Loose Packing Research Articles

Impact of electron acceptors on mechanochromism in carbazole-based charge transfer complexes

The synthesis of a dicarbazole derivative (C4C) with a flexible alkyl chain was conducted, and its charge transfer complexes (CTCs) were prepared by incorporating three acceptors (3,4,5,6-tetrafluorophthalonitrile (TFPN), 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN), 1,2,4,5-tetracyanobenzene (TCNB)), aiming to investigate the influence of electron acceptors on their mechanofluorochromism (MFC). It was observed that CTC3 containing TCNB displayed the longest emission wavelength due to the lowest LUMO energy level of TCNB. Interestingly, while CTC1 with TFPN emitted green fluorescence, CTC2 incorporating TFTPN showed a shorter emission wavelength than that of CTC1 although TFTPN had a lower LUMO energy level than TFPN. Single-crystal structural analysis revealed that loose packing between donor and acceptor in CTC2 contributed to its shorter emission wavelength. Notably, CTC2 exhibited MFC because of enhanced charge transfer interaction after grinding. However, no MFC behaviors were observed for the other two complexes. These findings highlight that electron acceptors not only impact photoluminescent properties but also strongly influence response towards mechanical forces.

Triclinic polymorph of bis[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetrachloridocadmium(II)

The crystal structure of the title organic–inorganic hybrid salt, (C13H12N3)2[CdCl4], (I), has been reported with four molecules in the asymmetric unit in a monoclinic cell [Vassilyeva et al. (2021). RSC Advances, 11, 7713–7722]. While using two different aldehydes in the oxidative cyclization–condensation involving CH3NH2·HCl to prepare a new monovalent cation with the imidazo[1,5-a]pyridinium skeleton, a new polymorph was obtained for (I) in space group P 1 and a unit cell with approximately half the volume of the monoclinic form. The structural configurations of the two crystallographically non-equivalent organic cations as well as the geometry of the moderately distorted tetrahedral CdCl4 2– dianion show minor changes. In the crystal, identically stacked cations and tetrachlorocadmate anions form separate columns parallel to the a axis. The loose packing of the anions leads to a minimal separation of approximately 9.53 Å between the metal atoms in the triclinic form versus 7.51 Å in the monoclinic one, indicating that the latter is packed slightly more densely. The two forms also differ by aromatic stacking motifs. Similar to the monoclinic polymorph, the triclinic one excited at 364 nm shows an intense unsymmetrical photoluminescent band with maximum at 403 nm and a full width at half maximum of 51 nm in the solid state.

Effect of concentration and electrical charge of maltodextrin, and packing factor on electrospinning processing

The power law ηrel ∼ Ca of maltodextrins with higher entanglement concentrations (Ce) of dextrose equivalent (DE) 4, 10, and 18 exhibits an unusually high exponent a, ranging from 10.34 to 14.38 in congested solutions where particles occupy significant space. This contrasts with the dilute exponents (a ∼2) typically observed in polymer–solvent systems. To address this issue, several viscosity factors were evaluated using the Einstein–Roscoe and Mooney equations, which demonstrated viscosity dependence due to volume fraction (ϕ) > 0.35, shape, crowding factor (k) packing factor (1/k∼0.5) and centered cubic cell (CC), particularly for larger chain sizes (>20 glucoses) in DE-4. Chain electrical charges significantly stiffen the chain and increase its length beyond the theoretically predicted Kuhn persistent length (Lp), which seems to be responsible for the exponential increase in viscosity. Normalizing the viscosity/charge data revealed a log–log plot consistent with the exponent a of the general power law theory. In addition to concentration, electrospinning processing is influenced by strong particle–particle charge interactions, (ϕ), packing factor (1/k), CC, and chain sizes. The Maxwell model demonstrated poor interaction for DE-4 (modulus ∼286 Pa at maximum ϕ due to loose packing of CC, in contrast to DE-18, which exhibited a modulus of 994 Pa for a solution with maximum ϕ> 0.5 and a congested solution of 52% w/v, packing factor of 0.68, and high particle–particle interaction of the body-centered cubic (BCC) cell, favoring electrospun fiber formation. The packing factor, ϕ, and cell type, are highly sensitive and have potential applications in food systems, 3D bioprinting, among many other scientific domains.

