Coordinated design of cofactor and active site structures in development of new protein catalysts

New methods for the synthesis of artificial metalloenzymes are important for the construction of novel biocatalysts and biomaterials. Recently, we reported new methodology for the synthesis of artificial metalloenzymes by reconstituting apo-myoglobin with metal complexes (Ohashi, M. et al., Angew Chem., Int. Ed. 2003, 42, 1005-1008). However, it has been difficult to improve their reactivity, since their crystal structures were not available. In this article, we report the crystal structures of M(III)(Schiff base).apo-A71GMbs (M = Cr and Mn). The structures suggest that the position of the metal complex in apo-Mb is regulated by (i) noncovalent interaction between the ligand and surrounding peptides and (ii) the ligation of the metal ion to proximal histidine (His93). In addition, it is proposed that specific interactions of Ile107 with 3- and 3'-substituent groups on the salen ligand control the location of the Schiff base ligand in the active site. On the basis of these results, we have successfully controlled the enantioselectivity in the sulfoxidation of thioanisole by changing the size of substituents at the 3 and 3' positions. This is the first example of an enantioselective enzymatic reaction regulated by the design of metal complex in the protein active site.     

Ultrasound assisted extraction and decomposition of Cl-containing herbicide involved in model soil

This work focused on ultrasound assisted extraction and decomposition of MCPA [(4-chloro-2-methylphenoxy) acetic acid] from model soil under argon atmosphere. In the experiments, 10 g model soil containing 1.75 x 10(-5) mol MCPA mixed with 90 g of de-aired water was used. For a comparison, the experiments were also carried out using MCPA aqueous solution of which the concentration was adjusted to 1.75 x 10(-4) mol/l. The results showed that complete MCPA decomposition was achieved after 120 min in the case of MCPA aqueous solution. Meanwhile, in the case of model soil, the MCPA decomposition ratio of 0.9 was obtained after 600 min. This result was attributed to combined effect of MCPA adsorption on kaolin and to attenuation of ultrasound by solid particles of kaolin. To evaluate ultrasound attenuation in the presence of solid particles, experiments with slurry consisting of alumina particles and MCPA solution were carried out at alumina particles concentration range of 0.1-100g/l. The results showed that the MCPA initial decomposition rate significantly decreased with an increase in alumina particles concentration. Thus, it was concluded that the solid particles reduced the MCPA decomposition ratio by reducing the formation of reactive species such as hydroxyl radicals which are know to be necessary for MCPA decomposition.     

Crystal Transformation and Development of Tensile Properties upon Drawing of Poly(L-lactic acid) by Solid-State Coextrusion: Effects of Molecular Weight

Melt-crystallized films of poly(L -lactic acid) (PLLA) with M_v in the range of 3.8 ∼ 46 × 10⁴ consisting of α-form crystals were uniaxially drawn by solid-state coextrusion. The effects of M_v, extrusion draw ratio (EDR), and extrusion temperature (T_ext) on the crystal/crystal transformation from α- to β-form crystals and the resultant tensile properties of drawn products were studied. The crystal transformation proceeded with EDR and more rapidly for the higher M_v's. Furthermore, the crystal transformation proceeded most rapidly with EDR at a T_ext around 130 °C, independently of the M_v's. As a result of the optimum combination of processing variables influencing the the crystal transformation (M_v, T_ext, and drawability), highly oriented films consisting of β-form crystals alone were obtained by coextrusion of higher M_v samples at T_ext's slightly below the melting temperature (150 ∼ 170 °C) and at higher EDR's > 11. Both the tensile modulus and strength increased rapidly with EDR. The modulus at a given EDR was slightly higher for the samples with higher M_v's. In contrast, the strength at a given EDR was remarkably higher for the higher M _v's. The highest tensile modulus of 8.0 GPa and strength of 500 MPa were obtained with the sample of the highest M_v of 46 × 10⁴ coextruded at 170 °C to the highest EDR of 14.     

An objective quality assessment method for bit-reduction coding of wideband speech.

This paper proposes a new objective quality assessment method for bit-reduction coding of wideband speech taking into account the masking effect of quantizing noise. First, this paper analyzes the reliability and sensitivity of the speech quality assessment method, based on a paired-comparison test with a modulated noise reference signal, for the bit-reduction coding of high-quality wideband speech. Then, the perception of quantizing noise is studied using speech with noise synthesized similar to the quantizing noise. The detection of quantizing noise is found to be influenced by masking by the source signal. This leads to a new method of objectively estimating the quality of coding speech by multiple regression analysis. The factors for the estimation are segmental signal-to-noise ratio, spectrum envelope distance between source signal and quantizing noise, and the similarity of the noise power envelope to the source signal in the time domain. This estimation method is applied to the parameter optimization of wideband coding systems.     

