高分子聚合物的湍流减阻机理

对链状高分子聚合物进行球-棍模型简化,使得在描述其减阻机理时更加直观形象。利用流体流动控制方程和高分子本构方程进行直接数值模拟,根据模拟结果研究聚合物的主要减阻机理。在湍流条件下,聚合物反向扭矩从根本上抑制了湍流发卡型漩涡的迸发和再生,进而减少流体的湍流脉动及流动阻力损失。其中,聚合物的正向扭矩作用在发卡型漩涡的拱形头部和第2个发卡型漩涡的腿部,抑制湍流漩涡的迸发频率和强度,减少新的发卡型漩涡的生成;聚合物的反向扭矩作用在发卡型漩涡的卷曲方向,可以减小漩涡的弯曲率和倾斜角度。     

Neutron-mapping polymer flow: scattering, flow visualization, and molecular theory

Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent "tube model" molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.     

Modes of tilting during extensional core complex development

Crustal extension and formation of the Mineral Mountains core complex, Utah, involved tilting of the Mineral Mountains batholith and associated faults during hanging wall and footwall deformation. The batholith was folded in the hanging wall of the Beaver Valley fault between 11 and 9 million years ago yielding about 45 degrees of tilt. Subsequently, the batholith was unroofed along the Cave Canyon detachment fault, and the batholith and fault were tilted approximately 40 degrees during footwall uplift. Recognition of deformed dikes beneath the detachment fault establishes the importance of footwall tilt during formation of extensional core complexes and demonstrates that footwall rebound can be an important process during extension.     

Linking models of polymerization and dynamics to predict branched polymer structure and flow

We present a predictive scheme connecting the topological structure of highly branched entangled polymers, with industrial-level complexity, to the emergent viscoelasticity of the polymer melt. The scheme is able to calculate the linear and nonlinear viscoelasticity of a stochastically branched "high-pressure free radical" polymer melt as a function of the chemical kinetics of its formation. The method combines numerical simulation of polymerization with the tube/entanglement physics of polymer dynamics extended to fully nonlinear response. We compare calculations for a series of low-density polyethylenes with experiments on structural and viscoelastic properties. The method provides a window onto the molecular processes responsible for the optimized rheology of these melts, connecting fundamental science to process in complex flow, and opens up the in silico design of new materials.     

Helical conformation of alkanes in a hydrophobic cavitand

Alkanes adopt extended conformations in solution that minimize steric interactions and maximize surface area. Folding can reduce the amount of hydrophobic surface exposed to solvent, but sterically unfavorable gauche interactions result. However, we found that the alkyl chains of two common surfactants in aqueous solution adopt helical conformations when bound within a synthetic receptor. The receptor recognizes the helical alkane better than the extended conformation, even though 2 to 3 kilocalories per mole of strain is introduced. The proper filling of space and burial of hydrophobic surface drive the molecular recognition between the receptor and the coiled alkane.     

Protein conformation in solution: cross-linking of lysozyme

The cross-linking of lysozyme by reaction with phenol-2,4-disulfonyl chloride has been effected. The cross-linked protein retained enzymatic activity, has approximately the same molecular weight as native lysozyme, and has essentially the same conformation as native lysozyme as judged by optical rotatory dispersion analysis. The positions of sulfonylation were assigned by a standard degradation sequence; the presence of sulfonamide bonds was confirmed by infrared spectroscopy. Cross-links may thus be introduced without incurring major structural changes in the protein, and certain intramolecular distances that are allowed in the active enzyme may be deduced.     

Solution conformation of valinomycin-potassium ion complex

The complete conformation of the valinomycin-potassium ion complex in methanol is presented. Extension from the reported secondary structure requires arguments and data relating to ester orientation, direction of coiling, side-chain orientation, and conformational stability. Conformation of the valinomycin-potassium ion complex provides a clear-cut example in which elucidation of conformation is sufficient to gain an understanding of molecular function which, in this case, is selective ion transport by a carrier mechanism.     

