Molecular Engineering of Colloidal Atoms.

Creation of architectures with exquisite hierarchies actuates the germination of revolutionized functions and applications across a wide range of fields. Hierarchical self-assembly of colloidal particles holds the promise for materialized realization of structural programing and customizing. This review outlines the general approaches to organize atom-like micro- and nanoparticles into prescribed colloidal analogs of molecules by exploiting diverse interparticle driving motifs involving confining templates, interactive surface ligands, and flexible shape/surface anisotropy. Furthermore, the self-regulated/adaptive co-assembly of simple unvarnished building blocks is discussed to inspire new designs of colloidal assembly strategies.

Universal Fermi-surface anisotropy renormalization for interacting Dirac fermions with long-range interactions.

Recent experimental [I. Jo et al., Phys. Rev. Lett. 119, 016402 (2017)] and numerical [M. Ippoliti, S. D. Geraedts, R. N. Bhatt, Phys. Rev. B 95, 201104 (2017)] evidence suggests an intriguing universal relationship between the Fermi surface anisotropy of the noninteracting parent 2-dimensional (2D) electron gas and the strongly correlated composite Fermi liquid formed in a strong magnetic field close to half-filling. Inspired by these observations, we explore more generally the question of anisotropy renormalization in interacting 2D Fermi systems. Using a recently developed [H. -K. Tang et al., Science 361, 570 (2018)] nonperturbative and numerically exact projective quantum Monte Carlo simulation as well as other numerical and analytic techniques, only for Dirac fermions with long-range Coulomb interactions do we find a universal square-root decrease of the Fermi-surface anisotropy. For the [Formula: see text] composite Fermi liquid, this result is surprising since a Dirac fermion ground state was only recently proposed as an alternative to the usual Halperin-Lee-Read state. Our proposed universality can be tested in several anisotropic Dirac materials including graphene, topological insulators, organic conductors, and magic-angle twisted bilayer graphene.

Influence of chloride salt erosion on the adhesion of asphalt-aggregate interfaces considering mineral anisotropy: insights from molecular dynamics.

CONTEXT: Asphalt, a polymer mixture composed of various hydrocarbons, is extensively utilized due to its excellent performance. To evaluate the sensitivity of asphalt concrete to chloride salt damage at the nanoscale, considering the anisotropy of aggregate mineral crystal orientation, molecular dynamic simulations were employed to model the interface interactions between asphalt and aggregate mineral components (silica and calcite) under chloride salt exposure. The wetting processes of water droplets and chloride salt droplets on different crystal surfaces of silica and calcite were analyzed. Furthermore, the adhesive energy, decohesion energy, degradation ratio, and energy ratio of the interaction model between asphalt and aggregate mineral interfaces were analyzed to reveal the variations in the interfaces between the two components. The results demonstrated that the anisotropy of the minerals significantly affects the adhesion energy of asphalt and aggregate. Moreover, the surface hydrophilicity of calcite was larger than that of silica. The interfacial adhesion energy of asphalt-calcite was larger than that of asphalt-silica under dry condition and chloride salt attack, and the interfacial adhesion energy of both asphalt and mineral decreased with the increase of chloride salt concentration. The degradation ratio and energy ratio values of asphalt and calcite were larger than those of asphalt and silica, and the anisotropy of the mineral surface affected the degradation ratio and energy ratio values. This study provides a new method and theoretical basis for further research on the damage mechanism and strengthening measures of asphalt-aggregate under chloride salt attack. METHODS: To investigate the interaction between asphalt and mineral aggregates under chloride salt erosion, models of asphalt, aggregate, and asphalt/aggregate composite systems were constructed using the Amorphous Cell module in Materials Studio 2020 software. Molecular dynamic simulations of the asphalt/aggregate composite system were then conducted using the Forcite module, employing the COMPASS II force field to describe atomic and molecular interactions. Initially, considering the crystal orientation and surface configuration of the aggregate minerals, the impact of mineral anisotropy on the asphalt-aggregate interface model was analyzed. Subsequently, by simulating the contact states of nano water droplets and chloride salt droplets with different mineral surfaces, the wetting characteristics of nano water droplets on silica and calcite surfaces were determined. Lastly, considering the corrosion effect of chloride solution at different concentrations, the adhesion energy, debonding energy, degradation ratio, and energy ratio of the asphalt-aggregate interface interaction model were analyzed.

Effect of Differential Surface Anisotropy on Dissolution Behavior of Fenofibrate Crystal Habits: Comparative Study using USP Type 2 and Type 4 Dissolution Apparatuses.

