decreases. It is shown that the reduction in SCL is suppressed under the addition of alumina particles into luminol aqueous solution. As the amount of alumina particles increases, the range of acoustic amplitude for suppressing the reduction in SCL is enlarged toward high amplitude, and the intensity of the SCL increases. Simultaneous addition of alumina particles into the solution and hydrophobic polytetrafluoroethylene (Teflon) particles onto the liquid surface is also effective. Examination of SCL images revealed that alumina particles added to the liquid at high acoustic amplitude caused the entire region of the reaction volume to be homogeneously luminous. If hydrophobic particles cover the solution surface, the surface vibration at high acoustic amplitude is fixed and the sound field becomes stable. This is responsible for suppression of the reduction in SCL and leads to a high rate of sonochemical reaction, even at high acoustic amplitude.     

FEM calculation of an acoustic field in a sonochemical reactor

The spatial distribution of the acoustic amplitude in a sonochemical reactor has been numerically calculated using the finite element method (FEM). In the FEM program, the acoustic field in a sonochemical reactor is coupled with the vibration of the reactor's wall. The present calculations have revealed that the thin (thick) glass or stainless steel wall is nearly a free (rigid) boundary and that the glass wall is freer than the stainless steel wall. The influence of the attenuation coefficient of ultrasound on the acoustic field has also been studied in order to see the effect of bubbles on the acoustic field. As the attenuation coefficient increases, the vibration amplitude of the reactor's wall becomes smaller and the acoustic emission from the vibrating wall becomes weaker. The qualitative feature of the spatial pattern of sonochemiluminescence from an aqueous luminol solution has been reproduced by the calculation when the attenuation coefficient is in the range of 0.5-5m(-1). When the attenuation coefficient is less than about 0.05 m(-1), the standing wave pattern of an acoustic field in the liquid is very complex due to the acoustic emission from the vibrating wall. The present calculations have also revealed that some stripes of pressure antinodes have also been disconnected when the radius of the transducer is much smaller than the side length of the vibrating plate. The dependence of the acoustic field on the liquid height is also discussed.