Modeling the aspect ratio of commercial catalysts

AbstractMathematical modeling plays a diverse and crucial role in the chemical industry and academia. This manuscript describes how the physical and mechanical engineering disciplines help the commercialization of catalysts from evaluation to scale‐up and manufacturing. Forming and shaping the catalyst is the first basic step in the catalyst manufacturing industry. Part A shows some of the classic process methods that are employed for this purpose. Catalyst extrudates require proper engineering and process control of their aspect ratio. Catalyst extrudates with a high aspect ratio tend to yield a low reactor fill due to a loose packing. Catalyst extrudates with a low aspect ratio tend to yield high pressure drop. Part B introduces the tensile strength of the catalyst in order to predict the aspect ratio of catalyst extrudates in commercial plants. A force‐balance between the tensile strength of the catalyst and the impact forces due to collision experienced during manufacture leads to the dimensionless group . The group allows to introduce and quantify the severity of equipment and the severity of entire commercial plants.

Interstitial Optical Fiber-Mediated Multimodal Phototheranostics Based on an Aggregation-Induced NIR-II Emission Luminogen for Orthotopic Breast Cancer Treatment.

One-for-all phototheranostics based on a single molecule is recognized as a convenient approach for cancer treatment, whose efficacy relies on precise lesion localization through multimodal imaging, coupled with the efficient exertion of phototherapy. To unleash the full potential of phototheranostics, advancement in both phototheranostic agents and light delivery methods is essential. Herein, an integrated strategy combining a versatile molecule featuring aggregation-induced emission, namely tBuTTBD, with a modified optical fiber to realize comprehensive tumor diagnosis and "inside-out" irradiation in the orthotopic breast tumor, is proposed for the first time. Attributed to the intense donor-acceptor interaction, highly distorted conformation, abundant molecular rotors, and loose intermolecular packing upon aggregation, tBuTTBD can synchronously undergo second near-infrared (NIR-II) fluorescence emission, photothermal and photodynamic generation under laser irradiation, contributing to a trimodal NIR-II fluorescence-photoacoustic (PA)-photothermal imaging-guided phototherapy. The tumor treatment is further carried out following the insertion of a modified optical fiber, which is fabricated by splicing a flat-end fiber with an air-core fiber. This configuration aims to enable effective in situ phototherapy by maximizing energy utilization for therapeutic benefits. This work not only enriches the palette of NIR-II phototheranostic agents but also provides valuable insight for exploring an integrated phototheranostic protocol for practical cancer treatment.

Origins of non-ideal behaviour in voltammetric analysis of redox-active monolayers.

Disorder in redox-active monolayers convolutes electrochemical characterization. This disorder can come from pinhole defects, loose packing, heterogeneous distribution of redox-active headgroups, and lateral interactions between immobilized redox-active molecules. Identifying the source of non-ideal behaviour in cyclic voltammograms can be challenging as different types of disorder often cause similar non-ideal cyclic voltammetry behaviour such as peak broadening, large peak-to-peak separation, peak asymmetry and multiple peaks for single redox processes. This Review provides an overview of ideal voltammetric behaviour for redox-active monolayers, common manifestations of disorder on voltammetric responses, common experimental parameters that can be varied to interrogate sources of disorder, and finally, examples of different types of disorder and how they impact electrochemical responses.

Magmatic to solid-state evolution of a shallow emplaced agpaitic tinguaite (the Suc de Sara dyke, Velay volcanic province, France): implications for peralkaline melt segregation and extraction in ascending magmas

