Controlled evaporative self-assembly of polymer nanoribbons using oscillating capillary bridges

Evaporative self-assembly (ESA), based on the “coffee-ring” effect, is a versatile technique for assembling particle solutions into mesoscale patterns and structures on different substrates. ESA works with a wide variety of organic and inorganic materials, where the solution is a combination of volatile solvent and nonvolatile solute. Modified ESA methods, such as “stop-and-go flow coating,” use a programmed meniscus “stick–slip” motion to create mesoscale assemblies with controlled shape, size, and architecture. However, current methods are not scalable for increased production volumes or patterning large surface areas. We demonstrate a new ESA method, where an oscillating blade controls the meniscus depinning and drives the evaporative assembly of solutes at the pinned meniscus. Results show that oscillation frequency and substrate speed control time/distance intervals between successive meniscus depinning, and the assembly dimensions depend on solution concentration, oscillation frequency, substrate speed, and meniscus height. We report the mechanism of the meniscus depinning and the control over assembly cross-sectional dimensions. This advance provides a scalable ESA method with faster processing times and maintained advantages. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1545–1551     

Impact of surface forces on wetting of hierarchical surfaces and contact angle hysteresis

The influence of the long-range surface forces on the wetting of multi-scale partially wetted surfaces is discussed. The possibility of partial wetting is stipulated by a specific form of the Derjaguin isotherm. Equilibrium of a liquid meniscus inside a cylindrical capillary is used as a model. The interplay of capillary and disjoining pressures governs the equilibrium of the liquid in the nano- and micrometrically scaled pores constituting the relief of the surface. It is shown that capillaries with a radius smaller than a critical one will be completely filled by water, whereas the larger capillaries will be filled only partially. Thus, small capillaries will show the Wenzel type of wetting behavior, while the same liquid inside the large capillaries will promote the Cassie-Baxter type of wetting. Consideration of disjoining/conjoining pressure allows explaining of the “rose petal effect”, when a high apparent contact angle is accompanied with a high contact angle hysteresis.     

Wetting: Inverse Dynamic Problem and Equations for Microscopic Parameters

Movement of a liquid meniscus in a low-diameter capillary while it is being filled or emptied is considered. The liquid is nonvolatile. Assuming low Reynolds number and low capillary number, the liquid-gas interface shape is studied. Angles of inclination of this boundary to the solid near the contact line are small. Consideration is given to the inverse problem in wetting dynamics: to establish an analytic expression for the universal constant that influences the dynamics of a three-phase contact line. Inverse relations for microscopic parameters in terms of macroscopic measured values obtained in experiments with a meniscus moving through a capillary are derived. The inverse relations are substantiated independently. To do so, numerical experiments for a van der Waals liquid have been carried out, using the de Gennes model of partial wetting. General formulas for microparameters agree well with numerical experiments. The article provides the similarity criterion which influences the wetting in the case of a van der Waals liquid meniscus. The inverse dynamic problem for both an advancing and a receding meniscus is solved. A relation for the critical speed of meniscus recession is proposed. Two contact angles for a meniscus are discussed. Behavior of dynamic contact angles in the vicinity of the critical speed is studied. One of the angles is shown to vanish at less than the critical speed, and the other one, exactly at the critical speed. In the case of an advancing meniscus the equations for microparameters are valid for both partial and complete wetting. The proposed inverse expression for complete wetting allows determination of the maximum precursor film thickness and its dependence on the motion speed (also determination of the Hamaker constant in the case of a van der Waals liquid). Copyright 2000 Academic Press.     

Problems on the Evaluation of the Critical Wavelength of Sunscreens for “Broad Spectrum” Approval Brought on by Viscous Fingering During Sunscreen Application

When a viscous liquid is applied to a solid substrate, a patterned liquid layer is usually formed by the phenomenon called viscous fingering, since the moving liquid surface is in far‐from‐equilibrium conditions to let the morphological fluctuation to grow. Pseudosunscreen solutions were prepared and applied on a flat quartz plate. A spatially periodic stripe pattern was formed on the pseudosunscreen layer when a block applicator was used, whereas a flat surface layer was formed when a four‐sided applicator was used. UV absorbance of the patterned layer was lower than that of the flat layer having the same average thickness. In addition, a larger decrease in the UV absorbance by the pattern formation was observed at wavelengths at which the UV absorbance of the flat layer was large, which was consistent with theoretical simulations. In 2011, US FDA introduced a new rule using the term “Broad Spectrum” for labeling the sunscreens. The different decrease in the UV absorbance at each wavelength was found to change the critical wavelength, which is a criterion for sunscreens to be labeled as “Broad Spectrum” protection. The result of this study makes the problem on the evaluation of the critical wavelength come to the surface.     

