An approach to developing a force field for molecular simulation of martensitic phase transitions between phases with subtle differences in energy and structure

d,l-Norleucine is one of only a few molecules whose crystals exhibit a martensitic or displacive-type phase transformation where the emerging phase shows a topotaxial relationship with the parent phase. The molecular mechanism for such phase transformations, particularly in molecular crystals, is not well understood. Crystalline phases that exhibit displacive phase transitions tend to be very similar in structure and energy. Consequently, the development of a force field for such phases is challenging as the phase behavior is determined by subtle differences in their lattice energies and entropies. We report an approach for developing a force field for such phases with an application to d,l-norleucine. The proposed procedure includes calculation of the phase diagram of the crystalline phases as a function of temperature to identify the best force field. d,l-Norleucine also presents an additional problem since in the solid state it exists as a zwitterion that is unstable in vacuo and therefore cannot be characterized using high-level ab initio calculations in the gas phase. However, a stable zwitterion could be obtained using Onsager's reaction-field continuum model for a solvent (SCRF) using both Hartree-Fock and density functional theory. A number of force fields and the various sets of partial charges obtained from the SCRF calculations were screened for their ability to reproduce the crystal structures of the two known phases, alpha and beta, of d,l-norleucine. Selected parameter sets were then employed in free energy minimizations to identify the best set on the basis of a correct prediction of the alpha-beta phase transition. The Williams' nonbonded parameters combined with partial charges from SCRF-Polarized Continuum Model calculation were found to reproduce the structures of the phases accurately and also maintained their stability in extended molecular dynamics simulations in the Parrinello-Rahman constant stress ensemble. Moreover, we were also able to successfully simulate the phase transformation of the beta- to the alpha-phase. The identified force field should enable detailed studies of the phase transformations exhibited by crystals of d,l-norleucine and hence enhance our understanding of martensitic-type transformations in molecular crystals.     

Size-dependent phase stability of a molecular nanocrystal: a proxy for investigating the early stages of crystallization

We make the link between the size-dependent phase stability of a nanocrystal and the phase-transition behavior of emerging crystallites during the earliest stages of crystallization, by using the former as a proxy for the latter. We outline an extension of the classical nucleation theory to describe crystal nucleation and subsequent transformations of competing polymorphic phases that characterize Ostwald's rule of stages. The theoretical framework reveals that the relative stability of the competing phases is a function of cluster size, which in turn varies with time, and therefore explains the complex transformation behavior observed for some systems. We investigated the stability of a nanocrystal of dl-norleucine by means of molecular simulation as a proxy for post-nucleation phase-transformation behavior in emerging crystallites. The simulations reveal that, for nanocrystals, the surface energy of the transition state of a transformation can dominate the barrier to phase change, thus causing metastable phases to be stabilized, not because they are thermodynamically stable, but rather due to kinetic hindering. Therefore, in the context of the earliest stages of crystal growth, not only does phase stability vary as a function of cluster size, and hence time, but thermodynamically feasible transformations are also prone to kinetic hindering.     

Densities,Refractive Indices,Ultrasonic Speeds and Excess Properties of Acetonitrile + Poly(ethylene glycol) Binary Mixtures at Temperatures from 298.15 to 313.15 K

The densities, ρ, refractive indices, n _D, and ultrasonic speeds, u, of binary mixtures of acetonitrile (AN) with poly(ethylene glycol) 200 (PEG200), poly(ethylene glycol) 300 (PEG300) and poly(ethylene glycol) 400 (PEG400) were measured over the entire composition range at temperatures (298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. From the experimental data, the excess molar volumes, \( V_{\text{m}}^{\text{E}} \) , deviations in refractive indices, \( \Delta n_{\text{D}} \) , excess molar isentropic compressibility, \( K_{{s , {\text{m}}}}^{\text{E}} \) , excess intermolecular free length, \( L_{\text{f}}^{\text{E}} \) , and excess acoustic impedance, Z ^E, have been evaluated. The partial molar volumes, \( \overline{V}_{\text{m,1}} \) and \( \overline{V}_{\text{m,2}} \) , partial molar isentropic compressibilities, \( \overline{K}_{{s , {\text{m,1}}}} \) and \( \overline{K}_{{s , {\text{m,2}}}} \) , and their excess values over whole composition range and at infinite dilution have also been calculated. The variations of these properties with composition and temperature are discussed in terms of intermolecular interactions in these mixtures. The results indicate the presence of specific interactions among the AN and PEG molecules, which follow the order PEG200 < PEG300 < PEG400.     

Bis[1,1′‐bis(diphenylphosphino)ferrocenium] hexadecachlorotetraantimony(III) ethanol solvate

In the title compound, [Fe(C₁₇H₁₄P)₂]₂[Sb₄Cl₁₆]·C₂H₆O, the Fe atoms lie on inversion centres and the pairs of cyclopentadienyl rings are consequently in a fully staggered conformation. The centrosymmetric anionic clusters formed by [Sb₄Cl₁₆]^4? are surrounded by the cations and are held together by weak C—H?Cl interactions. These formations stack along the a axis to form columns, and the columns are interconnected by another weak C—H?Cl interaction along the b axis.     