Abstract. In the last decades the mush model has been generalized to the complete trans-crustal magmatic system in which differentiation would be driven by segregation and extraction of trapped melts from crystal-rich mushes. Melt extraction processes involved are porous flow and strain localization, the latter being regarded as the main process acting during transfer through dykes and necks along which high differential stresses are acting on. We combine structural measurements together with petrological analyses and textural observations to constrain the model of emplacement and finally emphasize how shear deformation and strain localization structures promoted the residual melt segregation that occurred in a shallow silica-undersaturated peralkaline intrusion (Suc de Sara, Velay volcanic province, French Massif Central). In this study, we demonstrate that segregation and subsequent extraction of the CO2-rich residual melt occurred during magma ascent and final emplacement of the Suc de Sara tinguaite. Contrasting features of shear deformation between the margins that exhibited different permeabilities highlight that melt segregation started by compaction as a loose packing of emerging microlites and continued with melt filling of an anastomosed C/C′ band network developing in the crystal-rich mush subjected to high shear strain. Subsequent melt extraction throughout the country rock was controlled by the permeability of the hanging wall. Along the western hanging wall of the intrusion, extraction of the residual melt was prevented by the 15 cm thick chilled margin. In contrast, segregated melt circulated through the highly porous and permeable eastern margin, causing the fenitization of the country rock.

Local and global expansivity in water.

The supra-molecular structure of a liquid is strongly connected to its dynamics, which in turn control macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential to understand the thermal evolution of the dynamics ranging from the liquid to the glass. Here, we combine infrared spectroscopy (IR) measurements of the hydrogen (H) bond stretching vibration of water with molecular dynamics simulations and employ a quantitative analysis to extract the inter-molecular H-bond length in a wide temperature range of the liquid. The extracted expansivity of this H-bond differs strongly from that of the average nearest neighbor distance of oxygen atoms obtained through a common conversion of mass density. However, both properties can be connected through a simple model based on a random loose packing of spheres with a variable coordination number, which demonstrates the relevance of supra-molecular arrangement. Furthermore, the exclusion of the expansivity of the inter-molecular H-bonds reveals that the most compact molecular arrangement is formed in the range of ∼316-331K (i.e., above the density maximum) close to the temperature of several pressure-related anomalies, which indicates a characteristic point in the supra-molecular arrangement. These results confirm our earlier approach to deduce inter-molecular H-bond lengths via IR in polyalcohols [Gabriel et al. J. Chem. Phys. 154, 024503 (2021)] quantitatively and open a new alley to investigate the role of inter-molecular expansion as a precursor of molecular fluctuations on a bond-specific level.

Angle between DNA linker and nucleosome core particle regulates array compaction revealed by individual-particle cryo-electron tomography

The conformational dynamics of nucleosome arrays generate a diverse spectrum of microscopic states, posing challenges to their structural determination. Leveraging cryogenic electron tomography (cryo-ET), we determine the three-dimensional (3D) structures of individual mononucleosomes and arrays comprising di-, tri-, and tetranucleosomes. By slowing the rate of condensation through a reduction in ionic strength, we probe the intra-array structural transitions that precede inter-array interactions and liquid droplet formation. Under these conditions, the arrays exhibite irregular zig-zag conformations with loose packing. Increasing the ionic strength promoted intra-array compaction, yet we do not observe the previously reported regular 30-nanometer fibers. Interestingly, the presence of H1 do not induce array compaction; instead, one-third of the arrays display nucleosomes invaded by foreign DNA, suggesting an alternative role for H1 in chromatin network construction. We also find that the crucial parameter determining the structure adopted by chromatin arrays is the angle between the entry and exit of the DNA and the corresponding tangents to the nucleosomal disc. Our results provide insights into the initial stages of intra-array compaction, a critical precursor to condensation in the regulation of chromatin organization.

Thickness‐Dependent Formation Capacity and Mechanism of Planar (β)‐Conformation in Polydiarylfluorenes for Stable Deep‐Blue Polymer Light‐Emitting Diodes