Environmental stress cracking of polyethylene: Analysis of the three zones of behavior and determination of crack-front dimensions

Previous work has shown that in the environmental stress cracking (ESC) of polyethylene, there are three major zones of behavior depending on the applied stress and the nature of the liquid environment. These three zones correspond to “pure” ESC (zone 1), ESC controlled by the speed of penetration of the liquid within a growing crack (zone 2), and behavior as in the absence of liquid (zone 3). Analysis of the transitions between zones has shown that, in the present case, a given liquid will either be capable of giving rise to all three types of behavior depending on the stress applied, or will be totally inactive. A related analysis has enabled the order of magnitude of the dimensions of the crack tip to be estimated and this has been found to be in the range of a micron.     

pH‐Zone‐refining counter‐current chromatography for two new lipo‐alkaloids separated from refined alkaline extraction of Kusnezoff monkshood root

An efficient and refined method for the separation of six aconitine‐type alkaloids from the alkaline prepared “Kusnezoff monkshood root” was established. It is the first study that two new lipo‐alkaloids were successfully isolated from refined sample by pH‐zone‐refining counter‐current chromatography rather than synthetic method. It was of interest that a great deal of lipo‐alkaloids was produced in crude extract from the alkalization of “Kusnezoff monkshood root.” A refined sample method was proposed to enrich two types of alkaloids by liquid–liquid extraction, i.e. lipo‐alkaloids and monoester‐diterpenoid alkaloids. The pH‐zone‐refining counter‐current chromatography was performed with an optimized two‐phase solvent system composed of n‐hexane‐ethyl acetate–methanol–water (3:5:4:5, v/v), where upper organic phase was added to 3 mmol/L triethylamine as a retainer and lower aqueous mobile phase was added to 3 mmol/L hydrochloric acid as an eluter. As a result, six aconitum alkaloids, including two lipo‐alkaloids (8‐lino‐14‐benzoylaconine, 8‐pal‐14‐benzoylaconine), three monoester‐diterpenoid alkaloids (14‐benzoylmesaconine, 14‐benzoylaconine, beyzoyldeoxyaconine), and one aconine alkaloid (neoline) were acquired from the plant at the same time. The anti‐inflammatory activities of the two new lipo‐alkaloids were compared to the six alkaloids in vitro, in cyclo‐oxygen‐ase‐2 inhibition assays. The separation mechanism of six alkaloids by pH‐zone‐refining counter‐current chromatography was illustrated.     

Molecular dynamics simulation of two-sided chemical modification of carbon nanoribbons on a solid substrate

The position of a graphene nanoribbon on a solid substrate allows the chemical modification of only one of the nanoribbon sides. A method was proposed that enables the chemical modification of the other side, too. It was numerically modeled how a nanoribbon separated from a substrate rolls up into a roll and how the roll unrolls on a flat substrate. The dependences of the number of coils and the radii of rolls forming by hydrogenation on the nanoribbon length and width were determined.     

Explicit and implicit multi‐center integrations

We present truncated expansions of multicenter one‐electron nuclear attraction and two‐electron repulsion integrals over localized basis functions in terms of one‐ and two‐center integrals of “Coulomb,” “exchange,” and “hybrid” type. Two variants are discussed: the “Explicit Multi‐center Integrations” and the “Implicit Multi‐Center Integrations” (abbreviated as “EMCI” and “IMCI”, respectively). While EMCI also deals with individual integrals, the IMCI option is the more appealing one: it enables us to evaluate the entire matrix elements of “Restricted Hartree–Fock”‐type in a very effective and chemically meaningful way. Due to the diatomic nature of our expansions, integrations over “Slater‐Type Orbitals” become well‐feasible, too. © 2012 Wiley Periodicals, Inc.     

Liquid coating of moving fiber at the nanoscale

Using large scale molecular dynamics, we study the contact line motion of a liquid meniscus crossed by a moving nanofiber. Varying the amplitude of the liquid/solid interactions, we analyze the shape of the meniscus versus time for a range of velocities. The associated contact angles are estimated by fitting the profiles using the James equation. The corresponding flux lines describing the displacement of the liquid molecules inside the meniscus have also been measured. The analysis of the dynamic contact angle is in agreement with the molecular-kinetic theory and confirms the existence of an optimal speed for wetting.     