南海北部陆缘地壳结构及其伸展破裂过程的差异性

系统分析了南海北部地壳岩石圈结构及其新生代伸展变形的差异性,并探讨了其成因机制。基于南海北部陆缘重磁震联合反演所获得的Moho面深度和地壳厚度,发现地壳的伸展薄化具有“南北分带、东西分段”差异,由北向南可分为陆架均匀薄化带(地壳伸展系数β<1.2)、上陆坡楔形薄化带(1.2<β<2)、下陆坡强烈薄化带(β>2)共3个带;而陆缘深水区由东向西以4条NW-SE向基底隐伏断裂带为界可分为5段：台西南盆地陆缘,珠江口盆地陆缘的东段陆缘、中段陆缘、西段陆缘,琼东南盆地陆缘。不同区段地壳薄化程度交替变化,强烈薄化区呈指状向陆延伸,其所对应的沉积盆地断裂样式、充填结构、裂后沉降、岩浆活动等均表现出不同特征。上述差异表明,南海北部陆缘岩石圈在新生代的伸展薄化过程中,显著受控于先存中生代主动陆缘所形成的基底构造格局及其所对应的岩石圈结构差异;在伸展过程中岩浆大量底侵至下地壳,其热效应导致下地壳的韧性增强,进而改变地壳薄化方式,而先存NE-SW向走滑断裂成为伸展过程中岩浆大量底侵至下地壳的通道。依据岩石圈结构差异及其与沉积盆地响应关系,可将南海北部陆缘岩石圈伸展破裂过程总结为自上而...     

Trends in polymer development

Polymer science and technology has flourished as polymers with many new compositions have been, synthesized. The range of properties attainable has been continually extended, providing materials with higher strength, better reinforcing capabilities, and greater resistance to extreme thermal and corrosive environments. Examples of evolutionary developments in the polyamides, the fluorocarbon resins, and the aromatic engineering plastics are used to illustrate the trends. It is expected that this process will continue in order to meet changing needs and that emphasis will be put on selective polymer design for specific applications.     

DNA conformation, dynamics, and interactions in solution

The conformation and dynamics of the d(CGCGAATTCGCG) duplex, its analogs containing mismatched base pairs and helix interruptions, and its complexes with actinomycin and Netropsin, bound separately and simultaneously, have been investigated by nuclear magnetic resonance spectroscopy in aqueous solution. Structural information has been deduced from chemical shift and nuclear Overhauser effect parameters, while the kinetics have been probed from line width and saturation recovery experiments on proton and phosphorus markers at the individual base pair level. These studies lead to an improved understanding of the role of nucleic acid sequence on the structure, flexibility, and conformational interconversions in the duplex state. The nuclear magnetic resonance measurements readily identify helix modification and antibiotic binding sites on the nucleic acid and estimate the extent to which the observed conformational and dynamic perturbations are transmitted to adjacent base pair regions.     

考虑吸附滞后的页岩气藏流动物质平衡方程

页岩气是一种以游离、吸附、溶解状态赋存于泥页岩中的非常规天然气,可以有效缓解能源短缺问题。动用储量的准确计算对页岩气藏开采及合理生产、减少储量损失具有重要意义。已有学者研究发现页岩气解吸存在滞后现象,但目前的页岩气藏动用储量计算方法尚未考虑吸附滞后理论。从物质平衡的角度出发,在页岩气藏吸附滞后理论的基础上提出了一种新的页岩气储层流动物质平衡方程。该方法综合考虑了页岩气藏裂缝、基质中游离气和基质中吸附气、干酪根中的溶解气以及吸附相体积变化的影响,并修正了气体的偏差因子和综合压缩系数,改进了页岩气藏储量的计算方法。实例证明,采用Langmuir吸附等温式计算得到的吸附气量远小于采用解吸等温式计算的吸附气量,吸附滞后效应对剩余吸附气储量的影响显著;裂缝中的游离气约占总储量的8.83%。因此,在进行页岩气藏储量评价时应考虑吸附滞后效应及天然裂缝的影响,令储量计算模型更贴合实际。     

