Local similarity in organic crystals and the non-uniqueness of X-ray powder patterns

Two new concepts for molecular solids, 'local similarity' and 'boundary-preserving isometry', are defined mathematically and a theorem which relates these concepts is formulated. 'Locally similar' solids possess an identical short-range structure and a 'boundary-preserving isometry' is a new mathematical operation on a finite region of a solid that transforms mathematically a given solid to a locally similar one. It is shown further that the existence of such a 'boundary-preserving isometry' in a given solid has infinitely many 'locally similar' solids as a consequence. Chemical implications, referring to the similarity of X-ray powder patterns and patent registration, are discussed as well. These theoretical concepts, which are first introduced in a schematic manner, are proved to exist in nature by the elucidation of the crystal structure of some diketopyrrolopyrrole (DPP) derivatives with surprisingly similar powder patterns. Although the available powder patterns were not indexable, the underlying crystals could be elucidated by using the new technique of ab initio prediction of possible polymorphs and a subsequent Rietveld refinement. Further ab initio packing calculations on other molecules reveal that 'local crystal similarity' is not restricted to DPP derivatives and should also be exhibited by other molecules such as quinacridones. The 'boundary-preserving isometry' is presented as a predictive tool for crystal engineering purposes and attempts to detect it in crystals of the Cambridge Structural Database (CSD) are reported.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

LOCAL MAIN-CHAIN DYNAMICS OF PHENOLPHTHALEIN POLYETHERSULFONE

Local main chain dynamics of dissolved phenolphthalein polyethersulfone (PES-C) in solution with chloroform-d(1) were examined through C-13 NMR relaxation measurements. Spin-lattice relaxation times and NOE (nuclear Overhauser effects) factors were measured as a function of temperature. The relaxation data were interpreted in terms of main chain segmental motion by using the damped orientational diffusion model (DAMP) and the conformation jump model (VJGM) derived by Valeur, Jarry, Geny, and Monnerie. The simulation method used is N-SIMPLEX, which gives, in this study, a result of the object function less than 10(-4). Correlation times were obtained for the main chain motion of PES-C with these models and the results indicate that the main chain of PES-C are flexible. The comparison between PES-C and 1,2-polybutadiene is proposed. The distribution of the correlation time for the main chain motion by using VJGM model is discussed. The temperature dependence of correlation times for PES-C indicating the dynamical rigidity of its chains is obtained.

ENHANCED AMPEROMETRIC DETECTOR FOR LOCAL-ANESTHETICS IN LIQUID-CHROMATOGRAPHY WITH METAL-OXIDE DISPERSED GLASSY-CARBON ELECTRODES

Chemically modified electrodes (CMEs) prepared by the dispersion of metal oxide particles on a glassy carbon (GC) substrate greatly enhance the voltammetric response and amperometric detection of local anesthetics following liquid chromatography (LC). The enhancement is more pronounced with the GC electrodes dispersed by the metal oxides of higher oxidation states (+3, +4) and for the species exhibiting relatively slow electrode kinetics under given conditions. With an applied potential of 1.2 V (vs. SCE), LC amperometric detection of the analytes at the alpha-alumina modified GC surface gives detection limits 2-5 times lower than those obtained at the bare electrode. The metal oxide-dispersed electrodes display significant improvement in sensitivity, and selectivity and indicate excellent preparation reproducibility and performance stability.

Refining near-native protein-protein docking decoys by local resampling and energy minimization

How to refine a near-native structure to make it closer to its native conformation is an unsolved problem in protein-structure and protein-protein complex-structure prediction. In this article, we first test several scoring functions for selecting locally resampled near-native protein-protein docking conformations and then propose a computationally efficient protocol for structure refinement via local resampling and energy minimization. The proposed method employs a statistical energy function based on a Distance-scaled Ideal-gas REference state (DFIRE) as an initial filter and an empirical energy function EMPIRE (EMpirical Protein-InteRaction Energy) for optimization and re-ranking. Significant improvement of final top-1 ranked structures over initial near-native structures is observed in the ZDOCK 2.3 decoy set for Benchmark 1.0 (74% whose global rmsd reduced by 0.5 angstrom or more and only 7% increased by 0.5 angstrom or more). Less significant improvement is observed for Benchmark 2.0 (38% versus 33%). Possible reasons are discussed.