Ultramicro zone melting

A systematic classification of zone melting is discussed with respect to the volume, i.e. weight, of the ingot. A new apparatus and technique of “ultra-micro zone melting'' are described for amounts less than 500 μg. The plates of the heating and cooling blocks are placed into one another like two combs; an iron-nickel alloy with a very low coefficient of expansion permits “zone melting units” between 1.7 mm and 2.5 mm in size. Because of the close packing of the 30 “units” and a steep temperature gradient, separation effects can be achieved after a few hours. For work at low temperatures and under inert gas, the apparatus can be enclosed in an air-tight plastic cylinder. The sample capillaries are prepared by capillary action followed by centrifuging. Ultramicro zone melting finds application in natural product chemistry and radiochemistry.     

Investigations of the reactivity of “kick‐started” oxetanes in photoinitiated cationic polymerization

The ability of certain alkyl substituted epoxides to accelerate the photoinitiated cationic ring‐opening polymerizations of oxetane monomers by substantially reducing or eliminating the induction period altogether has been termed by us “kick‐starting.” In this communication, the rates of photopolymerization of several model “kick‐started” oxetane systems were quantified and compared with the analogous biscycloaliphatic epoxide monomer, 3,4‐epoxycyclohexylmethyl 3′,4′‐epoxycyclohexanecarboxylate (ERL). It has been found that the “kick‐started” systems undergo photopolymerization at rates that are at least two‐fold faster than ERL. These results suggest that “kick‐started” oxetanes could replace ERL in many applications in which high speed ultraviolet induced crosslinking photopolymerizations are carried out. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 586–593     

The NMR spectra of porphyrins—12: 13C and proton NMR spectra of the zinc(ii)coproporphyrin isomers2

The ¹³C and proton NMR spectra of the zinc(II) complexes of the tetramethyl esters of the four coproporphyrin type isomers are reported and assigned. Effects of aggregation phenomena on these shifts are discussed and a method involving addition of a slight excess of pyrrolidine is proposed for measurement of the spectra of the “monomeric” species; spectra obtained under these conditions are capable of simple, straight-forward interpretation and assignment in terms of molecular symmetry. Thus, a facile distinction between the type isomers is obtained.The “monomer” chemical shifts so derived allow consistent SCS parameters to be derived. The C_β-Me SCS are shown to be related to the bond order of the C_β-C_β bond in the porphyrin ring, and are thus quite different from the corresponding SCS in pyrroles.Aggregation shifts in the ¹³C and proton spectra are shown to be consistent with the presence of “stacked” aggregates with the ring current of one molecule affecting the other, together with an additional effect on the chemical shifts of the meso carbons, which is probably steric in origin.     

Grand canonical Monte Carlo simulation study of capillary condensation between nanoparticles

Capillary condensation at the nanoscale differs from condensation in the bulk phase, because it is a strong function of surface geometry and gas-surface interactions. Here, the effects of geometry on the thermodynamics of capillary condensation at the neck region between nanoparticles are investigated via a grand canonical Monte Carlo simulation using a two-dimensional lattice gas model. The microscopic details of the meniscus formation on various surface geometries are examined and compared with results of classical macromolecular theory, the Kelvin equation. We assume that the system is composed of a lattice gas and the surfaces of two particles are approximated by various shapes. The system is modeled on the basis of the molecular properties of the particle surface and lattice gas in our system corresponding to titania nanoparticles and tetraethoxy orthosilicate molecules, respectively. This system was chosen in order to reasonably emulate our previous experimental results for capillary condensation on nanoparticle surfaces. Qualitatively, our simulation results show that the specific geometry in the capillary zone, the surface-surface distance, and the saturation ratio are important for determining the onset and broadening of the liquid meniscus. The meniscus height increases continuously as the saturation ratio increases and the meniscus broadens faster above the saturation ratio of 0.90. The change of the radius of curvature of the particle surface affects the dimensions of the capillary zone, which drives more condensation in narrow zones and less condensation in wide zones. The increase of surface-surface distance results in the decrease of the meniscus height or even the disappearance of the meniscus entirely at lower saturation ratios. These effects are significant at the nanoscale and must be carefully considered in order to develop predictive relationships for meniscus height as a function of saturation conditions.     