The solid-state properties of active pharmaceutical ingredient (API) have significant impact on its dissolution performance. In the present study, two different crystal habits viz. rod and plate shape of form I of FEN were evaluated for dissolution profile using USP Type 2 and Type 4 apparatuses. Molecular basis of differential dissolution performance of different crystal habits was investigated. Rod (FEN-R) and plate (FEN-P) shaped crystal habits of Form I of FEN were generated using anti-solvent crystallization method. Despite the same polymorphic form and similar particle size distribution, FEN-P demonstrated higher dissolution performance than FEN-R. Crystal face indexation and electrostatic potential (ESP) map provided information on differential relative abundance of various facets and their molecular environment. In FEN-R, the dominant facet (001) is hydrophobic due to the exposure of chlorophenyl moiety. Whereas, in FEN-P the dominant facet (01-1) was hydrophilic due to the presence of chlorine and ester carbonyl groups. Deeper insight on the impact of different facets on dissolution behavior was obtained by energy framework analysis by unveiling strength of intermolecular interactions along various crystallographic facets. Moreover, type 4 apparatus provided higher discriminatory ability over USP Type 2 apparatus, in probing the crystal habit induced differential dissolution performance of FEN. The findings of this study emphasize that crystal habit should be considered as an important critical material attribute (CMA) during formulation development of FEN and due considerations should be given to the selection of the appropriate dissolution testing set-up for establishing in vitro-in vivo correlation.

Varied Bulk Powder Properties of Micro-Sized API within Size Specifications as a Result of Particle Engineering Methods.

Micronized particles are commonly used to improve the content uniformity (CU), dissolution performance, and bioavailability of active pharmaceutical ingredients (API). Different particle engineering routes have been developed to prepare micron-sized API in a specific size range to deliver desirable biopharmaceutical performance. However, such API particles still risk varying bulk powder properties critical to successful manufacturing of quality drug products due to different particle shapes, size distribution, and surface energetics, arising from the anisotropy of API crystals. In this work, we systematically investigated key bulk properties of 10 different batches of Odanacatib prepared through either jet milling or fast precipitation, all of which meet the particle size specification established to ensure equivalent biopharmaceutical performance. However, they exhibited significantly different powder properties, solid-state properties, dissolution, and tablet CU. Among the 10 batches, a directly precipitated sample exhibited overall best performance, considering tabletability, dissolution, and CU. This work highlights the measurable impact of processing route on API properties and the importance of selecting a suitable processing route for preparing fine particles with optimal properties and performance.

Magnetic neutron scattering from spherical nanoparticles with Néel surface anisotropy: atomistic simulations.

A dilute ensemble of randomly oriented non-interacting spherical nanomagnets is considered, and its magnetization structure and ensuing neutron scattering response are investigated by numerically solving the Landau-Lifshitz equation. Taking into account the isotropic exchange interaction, an external magnetic field, a uniaxial magnetic anisotropy for the particle core, and in particular the Néel surface anisotropy, the magnetic small-angle neutron scattering cross section and pair-distance distribution function are calculated from the obtained equilibrium spin structures. The numerical results are compared with the well known analytical expressions for uniformly magnetized particles and provide guidance to the experimentalist. In addition, the effect of a particle-size distribution function is modelled.

Magnetic neutron scattering from spherical nanoparticles with Néel surface anisotropy: analytical treatment.

The magnetization profile and the related magnetic small-angle neutron scattering cross section of a single spherical nanoparticle with Néel surface anisotropy are analytically investigated. A Hamiltonian is employed that comprises the isotropic exchange interaction, an external magnetic field, a uniaxial magnetocrystalline anisotropy in the core of the particle and the Néel anisotropy at the surface. Using a perturbation approach, the determination of the magnetization profile can be reduced to a Helmholtz equation with Neumann boundary condition, whose solution is represented by an infinite series in terms of spherical harmonics and spherical Bessel functions. From the resulting infinite series expansion, the Fourier transform, which is algebraically related to the magnetic small-angle neutron scattering cross section, is analytically calculated. The approximate analytical solution for the spin structure is compared with the numerical solution using the Landau-Lifshitz equation, which accounts for the full nonlinearity of the problem. The signature of the Néel surface anisotropy can be identified in the magnetic neutron scattering observables, but its effect is relatively small, even for large values of the surface anisotropy constant.

Contributions of lunate cells and wax crystals to the surface anisotropy of Nepenthes slippery zone.

Nepenthes slippery zone presents surface anisotropy depending on its specialized structures. Herein, via macro-micro-nano scaled experiments, we analysed the contributions of lunate cells and wax crystals to this anisotropy. Macroscopic climbing of insects showed large displacements (triple body length within 3 s) and high velocities (6.16-20.47 mm s-1) in the inverted-fixed (towards digestive zone) slippery zone, but failed to climb forward in the normal-fixed (towards peristome) one. Friction force of insect claws sliding across inverted-fixed lunate cells was about 2.4 times of that sliding across the normal-fixed ones, whereas showed unobvious differences (1.06-1.11 times) between the inverted- and normal-fixed wax crystals. Innovative results from atomic force microscope scanning and microstructure examination demonstrated the upper layer of wax crystals causes the cantilever tip to generate rather small differences in friction data (1.92-2.72%), and the beneath layer provides slightly higher differences (4.96-7.91%). The study confirms the anisotropic configuration of lunate cells produces most of the anisotropy, whereas both surface topography and structural features of the wax crystals generate a slight contribution. These results are helpful for understanding the surface anisotropy of Nepenthes slippery zone, and guide the design of bioinspired surface with anisotropic properties.