Distal conformation of the thyroid hormone 3,5,3'-triiodo-L-thyronine

In the crystal structure of the thyroid hormone, 3,5,3'-triiodo-L-thyronine, the 3' iodine is observed in the distal position, away from the alaninebearing ring of the thyroid hormone. This result had been anticipated from stereochemical and biological activity studies. However, previous observations of structures in which the 3' iodine was proximal had cast some doubt on the stability of the 3' distal conformation. This observation suggests that the relative energies of the two conformers is similar and that perhaps the barrier to rotation is not as great as previously supposed since both the distal and proximal conformers have now been observed in the solid state.     

Conversion of PrP to a self-perpetuating PrPSc-like conformation in the cytosol

A rare conformation of the prion protein, PrPSc, is found only in mammals with transmissible prion diseases and represents either the infectious agent itself or a major component of it. The mechanism for initiating PrPSc formation is unknown. We report that PrP retrogradely transported out of the endoplasmic reticulum produced both amorphous aggregates and a PrPSc-like conformation in the cytosol. The distribution between these forms correlated with the rate of appearance in the cytosol. Once conversion to the PrPSc-like conformation occurred, it was sustained. Thus, PrP has an inherent capacity to promote its own conformational conversion in mammalian cells. These observations might explain the origin of PrPSc.     

Physical aging in polymer glasses

Physical aging refers to structural relaxation of the glassy state toward the metastable equilibrium amorphous state, and it is accompanied by changes in almost all physical properties. These changes, which must be taken into account in the design, manufacture, and use of glassy polymer materials and devices, present a daunting challenge to theorists.     

用滞回曲线法表征含蜡原油的触变过程

随着温度的降低,含蜡原油发生胶凝,此过程中由于形成蜡晶结构,整个原油体系表现出触变特性,其对于输油管道停输再启动压力的计算起着决定性作用。采用滞回曲线法对大庆原油和马惠原油的触变过程进行实验研究,结果表明:表征含蜡原油触变性相对强弱的滞回环面积的对数值随温度升高而线性递减,且偏差值都在1%以内。在凝点温度附近用滞回曲线法和按照SY/T7547-1996标准测得含蜡原油屈服值的结果偏差在10%以内,并且在凝点温度时该值偏差最小。     

Absence of correlation between base-pair sequence and RNA conformation

A survey of all available double-stranded RNA crystal structures shows that there is a considerable range of variation in local conformation of a given base-pair doublet, but that there is no significant correlation between base-pair sequence and RNA local conformation.     

Phosphorus-proton spin-spin coupling and conformation of a dinucleoside phosphate

The phosphorus-31 nuclear magnetic resonance spectrum of beta-adenosine-3'-beta-adenosine-5'-phosphoric acid in its aqueous solution (pH = 9.2) was studied. The signal consisted of eight peaks caused by the spin-spin coupling of the phosphorus nucleus with three protons, two on the 5' carbon, and one on the 3' carbon. The coupling constants were 3.4, 6.5, and 8.1 hertz; from these values the dihedral angles of the three P-O-C-H systems were estimated.     

An inward-facing conformation of a putative metal-chelate-type ABC transporter

The crystal structure of a putative metal-chelate-type adenosine triphosphate (ATP)-binding cassette (ABC) transporter encoded by genes HI1470 and HI1471 of Haemophilus influenzae has been solved at 2.4 angstrom resolution. The permeation pathway exhibits an inward-facing conformation, in contrast to the outward-facing state previously observed for the homologous vitamin B12 importer BtuCD. Although the structures of both HI1470/1 and BtuCD have been solved in nucleotide-free states, the pairs of ABC subunits in these two structures differ by a translational shift in the plane of the membrane that coincides with a repositioning of the membrane-spanning subunits. The differences observed between these ABC transporters involve relatively modest rearrangements and may serve as structural models for inward- and outward-facing conformations relevant to the alternating access mechanism of substrate translocation.