Observation of a reversible isomorphous phase transition and an interplay of ``sigma-holes'' and ``pi-holes'' in Fmoc-Leu-psiCH2-NCS]

Fmoc-Leu-psiCH2NCS] undergoes a reversible isomorphous phase transition upon cooling. The crystal structure at 100 K displays a short N=C=S center dot center dot center dot N=C=S intermolecular interaction, which has been characterized based on experimental charge density analysis, as a stabilizing interaction with both sigma-holes and pi-holes acting cooperatively.

An encaged sigma* orbital in 3-methoxy-2,4,10-trioxaadamantane. Preferred exo-anomeric effect as revealed by the crystal structure

In the titled tricyclic orthocarbonate derivative, the three endocyclic C-O bonds are longer than the exo-cyclic C-O bond (similar to 4.40 angstrom vs. similar to 1.37 angstrom). This indicates an anomeric-type interaction between the two electron lone pairs on the exocyclic oxygen atom and the antibonding orbitals of the two antiperiplanar endocyclic C-O bonds. The remaining endocyclic C-O bond - marginally shorter than the other two apparently adds to this effect. Intriguingly, the antibonding orbital of the exocyclic C-O bond extends into the interior of the adamantyl cage, and is stereoelectronically prevented from overlapping with any of the six adjacent lone pairs. The results also seem to indicate a preference for interaction between a single donor oxygen atom and multiple acceptor antibonding orbitals rather than vice versa. The results add insightfully to the substantial body of evidence favouring the antiperiplanar lone pair hypothesis (ALPH). (C) 2014 Elsevier B.V. All rights reserved.

Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

Crystallographic studies of the extracytoplasmic function sigma factor sigma(J) from Mycobacterium tuberculosis

Mycobacterium tuberculosis has multiple sigma factors which enable the bacterium to reprogram its transcriptional machinery under diverse environmental conditions. sigma(J), an extracytoplasmic function sigma factor, is upregulated in late stationary phase cultures and during human macrophage infection. sigma(J) governs the cellular response to hydrogen peroxide-mediated oxidative stress. sigma(J) differs from other canonical sigma factors owing to the presence of a SnoaL_2 domain at the C-terminus. sigma(J) crystals belonged to the tetragonal space group I422, with unit-cell parameters a = b = 133.85, c = 75.08 angstrom. Diffraction data were collected to 2.16 angstrom resolution on the BM14 beamline at the European Synchrotron Radiation Facility (ESRF).

Quantum and variational monte-carlo interaction potentials for li2 (x1-sigma-g+)

Optimized trial functions are used in quantum Monte Carlo and variational Monte Carlo calculations of the Li₂(X ¹Σ⁺_g) potential curve. The trial functions used are a product of a Slater determinant of molecular orbitals multiplied by correlation functions of electron—nuclear and electron—electron separation. The parameters of the determinant and correlation functions are optimized simultaneously by reducing the deviations of the local energy E_L (E_L  Ψ⁻¹_THΨ_T, where Ψ_T denotes a trial function) over a fixed sample. At the equilibrium separation, the variational Monte Carlo and quantum Monte Carlo methods recover 68% and 98% of the correlation energy, respectively. At other points on the curves, these methods yield similar accuracies.

Asymptotic scaling in the two-dimensional O(3) Nonlinear sigma model: a Monte Carlo study on parallel computers

We investigate the 2d O(3) model with the standard action by Monte Carlo simulation at couplings β up to 2.05. We measure the energy density, mass gap and susceptibility of the model, and gather high statistics on lattices of size L ≤ 1024 using the Floating Point Systems T-series vector hypercube and the Thinking Machines Corp.'s Connection Machine 2. Asymptotic scaling does not appear to set in for this action, even at β = 2.10, where the correlation length is 420. We observe a 20% difference between our estimate m/Λ^─_(Ms) = 3.52(6) at this β and the recent exact analytical result . We use the overrelaxation algorithm interleaved with Metropolis updates and show that decorrelation time scales with the correlation length and the number of overrelaxation steps per sweep. We determine its effective dynamical critical exponent to be z' = 1.079(10); thus critical slowing down is reduced significantly for this local algorithm that is vectorizable and parallelizable.