A broad deglacial delta C-13 minimum event in planktonic foraminiferal records in the Okinawa Trough

The equatorial Pacific upwelling zone has been suspected of playing an important role in the global atmospheric CO2 changes associated with glacial-interglacial cycles. In order to assess the influencing scope of the surface water deglacial delta(13)C minimum in the tropical low-latitude Pacific, the core DGKS9603, collected from the middle Okinawa Trough, was examined for 4513 C records of planktonic foraminifera N. dutertrei and G. ruber. The planktonic foraminiferal delta(13)C records show a clear decreasing event from 20 to 6 cal. kaBP., which is characterized by long duration of about 14 ka and amplitude shift of 0.4 x 10(-3). Its minimum value occurred at 15.7 cal kaBP. The event shows fairly synchrony with the surface water deglacial delta(13)C minimum identified in the tropical Pacific and its marginal seas. Because there is no evidence in planktonic foraminiferal fauna and 45180 records for upwelling and river runoff enhancement, the broad deglacial delta(13)C minimum event in planktonic foraminiferal records revealed in core DGKS9603 might have been the direct influencing result of the deglacial surface water of the tropical Pacific. The identification for the event in the Okinawa Trough provides new evidence that the water evolution in the tropical low-latitude Pacific plays a key role in large regional, even global carbon cycle.

Responses of summertime extreme wave heights to local climate variations in the East China Sea

We detected the responses of summertime extreme wave heights (H-top10, average of the highest 10% of significant wave heights in June, July and August) to local climate variations in the East China Sea by applying an empirical orthogonal function analysis to Htop10 derived from the WAVEWATCH- III wave model driven by 6 hourly sea surface wind fields from ERA-40 reanalysis over the period 1958-2002. Decreases in H-top10 in the northern East China Sea ( Yellow Sea) correspond to attenuation of the East Asian Summer Monsoon, while increases in the south are primarily due to enhancement of tropical cyclone activities in the western North Pacific.

Statistical distribution of depth-integrated local horizontal momentum for second-order random ocean waves in finite water depth

Based on the second-order random wave solutions of water wave equations in finite water depth, statistical distributions of the depth- integrated local horizontal momentum components are derived by use of the characteristic function expansion method. The parameters involved in the distributions can be all determined by the water depth and the wave-number spectrum of ocean waves. As an illustrative example, a fully developed wind-generated sea is considered and the parameters are calculated for typical wind speeds and water depths by means of the Donelan and Pierson spectrum. The effects of nonlinearity and water depth on the distributions are also investigated.

环境因子对有毒赤潮生物微型原甲藻（Prorocentrum minimum）生长增殖的影响

本文研究了温度、盐度、PH、营养盐（N、P）；维生素（B_(12)、B_1）、微量元素（Fe、Mn）、底泥抽提液和赤潮生物骨条藻与微型原甲藻生长的关系。结果表明，微型原甲藻增殖生长的适温范围为20－30 ℃，28 ℃时有最大生长率；最适盐度为10－35‰，25‰盐度生长率最高；PH 7.18-8.72范围内生长良好，影响不明显。N、P营养盐能促进微型原甲藻增殖生长，N盐以硝态氮效果最好，容易被吸收利用；氨盐为唯一N源时效果较差，浓度超过100uM时则有抑制作用；亚硝酸盐作用不明显。微型原甲藻主要是利用无机磷；有机磷作唯一P源时不能有效地被吸收利用，对微型原甲藻生长不利；维生素B_(12)促进微型原甲藻增殖生长效果明显，B_(12)与B_1综合效果更好；底泥抽提液、微量元素Fe、Mn都能有效地促进微型原甲藻增殖生长；研究证实底泥中腐植酸（HFA）虽有促进生长的作用，但效果尚不及抽提液，推测可能还有其他有效成分。研究发现中肋骨条藻有刺激微型原甲藻生长的作用，但其具体作用成分还有待研究。所得这些结果对进一步研究阐明微型原甲藻赤潮成因和机理有重要科学意义。

A comparison of future increased CO2 and temperature effects on sympatric Heterosigma akashiwo and Prorocentrum minimum