On the wake of a circular cylinder with nodal and saddle attachment

Flow field of a cylinder with a mid-span curvature was experimentally investigated in a wind tunnel and a water tunnel. The azimuthal orientation of the cylinder was changed to obtain a nodal, saddle and a mixed nodal–saddle type of flow attachment. Surface flow topology suggested that the nature of the attachment strongly influenced the spanwise distributions of foci structures that play a significant role in introducing three-dimensionality in the immediate wake. Flow visualization in the water tunnel revealed that the length of a vortex formation region also followed the changes in the nature of the attachment. A symmetric shedding of vortices was observed with a saddle type of attachment. Wake mean velocity profiles showed that the velocity defect and therefore the drag of a curved cylinder was minimum for nodal, and maximum for saddle type of attachment. Nomenclature of the wake was compared with asymptotic profiles and equilibrium parameters. Approach to self-preservation, similarity and other features are discussed.     

Superconductivity in Sr<Subscript>0.75</Subscript>Y<Subscript>0.75</Subscript>Ba<Subscript>1.5</Subscript>Cu<Subscript>3</Subscript> O<Subscript>7−<Emphasis Type="Italic">d</Emphasis></Subscript> compounds

The effect of simultaneous Sr substitution at the Ba and Y sites has been studied in the Sr_0.75Y_0.75Ba_1.5Cu₃O_7–dsystem. Attempts to replace 25% Y and 25% Ba have been successful and superconductivity was observed above 78 K for Sr_0.75Y_0.75Ba_1.5Cu₃O_7–d compound with high oxygen content, i.e., O_6.76, and having orthorhombic crystal symmetry. The compound was treated in argon gas at 800°C to reduce the oxygen content and to induce some structural changes. The Sr_0.75Y_0.75Ba_1.5Cu₃O_6.1 compound thus obtained has tetragonal symmetry and low oxygen content, O_6.1. It has also shown superconductivity at 28 K. The paper presents a careful comparison of the structural and electrical properties and infrared absorbance spectra of the two compounds with the same metallic composition, Sr_0.75Y_0.75Ba_1.5Cu₃, but with different oxygen content and crystal symmetry. The study clearly establishes the occurrence of superconductivity in tetragonal Sr-substituted (both at Y and Ba sites in) YBCO.     

Pyrrolidinones derived from (S)-pyroglutamic acid: penmacric acid and analogues

Alkylation reactions using alpha-halolactams or lactam enolates derived from bicyclic lactam templates can proceed with high endo- or exo- diastereoselectivity respectively. In the latter case, stereochemical correction by means of enolate generation and hindered phenol quench is possible with moderate efficiency. This protocol has been applied to the synthesis of protected penmacric acid and its analogues.     

9,10‐Di­phenyl‐9,10‐epi­dioxy­anthra­cene and 9,10‐di­hydro‐10,10‐di­methoxy‐9‐phenyl­anthracen‐9‐ol

9,10‐Di­phenyl‐9,10‐epi­dioxy­anthracene, C₂₆H₁₈O₂, (I), was accidentally used in a photo­oxy­genation reaction that produced 9,10‐di­hydro‐10,10‐di­methoxy‐9‐phenyl­anthracen‐9‐ol, C₂₂H₂₀O₃, (II). In both compounds, the phenyl rings are approximately orthogonal to the anthracene moiety. The conformation of the anthracene moiety differs as a result of substitution. Intramolecular C—H⃛O interactions in (I) form two approximately planar S(5) rings in each of the two crystallographically independent mol­ecules. The packing of (I) and (II) consists of molecular dimers stabilized by C—H⃛O interactions and of molecular chains stabilized by O—H⃛O interactions, respectively.     

Synthesis and antimicrobial activity of some novel 2-(substituted fluorobenzoylimino)-3-(substituted fluorophenyl)-4-methyl-1,3-thiazolines

The synthesis of several 2-(substituted fluorobenzoylimino)-3-(substituted fluorophenyl)-4-methyl-1,3-thiazolines (2a-t) was carried out by base-catalyzed cyclization of corresponding 1-(fluorobenzoyl)-3-(fluorophenyl)thioureas (1a-t) with 2-bromoacetone in aqueous medium. The structures of the synthesized compounds were confirmed by spectral and elemental analysis. All synthesized compounds were evaluated for in vitro antibacterial activity using Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis) and Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa). The minimum inhibitory concentration (MIC) was determined for the most active compounds. In vitro antifungal activity was also determined against the five fungal species (Rhizopus oryzae, Fusarium oxysporum, Aspergillus terreus, A. niger and A. fumigatus).