We also use the cluster Monte Carlo algorithms, which are non-local Monte Carlo update schemes which can greatly increase the efficiency of computer simulations of spin models. The major computational task in these algorithms is connected component labeling, to identify clusters of connected sites on a lattice. We have devised some new SIMD component labeling algorithms, and implemented them on the Connection Machine. We investigate their performance when applied to the cluster update of the two dimensional Ising spin model.

Finally we use a Monte Carlo Renormalization Group method to directly measure the couplings of block Hamiltonians at different blocking levels. For the usual averaging block transformation we confirm the renormalized trajectory (RT) observed by Okawa. For another improved probabilistic block transformation we find the RT, showing that it is much closer to the Standard Action. We then use this block transformation to obtain the discrete β-function of the model which we compare to the perturbative result. We do not see convergence, except when using a rescaled coupling β_E to effectively resum the series. For the latter case we see agreement for m/ Λ^─_(Ms) at , β = 2.14, 2.26, 2.38 and 2.50. To three loops m/Λ^─_(Ms) = 3.047(35) at β = 2.50, which is very close to the exact value m/ Λ^─_(Ms) = 2.943. Our last point at β = 2.62 disagrees with this estimate however.

Spectroscopic properties of Er3+-doped tellurite glass for 1.55 mu m optical amplifier

Er3+-doped TeO2-BaO (Li2O, Na2O)-La2O3 tellurite glass system was prepared and their density, characteristic temperatures and optical properties were determined and investigated. For the TeO2-BaO-La2O3-Er2O3 system, composition with 10 mol% BaO presented the highest thermal stability and good infrared transmittance. Intense and broad 1.53 mu m infrared fluorescence were observed under 977 nm diode laser excitation and the most full width at half-maximum (FWHM) is similar to 60nm. According to absorption spectrum, we calculated the optical parameters by means of Judd-Ofelt and McCumber theory such as the fluorescence lifetimes which are about 2.72-3.25 ms and the maximum emission cross-sections which are similar to 1.0pm(2) at 1.531 mu m. The sigma(e) x FWHM value of composition with 10 mol% BaO for gain bandwidth is similar to 600 exceeding those in silicon and phosphate glasses. Our results indicated this kind of tellurite glasses could be used as an ideal host glass for optical amplifier. (c) 2005 Elsevier B.V. All rights reserved.

Identificação da fase sigma em uma junta soldada pelo processo TIG manual autógeno de um aço hiperduplex SAF 2707HD (UNS S32707) por difração de raios-x.

O aço inoxidável hiperduplex possui alta resistência a corrosão por pite em ambientes contendo cloretos, quando comparado a outros aços inoxidáveis comercialmente conhecidos. Possui boas propriedades mecânicas, com limite de escoamento superior a 700MPa e limite de resistência a tração em torno de 1000MPa. Essas propriedades o tornam muito atrativos para aplicações em ambientes contendo cloretos, e por isso tem tido destaque na indústria de óleo e gás, refinarias, plataformas offshore, etc. A liga hiperduplex é composta por uma estrutura bifásica, contendo proporções aproximadamente iguais de ferrita e austenita. Esse material possui boa soldabilidade, mas por ser termodinamicamente metaestável, em altas temperaturas pode ocorrer a precipitação de fases intermetálicas não desejáveis, o que resulta em perda de propriedades mecânicas e diminuição da resistência a corrosão. A fase sigma tem sido fortemente estudada, pois é comum sua precipitação nos aços inoxidáveis da família duplex durante o procedimento de soldagem se este não for muito bem controlado. A fase sigma precipita preferencialmente na fase ferrítica, devido a maior concentração de Cr e Mo, que são os elementos formadores da fase. A resistência a corrosão é reduzida e as propriedades mecânicas do material são alteradas o tornando frágil devido a presença da fase sigma. É formada entre 600C e 1000C e possui uma estrutura tetragonal complexa. O objetivo do trabalho foi identificar a possível presença da fase sigma na junta soldada do aço inoxidável hiperduplex SAF 2707 HD (UNS S32707) pelo processo TIG autógeno manual através da difração de raios-x. Nessa pesquisa, foram analisadas uma junta soldada do material pelo processo TIG autógeno manual com arco pulsado. Complementando o estudo foram analisadas seis amostras do aço inoxidável superduplex, sendo que cinco amostras sofreram tratamento térmico para a proposital formação da fase sigma. O refinamento do resultado da difração das amostras foi feito utilizando o método de Rietveld no software Topas Academic versão 4.1. O resultado da amostra soldada de hiperduplex apresentou as fases austenita, ferrita e alguns prováveis óxidos. Os resultados das amostras de superduplex tratadas termicamente apresentaram a fase sigma, conforme esperado na pesquisa, e as fases austenita e ferrita.

