Synthesis of Colloidal Molecules: Recent Advances and Perspectives

The synthesis and study of colloidal molecules, that is to say clusters of a small number of colloidal entities that resemble the configuration of atoms in molecules both in constituent size and angular arrangement to that of valence shell electron pair repulsion model‐related space‐filling geometries, are of continued and significant interest. The rapid development in this research area has attracted intense interest from researchers with diverse expertise, and numerous methods towards the synthesis of colloidal molecules have been reported. In this Minireview, we attempt to give an overview of these latest developments, classifying them in processes based on controlled phase separation phenomena, on controlled surface nucleation and growth, and on controlled clustering. We also discuss the potential use of colloidal molecules as building blocks to fabricate new hierarchically organized superstructures and functional materials.     

Synthesis,spectral characteristics,and the crystal and molecular structures of 2,3-dimethyl-1-phenyl-4-(<Emphasis Type="Italic">N</Emphasis>-phthalimido)pyrazolone-5

2,3-Dimethyl-1-phenyl-4-(N-phthalimido)pyrazolone-5 (I) is synthesized and isolated in the form of single crystals. The crystal structure of compound I is determined using X-ray diffraction. The phthalimide and pyrazolone rings in the molecule are not coplanar: the angle between their median planes is 56.4°. The bond lengths in the rings level off, which indicates the delocalization of the electron density. The spectral characteristics (IR and electronic spectra) of molecule I are determined.     

Mixed-mode oscillations in complex-plasma instabilities

Instabilities in dusty plasmas are frequent phenomena. We show that some instabilities can be described by mixed-mode oscillations often encountered in chemical systems or neuronal dynamics and studied through dynamical system theories. The time evolution of these instabilities is studied through the change in the associated waveform. Frequency and interspike interval are analyzed and compared to results obtained in other scientific fields concerned by mixed-mode oscillations.     

Changes in the photoluminescence spectrum near twin boundaries in ZnTe crystals produced by rapid crystallization

{111} ZnTe crystals with various densities of twin boundaries in the growth direction were produced at ～670°C by the chemical vapor deposition method with the vapor environment offset toward an excess of Zn. Defects are formed in conical crystallites (up to 5 mm in height and with lateral dimensions of 10–500 μm at the bottom and up to 2 mm at the top) due to instabilities in the crystallization front, which arise because of convection-type heat and mass exchange in the oversaturated vapor medium. The influence of twin boundaries on the distribution of chemical impurities and the electronic spectrum of ZnTe was studied using x-ray diffractometry, scanning electron microscopy, and low-temperature photoluminescence (PL). It is found that rapid low-temperature growth of [111] ZnTe polycrystals from the vapor phase with an excessive Zn content favors the intensive formation of rotation and reflection twins. The incoherent [111] boundary of reflection twins is conductive to the separation and accumulation of impurities. In the regions of a crystal with a high density of reflection twins, exciton-impurity complexes (I _C , I _X ) and a Y strip, which is usually related to extended defects (dislocations, twins, crystallite boundaries), are found in the low-temperature PL spectra. Additional studies show that I _X is related to excitons trapped by neutral isoelectronic or charged defects and that I _C is probably due to an impurity of group IV of the Periodic Table.     

Dielectric relaxation in TGS crystals doped with orthophosphoric and phosphorous acids

Polarization switching and temperature dependences of the complex permittivity of triglycine sulfate crystals doped with orthophosphoric and phosphorous acids are studied in the frequency range 100 Hz-1 MHz at temperatures of 140–340 K. It is found that, for a comparatively low solubility of the dopants (not over 1 mol %), doping of the crystals gives rise to a noticeable change in the parameters of the dielectric hysteresis loop, as well as in the magnitude and character of the temperature dependence of dielectric losses, thus implying an increase in the ferroelectric phase of the doped crystals of the activation energies and relaxation times of domain walls as a result of their interaction with the dopants.     

Investigation of perceptual constancy in the temporal-envelope domain

The ability to discriminate complex temporal envelope patterns submitted to temporal compression or expansion was assessed in normal-hearing listeners. An XAB, matching-to-sample-procedure was used. X, the reference stimulus, is obtained by applying the sum of two, inharmonically related, sinusoids to a broadband noise carrier. A and B are obtained by multiplying the frequency of each modulation component of X by the same time expansion/compression factor, alpha (alphain[0.35-2.83]). For each trial, A or B is a time-reversed rendering of X, and the listeners' task is to choose which of the two is matched by X. Overall, the results indicate that discrimination performance degrades for increasing amounts of time expansion/compression (i.e., when alpha departs from 1), regardless of the frequency spacing of modulation components and the peak-to-trough ratio of the complex envelopes. An auditory model based on envelope extraction followed by a memory-limited, template-matching process accounted for results obtained without time scaling of stimuli, but generally underestimated discrimination ability with either time expansion or compression, especially with the longer stimulus durations. This result is consistent with partial or incomplete perceptual normalization of envelope patterns.     