IR-ATR investigation of surface anisotropy in silicate glasses.

Several samples of flat soda-lime silicate glass were investigated by the Infrared Attenuated Total Reflection (IR-ATR) spectroscopy technique. The specular reflectance spectra together with the results of the performed dispersion analysis and the generated reflectance spectra, using Fresnel equations, suggest that the samples are isotropic. In contrast, spectra recorded by the ATR technique suggest an anisotropic structure on the surface of the specimen different from that in the bulk. This is established through differences in the s- and p-polarized IR-ATR spectra, which cannot be simply transformed into one another employing Fresnel formula for an isotropic case. It appears that this thin film having a structure different from the bulk is larger than the ATR effective penetration depth of the evanescent ray for each incidence angle above the critical one. The investigation suggests C2 symmetry of the SiO4 unit.

Effect of differential surface anisotropy on performance of two plate shaped crystals of aspirin form I.

Differential surface anisotropy of different crystals of the same API can have a significant impact on their pharmaceutical performance. The present work investigated the impact of differential surface anisotropy of two plate-shaped crystals of aspirin (form I) on their hygroscopicity, stability and compaction behavior. These crystals differed in their predominant facets (100) and (001) and were coded as AE-100 & E-001. (100) facets exposed polar carbonyl groups which provided hydrophilicity to the facets. In contrast, (001) facets possessed hydrophobicity as they exposed non-polar aryl and methyl groups. Both the samples showed different degradation behavior, at various stability conditions (i.e. 40°C/75%RH, 30°C/90%RH and 30°C/60%RH) and different time intervals. Polar groups of aspirin have been reported to be prone to hydrolysis due to which AE-100 was less stable than E-001. Dynamic vapor sorption (DVS) analysis at different simulated stability conditions also supported this observation, wherein AE-100 showed higher moisture sorption than E-001. Both the samples having similar particle size, shape, surface area and hardness value, showed differences in their compactibility. However, milling narrowed down the predominance of facets and both the milled samples showed similar stability and compaction behavior. This study was also supported by surface free energy determination, molecular modeling and face indexation of unmilled and milled samples.

The growth of α-sexithiophene films on Ag(111) studied by means of PEEM with linearly polarized light.

In this study, we used photo electron emission microscopy (PEEM) to investigate the growth of α-sexithiophene (α-6 T) on Ag(111) surfaces. The experiments were carried out with linearly polarized ultraviolet-light (Hg lamp with hν=4.9 eV) in order to probe the alignment of the molecules on the surface. In particular, we acquired images before, during, and after growth while changing the polarization in a stepwise manner. For the stationary states of the clean and the α-6 T covered surfaces, we monitored the local electron yield and the intensity of the ultraviolet C-light (100-280 nm) reflected from the whole sample using PEEM and a photodiode, respectively. Due to the high ionization potential (IP>5 eV), there is no direct photoelectron emission from the organic crystallites. However, the photoelectron emission of the metal/organic interface is influenced by anisotropic absorption of the incident light beam, since the adsorbed molecules act as dichroic filters with distinct orientations.

Impact of differential surface molecular environment on the interparticulate bonding strength of celecoxib crystal habits.

The present work investigates the impact of milling on differential compactibility behavior of celecoxib (CEL) crystal habits. Plate shaped (CEL-P) crystals showed better compactibility over acicular (CEL-A) crystals. Milling improved the compactibility of both the forms. However, despite similar particle shape, size, and surface area, milled fractions of the two habits showed significantly different interparticulate bonding strength. The greater bonding strength of milled CEL-P (MCEL-P) over milled CEL-A (MCEL-A) was attributed to the differential cleavage behavior of the two habits that conferred the different surface molecular environment to the milled powders. The preferred cleavage of CEL-P across {020} plane exposed the -CF3 group and the methyl phenyl ring on the surface of MCEL-P. On the other hand, CEL-A preferentially fractured along their shortest axis that increased the exposure of {100} plane on the surface of MCEL-A, which exposed the -CF3 group and the pyrazole ring. Surface free energy quantified by determining advancing contact angle revealed greater dispersive component of MCEL-P over MCEL-A. This is consistent with the differential cleavage behavior of CEL-P and CEL-A. This confirmed the role of dispersive component of surface free energy in governing interparticulate bonding strength of CEL. The study supports the postulate that tablet tensile strength is governed by the dispersive intermolecular interactions formed over the interparticulate bonding area.