Very little is known about how global anthropogenic changes will affect major harmful algal bloom groups. Shifts in the growth and physiology of HAB species like the raphidophyte Heterosigma akashiwo and the dinoflagellate Prorocentrum minimum due to rising CO2 and temperature could alter their relative abundance and environmental impacts in estuaries where both form blooms, such as the Delaware Inland Bays (DIB). We grew semi-continuous cultures of sympatric DIB isolates of these two species under four conditions: (1) 20 degrees C and 375 ppm CO2 (ambient control), (2)20 degrees C and 750 ppm CO2 (high CO2),(3) 24 degrees C and 375 ppm CO2 (high temperature), and (4) 24 degrees C and 750 ppm CO2 (combined). Elevated CO2 alone or in concert with temperature stimulated Heterosigma growth, but had no significant effect on Prorocentrum growth. P-Bmax (the maximum biomass-normalized light-saturated carbon fixation rate) in Heterosigma was increased only by simultaneous CO2 and temperature increases, whereas P-Bmax in Prorocentrum responded significantly to CO2 enrichment, with or without increased temperature. CO2 and temperature affected photosynthetic parameters alpha, Phi(max), E-k, and Delta F/F'(m) in both species. Increased temperature decreased and increased the Chl a content of Heterosigma and M Prorocentrum, respectively. CO2 availability and temperature had pronounced effects on cellular quotas of C and N in Heterosigma, but not in Prorocentrum. Ratios of C:P and N:P increased with elevated carbon dioxide in Heterosigma but not in Prorocentrum. These changes in cellular nutrient quotas and ratios imply that Heterosigma could be more vulnerable to N limitation but less vulnerable to P-limitation than Prorocentrum under future environmental conditions. In general, Heterosigma growth and physiology showed a much greater positive response to elevated CO2 and temperature compared to Prorocentrum, consistent with what is known about their respective carbon acquisition mechanisms. Hence, rising temperature and CO2 either alone or in combination with other limiting factors could significantly alter the relative dominance of these two co-existing HAB species over the next century. (c) 2007 Elsevier B.V. All rights reserved.

Local warming about 1.3 degrees C in alpine meadow has no effect on root vole (Microtus oeconomus L.) population during winter

The influence of air and soil warming on root vole (Microtus oeconomus L.) population was studied in winter period in top open chambers (OTC) (0.8-1.8 m(2) warmed by conical fiberglass material and situated in alpine meadow (3250 m) at Qinghai-Tibet Plateau, China. The OTCs were distributed on an area of 30 x 30 m of experimental warming site; another site of the same area was a control one. The root vole population was investigated on two pairs of sites in "low-grazing" and "high-grazing" (by sheep) parts of the meadow; mark-recapture method was used. The winter-season averaged air and soil temperature inside of the chambers were 1.3 degrees C higher than the temperature outside the chambers. The warming in the chambers had no statistically significant effect on root vole numbers, on average body mass of individual, and on average body mass of males and females. In conclusion, as small as 1.3 degrees C warming of soil and air introduced locally and on small (several m(2)) scale, in the alpine meadow habitat in winter period, has possibly no effect on root vole numbers and biomass.

基于势场法的移动机器人路径规划仿真研究

针对势场法的障碍物附近目标不可达(GNRON)问题,采用改进斥力势场函数,把机器人和目标的相对距离考虑进去,从而确保目标点为整个势场的全局最小点,使得机器人能够顺利到达目标。针对局部极小引起的陷阱区域问题,提出了增加引导点的方法,使得机器人能够快速走出陷阱区域,向目标点移动。通过仿真实验,还实现了机器人在限定区域内漫游。改进后的势场法适用于复杂环境下的移动机器人路径规划。仿真结果证明了此方法的有效性。

基于SVD和能量最小原则的图像自适应降噪算法

基于奇异值分解和能量最小原则,提出了一种自适应图像降噪算法,并给出了基于有界变差的能量降噪模型的代数形式。通过在矩阵范数意义下求能量最小,自适应确定去噪图像重构的奇异值个数。该算法的特点是将能量最小法则和奇异值分解结合起来,在代数空间中建立了一种自适应的图像降噪算法。与基于压缩比和奇异值分解的降噪方法相比,由于该算法避免了图像压缩比函数及其拐点的计算,因此具有快速去噪和简单可行的优点。实验结果证明,该算法是有效的。

利用BP神经网络实现三维物体姿态的测定

本文利用BP(Back-Propagation)人工神经网络对三维物体的姿态测定进行了研究。姿态测定一直缺少通用而实际的方法,人工神经网络由于具有强大的自组织、自适应学习能力,迅速的并行信息处理能力,可望解决这个问题。但现有BP算法存在训练慢和易陷入局部最小两个问题.本文提出的级联形式网络结构,使BP网络的训练速度大为提高,陷入局部最小的可能性大为降低。利用这种级联结构对飞机模型姿态测定,取得了较好的实验结果。