cis-Dihydroxylation and epoxidation of alkenes by [Mn(2)O(RCO(2))(2)(tmtacn)(2)]: tailoring the selectivity of a highly H(2)O(2)-efficient catalyst

The carboxylic acid promoted cis-dihydroxylation and epoxidation of alkenes catalyzed by [MnIV2O3(tmtacn)2]2+ 1 employing H2O2 as oxidant is described. The use of carboxylic acids at cocatalytic levels not only is effective in suppressing the inherent catalase activity of 1, but also enables the tuning of the catalyst's selectivity. Spectroscopic studies and X-ray analysis confirm that the control arises from the in situ formation of carboxylate-bridged dinuclear complexes, for example, 2 {[MnIII2O(CCl3CO2)2(tmtacn)2]2+} and 3 {[MnII2(OH)(CCl3CO2)2(tmtacn)2]+}, during catalysis. For the first time, the possibility to tune, through the carboxylate ligands employed, both the selectivity and activity of dinuclear Mn-based catalysts is demonstrated. To our knowledge, the system 1/2,6-dichlorobenzoic acid (up to 2000 turnover numbers for cis-cyclooctanediol) is the most active Os-free cis-dihydroxylation catalyst reported to date.     

Abstract multiparameter theory,I

In this paper we continue our investigation of multiparameter spectral theory. Let H₁,…, H_k be separable Hilbert spaces and H = ?_{r = 1}^kH_r, be their tensor product. In each space H_r we have densely defined self-adjoint operators T_r and continuous Hermitian operators V_rs. The multiparameter eigenvalue problem concerns eigenvalues λ = (λ₁,…, λ_n) ?R^k and eigenvectors $\text{? = ?}{}_1\text{? ··· ? ?}{}_{\mathrm{k}}\text{? H}$ such that $\text{T}{}_{\mathrm{r}}\text{?}{}_{\mathrm{r}}\text{+ ∑}{}_{\mathrm{s\; =\; 1}}{}^{\mathrm{k}}\text{λ}{}_{\mathrm{s}}\text{V}{}_{\mathrm{rs}}\text{?}{}_{\mathrm{r}}\text{= 0}$. We develop a spectral theory for such systems leading to a Parseval equality and generalized eigenvector expansion. The results are applied to a k × k system of linked secondorder differential equations.     

Structure in the subthreshold 232Th(n,f) cross section

The fission cross section of ²³²Th has been measured over the neutron energy range 0.1 MeV to 30 MeV at the Livermore 100 MeV electron linac. The observed structure in the cross section between 0.7 MeV and 1.4 MeV, attributed to vibrational states in the second well of the double-humped fission barrier, is clearly correlated with the angular anisotropy of fission fragments measured by others.     

Nonlinear multiparameter Sturm-Liouville problems

We study a linked system of nonlinear Sturm-Liouville equations in which the linking occurs via the spectral parameters. The system is the multiparameter analog of an equation recently discussed by R. E. L. Turner. We present an existence theorem for continua of solutions of the system—the solutions being required to have specified nodal properties.     

The effect of saccharides on the post-thaw recovery of cane toad (Bufo marinus) spermatozoa

The effect of monosaccharides (glucose, fructose) and disaccharides (maltose, sucrose, trehalose) as diluents, in cryoprotective additives containing 15% (v/v) DMSO or glycerol as cryoprotectants, were investigated on the recovery of sperm motility after cryopreservation of cane toad (Bufo marinus) spermatoazoa at low (approximately 5 degrees C/min(-1)) and high cooling rates (approximately 35 degrees C/min(-1)). The results show that: 1. recovery of percentage motility was higher with slow cooling than with high cooling rates (37.0 +/- 2.5%, 15.3 +/- 1.6%, P<0.001, respectively), 2. disaccharides were more effective than monosaccharides in protecting spermatozoa with slow cooling (43.9 +/- 1.2%, 26.8 +/- 2.5%, P<0.02, respectively), 3. glycerol was more effective than DMSO with fast cooling (18.3 +/- 2.2%, 12.6 +/- 2.3%, P<0.02, respectively), 4. trehalose with glycerol was the most effective cryoprotective additive with fast cooling (31.0 +/- 3.2%, P<0.05), and 5. overall the recovery of degree (vigour) of motility (range, 1.9 - 3.2) was more resilient to cryopreservation than recovery of percentage motility (range, 8.9 - 51.5 %). Comparison of post-thaw percentage and vigour of sperm motility up to 24 minutes after activation showed disaccharides supported greater duration sperm motility than monosaccharides This result and the recovery of spermatozoa immediately after freeze-thaw, show the main effect of saccharides are as cryoprotectants and not as exogenous energy substrates.     

Constraints on cosmological parameters from the analysis of the cosmic lens all sky survey radio-selected gravitational lens statistics

We derive constraints on cosmological parameters and the properties of the lensing galaxies from gravitational lens statistics based on the final Cosmic Lens All Sky Survey data. For a flat universe with a classical cosmological constant, we find that the present matter fraction of the critical density is Omega(m)=0.31(+0.27)(-0.14) (68%)+0.12-0.10 (syst). For a flat universe with a constant equation of state for dark energy w=p(x)(pressure)/rho(x)(energy density), we find w<-0.55(+0.18)(-0.11) (68%).     

Measurement of day and night neutrino energy spectra at SNO and constraints on neutrino mixing parameters

The Sudbury Neutrino Observatory (SNO) has measured day and night solar neutrino energy spectra and rates. For charged current events, assuming an undistorted 8B spectrum, the night minus day rate is 14.0%+/-6.3%(+1.5%)(-1.4%) of the average rate. If the total flux of active neutrinos is additionally constrained to have no asymmetry, the nu(e) asymmetry is found to be 7.0%+/-4.9%(+1.3%)(-1.2%). A global solar neutrino analysis in terms of matter-enhanced oscillations of two active flavors strongly favors the large mixing angle solution.     

Direct evidence for neutrino flavor transformation from neutral-current interactions in the Sudbury Neutrino Observatory

Observations of neutral-current nu interactions on deuterium in the Sudbury Neutrino Observatory are reported. Using the neutral current (NC), elastic scattering, and charged current reactions and assuming the standard 8B shape, the nu(e) component of the 8B solar flux is phis(e) = 1.76(+0.05)(-0.05)(stat)(+0.09)(-0.09)(syst) x 10(6) cm(-2) s(-1) for a kinetic energy threshold of 5 MeV. The non-nu(e) component is phi(mu)(tau) = 3.41(+0.45)(-0.45)(stat)(+0.48)(-0.45)(syst) x 10(6) cm(-2) s(-1), 5.3sigma greater than zero, providing strong evidence for solar nu(e) flavor transformation. The total flux measured with the NC reaction is phi(NC) = 5.09(+0.44)(-0.43)(stat)(+0.46)(-0.43)(syst) x 10(6) cm(-2) s(-1), consistent with solar models.     

Thermal states as universal resources for quantum computation with always-on interactions

Measurement-based quantum computation utilizes an initial entangled resource state and proceeds with subsequent single-qubit measurements. It is implicitly assumed that the interactions between qubits can be switched off so that the dynamics of the measured qubits do not affect the computation. By proposing a model spin Hamiltonian, we demonstrate that measurement-based quantum computation can be achieved on a thermal state with always-on interactions. Moreover, computational errors induced by thermal fluctuations can be corrected and thus the computation can be executed fault tolerantly if the temperature is below a threshold value.