AbstractConjugated polymers with p‐orbital overlap show intramolecular‐conformation‐dependent photophysical and electrical properties. Compared to the non‐planar segments, the planar conformation segments have a relatively long effective conjugated length and rigid backbone structure, which are beneficial for the enhancement of optoelectronic properties. Herein, the effect of film thickness on the formation capacity of planar (β) conformations in polyfluorene (poly[4‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl]‐co‐[5‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl], PODPF) for the fabrication of stable deep‐blue polymer light‐emitting diodes (PLEDs) is explored. Thickness‐tunable films with thicknesses ranging from 15 to 270 nm by controlling the concentration of precursor solution are prepared. The main observations are as follows. The PODPF chains in thin films are less likely to adopt the β conformations associated with the loose interchain packing in nano‐aggregates than those in thick films. Red‐shifted and well‐resolved emission spectra are observed for the annealed film with a high thickness, indicating the greater presence of β‐conformation segments. More interestingly, interchain aggregation is a necessary but not sufficient condition for the formation of β conformations. Finally, PLEDs based on β‐conformation segments have outstanding brightness, low turn‐on voltage, and stable deep‐blue electroluminescent behavior, confirming the unique advantage of planar conformation for optoelectronic applications.

Co/C Nanocomposites with Tunable Condensed States Induced by Conformation-Mediated Strategy for Electromagnetic Wave Absorption.

The strategic regulation of condensed state structures in multicomponent nanomaterials has emerged as an effective approach for achieving controllable electromagnetic (EM) properties. Herein, a novel conformation-mediated strategy is proposed to manipulate the condensed states of Co and C, as well as their interaction. The conformation of polyvinylpyrrolidone molecules is adjusted using a gradient methanol/water ratio, whereby the coordination dynamic equilibrium effectively governs the deposition of metal-organic framework precursors. This process ultimately influences the combined impact of derived Co and C in the resulting Co/C nanocomposites post-pyrolysis. The experimental results show that the condensed state structure of Co/C nanocomposites transitions from agglomerate state → to biphasic compact state → to loose packing state. Benefiting from the tunable collaboration between interfacial polarization and defects polarization, and the appropriate electrical conductivity, the diphasic compact state of Co/C nanocomposites achieves an effective absorbing bandwidth of 7.12GHz (2.1mm) and minimum reflection loss of -32.8dB. This study highlights the significance of condensed state manipulation in comprehensively regulating the EM wave absorption characteristics of carbon-based magnetic metal nanocomposites, encompassing factors such as conductivity loss, magnetic loss, defect polarization, and interface polarization.

Biophysical Evidence for the Amyloid Formation of a Recombinant Rab2 Isoform of Leishmania donovani.

The most fatal form of Visceral leishmaniasis or kala-azar is caused by the intracellular protozoan parasite Leishmania donovani. The life cycle and the infection pathway of the parasite are regulated by the small GTPase family of Rab proteins. The involvement of Rab proteins in neurodegenerative amyloidosis is implicated in protein misfolding, secretion abnormalities and dysregulation. The inter and intra-cellular shuttlings of Rab proteins are proposed to be aggregation-prone. However, the biophysical unfolding and aggregation of protozoan Rab proteins is limited. Understanding the aggregation mechanisms of Rab protein will determine their physical impact on the disease pathogenesis and individual health. This work investigates the acidic pH-induced unfolding and aggregation of a recombinant Rab2 protein from L. donovani (rLdRab2) using multi-spectroscopic probes. The acidic unfolding of rLdRab2 is characterised by intrinsic fluorescence and ANS assay, while aggregation is determined by Thioflavin-T and 90⁰ light scattering assay. Circular dichroism determined the secondary structure of monomers and aggregates. The aggregate morphology was imaged by transmission electron microscopy. rLdRab2 was modelled to be a Rab2 isoform with loose globular packing. The acidinduced unfolding of the protein is a plausible non-two-state process. At pH 2.0, a partially folded intermediate (PFI) state characterised by ~ 30% structural loss and exposed hydrophobic core was found to accumulate. The PFI state slowly converted into well-developed protofibrils at high protein concentrations demonstrating its amyloidogenic nature. The native state of the protein was also observed to be aggregation-prone at high protein concentrations. However, it formed amorphous aggregation instead of fibrils. To our knowledge, this is the first study to report in vitro amyloid-like behaviour of Rab proteins in L donovani. This study provides a novel opportunity to understand the complete biophysical characteristics of Rab2 protein of the lower eukaryote, L. donovani.

