Formation of crystal nuclei near critical supersaturation in small volumes

This work deals with the nucleation of crystals in confined systems in response to the recent high interest in research on crystallization in emulsion and microemulsion droplets. In these confined systems, crystallization often occurs at high supercooling; thus, nucleation determines the overall crystallization process. A decrease in the volume of the confined mother phase leads to the higher supercooling needed for the phase transition. We have numerically solved kinetic equations in order to determine the conditions under which the first crystal nuclei are formed by homogeneous and heterogeneous nucleation from supercooled melt and supersaturated solution, depending on the volume of the mother phase. Supersaturation (or supercooling) increases with decreasing volume of the mother phase. The nucleation barrier depends linearly on the logarithm of volume of the mother phase in all cases under consideration, as follows from the numerical solution of kinetic equations.     

Configuration dependent critical nuclei in the self assembly of magic clusters

Evidence for the formation of various 2-D structures possessing different numbers of Co-Si magic clusters (size approximately 10.0 +/- 0.5 A), configurations and lifetimes are studied in real time on a Si(111)-(7 x 7) surface at elevated temperature in the STM. Observations of individual cluster diffusion, attachment and detachment dynamics resolve unequivocally the question of self assembly over surface reconstruction. The smallest stable structure consisting of seven individual Co-Si magic clusters arranged in a hexagonal closed packed formation (i = 7) is found to retain sufficient cohesive energy to avoid dissociation. A configuration dependent critical 2-D nuclei (i* = 6) is determined to exist in facilitating the self assembly dynamics.     

Surface tension and scaling of critical nuclei in diatomic and triatomic fluids

Density functional theory has been used to investigate surface tension and scaling of critical clusters in fluids consisting of diatomic and rigid triatomic molecules. The atomic sites are hard spheres with attractive interactions obtained from the tail part of the Lennard-Jones potential. Asymmetry in attractive interactions between the atomic sites has been introduced to cause molecular orientation and oscillatory density profiles at liquid-vapor interfaces. The radial dependence of cluster surface tension in fluids showing modest orientation in unimolecular layer at the interface or no orientation at all resembles the surface tension behavior of clusters in simple monoatomic fluids, although the surface tension maximum becomes more pronounced with increasing chain length of the molecule. Surface tension of clusters having multiple oscillatory layers at the interface shows a prominent maximum at small cluster sizes; however, the surface tension of large clusters is lower than the planar value. The scaling relation for the number of molecules in the critical cluster and the nucleation barrier height developed by McGraw and Laaksonen [Phys. Rev. Lett. 76, 2754 (1996)] are well obeyed for fluids with little structure at liquid-vapor interface. However, fluids having enhanced interfacial structure show some deviation from the particle number scaling, and the barrier height scaling breaks up seriously.     

Fluid phase separation inside a static periodic field: an effectively two-dimensional critical phenomenon

When a fluid with a bulk liquid-vapor critical point is placed inside a static external field with spatial periodic oscillations in one direction, a new phase arises. This new phase-the so-called "zebra" phase-is characterized by an average density roughly between that of the liquid and vapor phases. The presence of the zebra phase gives rise to two new phase transitions: one from the vapor to the zebra phase, and one from the zebra to the liquid phase. At appropriate values of the temperature and chemical potential, the latter two transitions become critical. This phenomenon is called laser-induced condensation [I. O. Go?tze, J. M. Brader, M. Schmidt, and H. Lo?wen, Mol. Phys. 101, 1651 (2003)]. The purpose of this paper is to elucidate the nature of the critical points, using density functional theory and computer simulation of a colloid-polymer mixture. The main finding is that critical correlations develop in two-dimensional sheets perpendicular to the field direction, but not in the direction along the field: the critical correlations are thus effectively two-dimensional. Hence, static periodic fields provide a means to confine a fluid to effectively two dimensions. Away from criticality, the vapor-zebra and liquid-zebra transitions become first-order, but the associated surface tensions are extremely small. The consequences of the extremely small surface tensions on the nature of the two-phase coexistence regions are analyzed in detail.     

Reorganization and growth of metastable alpha-N2 critical nuclei into stable beta-N2 crystals

We report on results on the crystal nucleation and growth of nitrogen. Using molecular dynamics simulations, we show that while nucleation proceeds into the metastable alpha-phase (i.e., the crystalline phase associated with the lowest free energy barrier of formation), growth of the crystallite proceeds through a reorganization of the nucleus into the thermodynamically stable beta-phase.     

Evaluation of parameters critical to observing proteins inside living Escherichia coli by in-cell NMR spectroscopy

Our recently developed in-cell NMR procedure now enables one to observe protein conformations inside living cells. Optimization of the technique demonstrates that distinguishing the signals produced by a single protein species depends critically on protein overexpression levels and the correlation time in the cytoplasm. Less relevant is the selective incorporation of (15)N. Poorly expressed proteins, insoluble proteins, and proteins that cannot tumble freely due to associations within the cell cannot yet be observed. We show in-cell NMR spectra of bacterial NmerA and human calmodulin and discuss limitations of the technique as well as prospects for future applications.     