Sigma-Delta模数转换器的设计研究

Submitted by zhangdi (zhangdi@red.semi.ac.cn) on 2009-04-13T11:45:31Z

高性能开关电流存储单元及其Sigma-Delta 调制器的研究

Submitted by zhangdi (zhangdi@red.semi.ac.cn) on 2009-04-13T11:45:31Z

A direct digital frequency synthesizer with fourth-order phase domain Delta Sigma noise shaper and 12-bit current-steering DAC

This paper presents a direct digital frequency synthesizer (DDFS) with a 16-bit accumulator, a fourth-order phase domain single-stage Delta Sigma interpolator, and a 300-MS/s 12-bit current-steering DAC based on the Q(2) Random Walk switching scheme. The Delta Sigma interpolator is used to reduce the phase truncation error and the ROM size. The implemented fourth-order single-stage Delta Sigma noise shaper reduces the effective phase bits by four and reduces the ROM size by 16 times. The DDFS prototype is fabricated in a 0.35-mu m CMOS technology with active area of 1.11 mm(2) including a 12-bit DAC. The measured DDFS spurious-free dynamic range (SFDR) is greater than 78 dB using a reduced ROM with 8-bit phase, 12-bit amplitude resolution and a size of 0.09 mm(2). The total power consumption of the DDFS is 200)mW with a 3.3-V power supply.

A direct digital frequency synthesizer with single-stage delta-sigma interpolator and current-steering DAC

This paper presents a direct digital frequency synthesizer (DDFS) with a 16-bit accumulator, a 4th-order single-stage pipelined delta-sigma interpolator and a 300MS/s 12-bit current-steering DAC based on Q(2) Random Walk switching scheme. The delta-sigma interpolator is used to reduce the phase truncation error and the ROM size. The measured spurious-free dynamic range (SFDR) is greater than 80 dB for 8-bit phase value and 12-bit sine-amplitude output. The DDFS prototype is fabricated in a 0.35um CMOS technology with core area of 1.11mm(2).

A direct digital frequency synthesizer with fourth-order phase domain Delta Sigma noise shaper and 12-bit current-steering DAC

This paper presents a direct digital frequency synthesizer (DDFS) with a 16-bit accumulator, a fourth-order phase domain single-stage Delta Sigma interpolator, and a 300-MS/s 12-bit current-steering DAC based on the Q(2) Random Walk switching scheme. The Delta Sigma interpolator is used to reduce the phase truncation error and the ROM size. The implemented fourth-order single-stage Delta Sigma noise shaper reduces the effective phase bits by four and reduces the ROM size by 16 times. The DDFS prototype is fabricated in a 0.35-mu m CMOS technology with active area of 1.11 mm(2) including a 12-bit DAC. The measured DDFS spurious-free dynamic range (SFDR) is greater than 78 dB using a reduced ROM with 8-bit phase, 12-bit amplitude resolution and a size of 0.09 mm(2). The total power consumption of the DDFS is 200)mW with a 3.3-V power supply.

A Novel 0.72-6.2GHz Continuously-Tunable Delta Sigma Fractional-N Frequency Synthesizer

This paper presents a wideband Delta Sigma-based fractional-N synthesizer with three integrated quadrature VCOs for multiple-input multiple-output (MIMO) wireless communication applications. It continuously covers a wide range frequency from 0.72GHz to 6.2GHz that is suitable for multiple communication standards. The synthesizer is designed in 0.13-um RE CMOS process. The dual clock full differential multi-modulus divide (MMD) with low power consumption can operate over 9GHz under the worst condition. In the whole range frequency from 0.72GHz to 6.2GHz, the maximal tuning range of the QVCOs reaches 33.09% and their phase noise is -119d8/Hz similar to 124d8/Hz @1MHz. Its current is less than 12mA at a 1.2V voltage supply when it operates at the highest frequency of 6.2GHz.