Grain boundary plasticity initiated by excess volume

Grain boundaries (GBs) serve not only as strong barriers to dislocation motion, but also as important carriers to accommodate plastic deformation in crystalline solids. During deformation, the inherent excess volume associated with loose atomic packing in GBs brings about a microscopic degree of freedom that can initiate GB plasticity, which is beyond the classic geometric description of GBs. However, identification of this atomistic process has long remained elusive due to its transient nature. Here, we use Au polycrystals to unveil a general and inherent route to initiating GB plasticity via a transient topological transition process triggered by the excess volume. This route underscores the general impact of a microscopic degree of freedom which is governed by a stress-triaxiality-based criterion. Our findings provide a missing perspective for developing a more comprehensive understanding of the role of GBs in plastic deformation.

Properties of packings and dispersions of superellipse sector particles.

Superellipse sector particles (SeSPs) are segments of superelliptical curves that form a tunable set of hard-particle shapes for granular and colloidal systems. SeSPs allow for continuous parametrization of corner sharpness, aspect ratio, and particle curvature; rods, circles, rectangles, and staples are examples of shapes SeSPs can model. We compare three computational processes: pair-wise Monte Carlo simulations that explore particle-particle geometric constraints, Monte Carlo simulations that reveal how these geometric constraints play out over dispersions of many particles, and Molecular Dynamics simulations that form random loose and close packings. We investigate the dependence of critical random loose and close packing fractions on particle parameters, finding that both values increase with opening aperture and decrease with increasing corner sharpness. The identified packing fractions are compared with the mean-field prediction of the random contact model; we find deviations from the model's prediction due to correlations between particle orientations. The complex interaction of spatial proximity and orientational alignment is also explored with a generalized spatioorientational distribution area (SODA) plot, which shows how higher density packings are achieved through particles assuming a small number of preferred configurations that depend sensitively on particle shape and system preparation.

Synthesis of novel colorless polyimides from benzimidazole diamines with various linearity

AbstractTo synthesize colorless superheat‐resistant polyimide films, one of the valid approaches is the incorporation of the asymmetric and warped structures in the main chain. Applying this approach on 5(6)‐amino‐2‐(4‐aminobenzene)benzimidazole (PABZ) and changing its linearity, 6, 5′‐diamine‐2′‐methyl‐1‐methyl‐2‐phenylbenzimidazole (5a) and 6, 3′‐diamine‐2′‐methyl‐1‐methyl‐2‐phenylbenzimidazole (5b) were devised and synthesized successfully, then polymerized with 1,2,4,5‐cyclohexanetetracarboxylic dianhydride (HPMDA). The prepared poly(benzimidazole imide)s (PBIIs) with the rigid main chain and loose packing had the excellent heat‐resistant level (Tg > 400°C) and optical properties (T400 > 80%). Besides, the alterations resulting from various linearities were discussed comprehensively. This research is beneficial to the application of optical field, providing a promising candidate of heat‐resistant colorless materials.

Thermal insulation refractory materials and products (review)

A literature review of manufacturing technologies, properties, and applications of thermal insulation refractory materials and products was carried out. It was shown that thermal insulation refractory materials are relevant for modern industry and science, as they contribute to solving many problems related to improving the efficiency, safety, and ecology of various technological processes. They are a promising object of research and development, as they are constantly being adapted to different operating conditions. Various methods of porosization (swelling (foaming); evaporation or burning of the pore­forming agent; loose packing; contact monolithization; bulk monolithization; and creation of combined structures) were shown to produce lightweight insulating refractories. A separate part of the review was devoted to fiber refractory materials and products as the most modern and relevant materials. The technologies for obtaining both refractory glass fibers and polycrystalline fibers, their properties, and applications were described. Based on the literature review on the classification, manufacturing technologies, and applications of thermal insulation refractory materials and products, the main directions of further research in the field of refractory fiber thermal insulation were identified.