Investigation of experimental observables in search of the chiral magnetic effect in heavy-ion collisions in the STAR experiment

The chiral magnetic effect(CME)is a novel transport phenomenon,arising from the interplay between quantum anomalies and strong magnetic fields in chiral systems.In high-energy nuclear collisions,the CME may survive the expansion of the quark-gluon plasma fireball and be detected in experiments.Over the past two decades,experimental searches for the CME have attracted extensive interest at the Relativistic Heavy Ion Collider(RHIC)and the Large Hadron Collider(LHC).The main goal of this study is to investigate three pertinent experimental approaches:the$\gamma$correlator,the R correlator,and the signed balance functions.We exploit simple Monte Carlo simulations and a realistic event generator(EBE-AVFD)to verify the equivalence of the core components among these methods and to ascertain their sensitivities to the CME signal and the background contributions for the isobar collisions at the RHIC.     

New Hofmann-like spin crossover compound with 3,5-lutidine

A new type III of 3,5-lutidine spin crossover coordination compound with formula Fe(3,5-lutidine)₂Ni(CN)₄·2[(H₂O)(3,5-lutidine)] 2c has been obtained. The ratio of the high spin state (HS) iron (II) changing to the low spin state (LS) iron (II) in 2c is higher than that of type I and type II 3,5-lutidine coordination polymer 2a and 2b previously reported. ⁵⁷Fe Mössbauer spectra of 2c show two different doublets which correspond to HS1 (inner doublet lines) and HS2 (outer doublet lines). The intensity of the HS1 doublet decreases on cooling to 80 K while the intensity of another component, the LS singlet, increases. The 90 % of the HS1 doublet change to the LS singlet is probably due to suitable environments of octahedral iron (II) ions coordinated by four nitrogen atoms of cyano groups and two nitrogen atoms of 3,5-lutidine ligands. We also prepared the Hofmann-like 3,5-dichloropyridine coordination compound Fe(3,5-dichloropyridine)₂Ni(CN)₄ ·2[(3,5-dichloropyridine)(H₂O)] 2d to compare it with 2c. ⁵⁷Fe Mössbauer spectra of 2d show that 2d is not a spin crossover coordination compound.     

An improved synthesis of the C42–C52 segment of ciguatoxin 3C

In our previously reported method for the construction of the IJKLM-ring of ciguatoxin 3C (CTX3C), the lengthy synthetic process for the intermediate C42–C52 (L-ring) segment was problematic. Therefore, a new and improved procedure for the C42–C52 segment, having modified protecting groups, was developed. The new route includes a chirality transferring Ireland-Claisen rearrangement for the construction of the vicinal dimethyl branching at C47–48, a one-pot cyclization process for the establishment of the stereocenters at C45 and C46 as well as the γ-hydroxy δ-lactone framework corresponding to the L-ring, and Brown’s asymmetric crotylboration for the installation of the stereocenters at C43 and C44. The new C42–C52 segment was successfully coupled with the previously reported C32–C41 (I-ring) segment to produce the IJKLM-ring.     

Photoelectrochemical reaction and H2 generation at zero bias optimized by carrier concentration of n-type GaN

The authors studied the photoelectrochemical properties dependent on carrier concentration of n-type GaN. The photocurrent at zero bias became the maximum value at the carrier concentration of 1.7x10(17) cm-3. Using the sample optimized carrier concentration, the authors achieved H2 gas generation at a Pt counterelectrode without extra bias for the first time. The authors also discussed the mechanism of the dependence of photocurrent on the carrier concentration of GaN.     

Numerical study comparing RANS and LES approaches on a circulation control airfoil

A numerical study over a nominally two-dimensional circulation control airfoil is performed using a large-eddy simulation code and two Reynolds-averaged Navier–Stokes codes. Different Coanda jet blowing conditions are investigated. In addition to investigating the influence of grid density, a comparison is made between incompressible and compressible flow solvers. The incompressible equations are found to yield negligible differences from the compressible equations up to at least a jet exit Mach number of 0.64. The effects of different turbulence models are also studied. Models that do not account for streamline curvature effects tend to predict jet separation from the Coanda surface too late, and can produce non-physical solutions at high blowing rates. Three different turbulence models that account for streamline curvature are compared with each other and with large eddy simulation solutions. All three models are found to predict the Coanda jet separation location reasonably well, but one of the models predicts specific flow field details near the Coanda surface prior to separation much better than the other two. All Reynolds-averaged Navier–Stokes computations produce higher circulation than large eddy simulation computations, with different stagnation point location and greater flow acceleration around the nose onto the upper surface. The precise reasons for the higher circulation are not clear, although it is not solely a function of predicting the jet separation location correctly.