Fast wave ultrasonic propagation in trabecular bone: numerical study of the influence of porosity and structural anisotropy

Our goal is to assess the potential of computational methods as an alternative to analytical models to predict the two longitudinal wave modes observed in cancellous bone and predicted by the Biot theory. A three-dimensional (3D) finite-difference time-domain method is coupled with 34 human femoral trabecular microstructures measured using microcomputed tomography. The main trabecular alignment (MTA) and the degree of anisotropy (DA) were assessed for all samples. DA values were comprised between 1.02 and 1.9. The influence of bone volume fraction (BV/TV) between 5% and 25% on the properties of the fast and slow waves was studied using a dedicated image processing algorithm to modify the initial 3D microstructures. A heuristic method was devised to determine when both wave modes are time separated. The simulations (performed in three perpendicular directions) predicted that both waves generally overlap in time for a direction of propagation perpendicular to the MTA. When these directions are parallel, both waves are separated in time for samples with high DA and BV/TV values. A relationship was found between the least bone volume fraction required for the observation of nonoverlapping waves and the degree of anisotropy: The higher the DA, the lower the least BV/TV.     

A Data-Driven Space-Time-Parameter Reduced-Order Model with Manifold Learning for Coupled Problems: Application to Deformable Capsules Flowing in Microchannels

An innovative data-driven model-order reduction technique is proposed to model dilute micrometric or nanometric suspensions of microcapsules, i.e., microdrops protected in a thin hyperelastic membrane, which are used in Healthcare as innovative drug vehicles. We consider a microcapsule flowing in a similar-size microfluidic channel and vary systematically the governing parameter, namely the capillary number, ratio of the viscous to elastic forces, and the confinement ratio, ratio of the capsule to tube size. The resulting space-time-parameter problem is solved using two global POD reduced bases, determined in the offline stage for the space and parameter variables, respectively. A suitable low-order spatial reduced basis is then computed in the online stage for any new parameter instance. The time evolution of the capsule dynamics is achieved by identifying the nonlinear low-order manifold of the reduced variables; for that, a point cloud of reduced data is computed and a diffuse approximation method is used. Numerical comparisons between the full-order fluid-structure interaction model and the reduced-order one confirm both accuracy and stability of the reduction technique over the whole admissible parameter domain. We believe that such an approach can be applied to a broad range of coupled problems especially involving quasistatic models of structural mechanics.     

Elongated bubbles in microchannels. Part II: Experimental study and modeling of bubble collisions

The collision of elongated bubbles has been studied along adiabatic glass microchannels of 509 and 790 μm internal diameters for refrigerant R-134a. The slug flow regime obtained here comes from the nucleation process inside a micro-evaporator located upstream. Using an optical measurement technique based on two lasers and two photodiodes, it was possible to determine the vapor bubble length distributions at the exit of the micro-evaporator and 70 mm downstream and thus characterize both diabatic and adiabatic bubble collisions. The database includes 412 coupled sets of distributions involving thousands of bubbles. Half of the database has been obtained under diabatic conditions and the second half under adiabatic conditions.     

Chemistry and Biology of HPAs: A Family of Ceramide Trafficking Inhibitors

In 2001, two years before the disclosure of the CERT‐associated Cer transfer machinery, N‐(3‐hydroxy‐1‐hydroxymethyl‐3‐phenylpropyl)alkanamides (HPAs) were described as the first, and to date unique, family of intracellular Cer trafficking inhibitors. The dodecanamide derivative, HPA‐12, turned out to be a benchmark as a cellular inhibitor of CERT‐mediated de novo sphingomyelin biosynthesis. In only 15 years after its first disclosure, this compound has prompted a growing number of biological and chemical studies. Its initial chemical development closely paralleled the study of the CERT protein. It was only after its structural revision in 2011 that HPA‐12 received broad attention from the synthetic chemistry community, leading to novel analogues with enhanced protein binding. This Minireview aims at presenting an exhaustive report of the syntheses of HPA‐12 and analogues. Biological activities of this CERT inhibitor and structure–activity relationships are also presented to afford a comprehensive overview of the chemistry and biology of the HPA series.