Géométrie de micelles à deux compartiments hydrophobes

We discuss a “comb block copolymer” with a hydrophilic backbone (N polar heads), Nf/2 side chains of type A, and Nf/2 side chains of type B. Imposing an area per head and a volume per side chain, we predict various conformations based on two spherical portions. In certain cases, two distinct conformations are permitted by this criterion: the best one should minimise the A/B interfacial energy. We also discuss “multiplets” (p polymers per double micelle) and “necklaces” (k double micelles for one polymer chain).     

Temperature effects in the environmental stress cracking of polyethylene

An already existing model describing three types of behavior in the environmental stress cracking (ESC) of polyethylene (PE) subjected to uniaxial tensile loading at 25°C has been extended to cover the temperature range 25-50°C. Three effects have been observed and are found to be qualitatively consistent with the model. The transition between “pure” ESC (zone 1) and liquid-flow-controlled behavior (zone 2) occurs at shorter times for higher temperatures—an effect mainly due to reduced liquid viscosity. “Pure” ESC is less temperature dependent than failure occurring without the liquid playing a significant role (zone 3). This has been attributed to a compensation of reduced mechanical resistance of the polymer at higher temperatures, by reduced stress concentrations at the crack tip due to local absorption of the liquid. The transition time between zones 2 and 3 increases with temperature. Although it is surprising at first sight, this effect is shown to be compatible with the ESC model.     

Propagative patterns in the convection of a nematic liquid crystal

We show here that the convective instability of a nematic liquid crystal subjected to an A.C. electric field (the conduction regime), is never stationary, contrary to the widely accepted picture. Indeed, we have found that the roll structure translates uniformly along the wavevector direction. In the low frequency part of the conduction regime, the structure is rather homogeneous in space and travels at a very low velocity, while inside the high frequency part, the rolls are localized inside stable domains and the propagation velocity is higher by three orders of magnitude. Closer to the cut-off frequency, we have also found a novel time dependent state, where the amplitude of the rolls oscillates periodically in time.     

New Fluorescence Domain “Excited Multimer” Formed upon Photoexcitation of Continuously Stacked Diaroylmethanatoboron Difluoride Molecules with Fused π‐Orbitals in Crystals

The crystal‐packing structures of seven derivatives of diaroylmethanatoboron difluoride ( 1 a – gBF₂ ) are characterized by no overlap of the π‐conjugated main units of two adjacent molecules (type I), overlap of the benzene ring π‐orbitals of two adjacent molecules (type II), and overlap of the benzene and dihydrodioxaborinine rings π‐orbitals of adjacent molecules (type III). The crystal‐packing structures govern the fluorescence (FL) properties in the crystalline states. The FL domain that is present in type I crystals, in which intermolecular orbital interactions are absent, leads to excited monomer‐like FL properties. In the case of the type II crystals, the presence of intermolecular overlap of the benzene rings π‐orbitals generates new FL domains, referred to as “excited multimers”, which possess allowed S₀–S₁ electronic transitions and, as a result, similar FL lifetimes at longer wavelengths than the FL of the type I crystals. Finally, intermolecular overlap of the benzene and dihydrodioxaborinine ring π‐orbitals in the type III crystals leads to “excited multimer” domains with forbidden S₀–S₁ electronic transitions and longer FL lifetimes at similar wavelengths as that in type I crystals.     

Novel skeletal rearrangement in addition reaction to tricyclo[4,2,2,02,5]deca-3,7-diene system

The “doping-addition” of RSCl to the tricyclo[4,2,2,0^2,5]deca-3,7-diene derivatives which are incapable of lactone ring closure proceeds to give the novel type of rearranged product, $\text{7}$, due to the two subsequent 1,2-shifts.     

General Design Strategy of Anti-aromatic Porphyrinoids

A systematic investigation to arrange the typical anti-aromatic porphyrinoids in sequence was performed. Based on density functional theory calculations, six rules are summarized to obtain the high-performance anti-aromatic porphyrinoids: (1) when two atoms are deleted/added on the 18π electron current ring flowing pipe, we will immediately obtain a 16π/20π electron anti-aromatic system; (2) it is a good idea to increase the number of pyrrole/thiophen/furan units on the π-electron current ring flowing pipe; (3) the heteroatom selecting order is −O− (optimal choice), −NH− (second choice), and −S− (last choice); (4) it is worth noting that the C−C=C−C unit is not beneficial for the anti-aromatic properties; (5) it is very significant to avoid the crowded environment in the core space of an anti-aromatic molecule. In this view, −O− is much better than −S− and −NH−; (6) the “circular” skeleton is much better than an “ellipse-like”, “rectangular”, or “parallelogram-like” one.