Catalysis inside dendrimers

Catalytic sites can be placed at the core, at interior positions or at the periphery of a dendrimer. There are many examples of the use of peripherally functionalized dendrimers in catalysis and this subject has been thoroughly reviewed in the recent literature. This review is concerned only with dendrimer based catalysis involving catalytic sites at the core of a dendrimer and within the interior voids. In covering the significant achievements in this area, we have concentrated on examples that highlight key features with respect to positive and/or negative catalytic activity.     

A study of homogeneous nucleation of ibuprofen in a flow chamber. Determination of the surface tension of critical nuclei

Homogeneous nucleation of ibuprofen vapor is studied in a nucleation flow chamber, a horizontal quartz tube equipped with an external heater. The area of the chamber where the nucleation proceeds most efficiently is determined, and the volume of this area is estimated. The temperature and supersaturation are determined and the homogeneous nucleation rate is calculated for this area. Saturation vapor pressure over liquid ibuprofen is measured in a temperature range of 353–383 K. Using an exact formula that has recently been derived for the nucleation rate based on the works by Kusaka, Reiss, as well as the Frenkel liquid-kinetics theory, surface tension and the radius of surface of tension of a critical nucleus σ= 25.9 mN/m and R _s = 1.6 nm, respectively, are calculated at 318 K. The measurement of the surface tension of an ibuprofen planar surface shows that, at 318 K, σ_∞ = 24.38 mN/m; i.e., σ is higher than σ_∞ by 6%. A critical nucleus is established as containing nearly 36 ibuprofen molecules.     

Molecular imprinting inside dendrimers

Synthetic hosts capable of binding porphyrins have been produced by a mixed-covalent-noncovalent imprinting process wherein a single binding site is created within cross-linked dendrimers. Two synthetic hosts were prepared, using as templates 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin and 5,10,15,20-tetrakis(3,5-dihydroxyphenyl)porphyrin. These two templates were esterified with, respectively, fourth- and third-generation Fréchet-type dendrons containing homoallyl end-groups. The resulting tetra- and octadendron macromolecules underwent the ring-closing metathesis reaction using Grubbs' Type I catalyst, RuCl(2)(P(C(6)H(5))(3))(2)(CHCH(2)C(6)H(5)), to give extensive interdendron cross-linking. Hydrolytic removal of the porphyrin cores afforded imprinted hosts whose ability to bind porphyrins with various peripheral substituents was investigated by UV-visible spectrophotometric titrations and size exclusion chromatography. The results indicate a high yield of imprinted sites that show high selectivity for binding of porphyrins capable of making at least four hydrogen bonds, but only a moderate degree of shape selectivity.     

Chemical polarization of nuclei

Conclusions The reaction of 2,6-di-tert-butyl-1,4-benzoquinonediazide with primary aliphatic amines leads to the formation of intermediate unstable triazenes which, in turn, break down through a radical mechanism to form 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-p-benzoquinone, the final reaction products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 771–775, April, 1977.     

注塑制品残余应力的研究进展

由于实际工艺条件往往与理想值存在一定偏差,制品在成形后通常会存在一些难以避免的缺陷,而残余应力正是最为常见的一种。注塑制品的残余应力是在注塑成形过程中,外界约束去除后,仍存在于塑件内部的应力,在后期使用过程中容易引起塑件的翘曲、变形、乃至断裂破损,多数情况下对制品不利。因此,在塑料制品设计时应充分考虑到残余应力的影响。本文较为全面地介绍了注塑制品残余应力的产生、检测、减小残余应力的措施及残余应力的计算机模拟等内容。     

Water inside a hydrophobic cavitand molecule

The structure and dynamics of water inside a water-soluble, bowl-shaped cavitand molecule with a hydrophobic interior are studied using molecular dynamics computer simulations. The simulations find that the number of inside water molecules is about 4.5, but it fluctuates from being completely empty to full on a time scale of tens of nanoseconds. The transition from empty to full is energetically favorable and entropically unfavorable. The water molecules inside have fewer hydrogen bonds than the bulk and in general weaker interactions; the lower energy results from the nearest-neighbor interactions with the cavitand atoms and the water molecules at the entrance of the cavitand, interactions that are lost upon dewetting. An analysis of translational and rotational motion suggests that the lower entropy of the inside water molecules is due to decreased translational entropy, which outweighs an increased orientational entropy. The cavitand molecule acts as a host binding hydrophobic guests, and dewetting can be induced by the presence of a hydrophobic guest molecule about 3 A above the entrance. At this position, the guest displaces the water molecules which stabilize the inside water molecules and the empty cavitand becomes more stable than the full.