An order of magnitude enhancement in ductility of a metallic glass of peak rejuvenation

Exceptional ductility has been a long-sought-after property of metallic glasses, and cryogenic thermal cycling rejuvenation has been actively explored to enhance the plasticity of metallic glasses. By tuning the holding time and number of cycles of cryogenic thermal cycling processing, we here report a (Zr0.8125Cu0.1875)79Ni10Al10Nb1 metallic glass of peak rejuvenation with the plasticity of an order of magnitude higher than that of the as-cast glass, without sacrificing its strength. Characterizations indicate that the loose atomic packing of the metallic glass of peak rejuvenation facilitates the generation and proliferation of shear bands in the early stage of plastic deformation, and the resultant dense shear bands tend to be deflected due to their interaction with each other and/or structural inhomogeneity in the matrix, hindering their rapid propagation and in turn increasing the plasticity. The combination of high relaxation enthalpy and high plasticity obtained here is outstanding from the previous rejuvenated metallic glasses which have either high relaxation enthalpy or high plasticity, while never both. This work identifies an alloy system with very high efficiency in plasticity improvement through cryogenic thermal cycling rejuvenation and represents a promising guide for improving the plasticity of metallic glasses.

Estimating the yield stress of soft materials via laser-induced breakdown spectroscopy

Taking three typical soft samples prepared respectively by loose packings of 77-, 95-, and 109-μm copper grains as examples, we perform an experiment to investigate the energy-dependent laser-induced breakdown spectroscopy (LIBS) of soft materials. We discovered a reversal phenomenon in the trend of energy dependence of plasma emission intensity: increasing initially and then decreasing separated by a well-defined critical energy. The trend reversal is attributed to the laser-induced recoil pressure at the critical energy just matching the sample’s yield strength. As a result, a one-to-one correspondence can be well established between the samples’ yield stress and the critical energy that is easily obtainable from LIBS measurements. This allows us to propose an innovative method for estimating the yield stress of soft materials via LIBS with attractive advantages including in-situ remote detection, real-time data collection, and minimal destructive to sample.

Preserving the Li {110} Texture to Achieve Long Cycle Life in Li Metal Electrode at High Rates

Abstract{110} textured Li metal electrode shows superior cycle performance when compared to its counterparts with other crystallographic textures or no texture. However, at high rates it suffers from a shortened cycle life that becomes significant with large cycling capacities – a common problem for most alkaline metal electrodes. In the present work, the morphological and structural evolution of the texture‐dependent Li electrodes cycled at different current densities is investigated and discovered that the cycling current density affected both the morphological and the crystallographic texture evolution of Li {110} metal electrode. In particular, loss of {110} texture at increased current densities accelerated the morphological deterioration of Li, leading to roughened Li plating and loose Li packing, and thus promoting the undesired consumption of Li and electrolyte. Thereafter a low‐rate‐healing strategy that significantly elongated the cycle life of Li metal electrode cycled at high rates is proposed. By adopting the healing strategy, a Li||Li symmetrical cell cycled at 10 mA cm−2 with a capacity of 10 mAh cm−2(with a 50% depth of discharge) can last for >800 runs, and a Li||LFP full cell can run for >300 cycles at 5 C with virtually no capacity degradation compared to the first cycle after activation.

Dynamic simulation of powder spreading processes toward the fabrication of metal-matrix diamond composites in selective laser melting

A novel method for the integrated production of structural and functional metal-matrix diamond composites is provided by selective laser melting (SLM) in the field of diamond tools. However, the uneven distribution of diamond particles and loose packing density in the powder bed can easily result in poor performance of diamond tools. In this work, a discrete element method model of diamond/CuSn composite powders is developed to simulate blade-spreading processes. It investigates how powder bed quality and particle dynamics are affected by diamond powder physical properties and powder spreading process parameters. The findings reveal that coarse diamond particles exhibit strong force chains at low velocities, whereas contact force chains are weak for fine CuSn particles at high velocities. It shows that diamond particles with irregular shapes have poor diffusivity and spreadability due to the large friction and mechanical locking forces, which causes diamond particles segregation. Therefore, the packing density and uniformity of the powder bed are both improved by reducing the volume fraction and particle size of diamond particles. In addition, the powder bed quality is improved by increasing the powder layer thickness and decreasing the translational speed of the blade, which weakens the shear expansion and jamming of diamond particles. The results have some significance for optimizing powder spreading processes toward the production of metal-matrix diamond composites in SLM.