Van Der Waals Interactions Research Articles

Structural evolution and thermoelectric performance in (GeTe)m(Sb2Te3)n compounds

Exploring the relationship between crystal structure and thermoelectric performance is a pivotal topic in the thermoelectric field. In this study, we have comprehensively investigated the correlation between the structural evolution of (GeTe)m(Sb2Te3)n pseudo-binary system and the thermoelectric properties. The proportion of van der Waals bonds increases with the rising Sb2Te3 content, resulting in an increase in the anisotropy of the electrical conductivity and a decrease in the average sound velocity. Additionally, the cation sites in the crystal lattice of these compounds exhibit a mixed occupancy of Ge/Sb atoms, although the cation sites adjacent to the van der Waals gaps are predominantly occupied by Sb atoms. The ultra-low lattice thermal conductivity of the GST124 and GST147 compounds is mainly attributed to the high concentration of van der Waals bonds and enhanced phonon scattering arising from Ge/Sb mixed cation occupancy and high density of defect structures. The high electrical conductivity combined with the low lattice thermal conductivity enables GST124 and GST147 compounds to achieve a maximum ZT value of 0.56 and 0.57, respectively. Higher thermoelectric performance can be achieved through optimization of the microstructure as well as the carrier concentration.

Formation and non-covalent interactions of binary and ternary complexes based on β-casein, Lentinus edodes mycelia polysaccharide, and taxifolin

Polyphenols, polysaccharides, and proteins are essential nutrients and functional substances present in food, and when present together these components often interact with each other to influence their structure and function. Proteins and polysaccharides are also excellent carrier materials for polyphenols. In this context, this study investigated the non-covalent interactions between taxifolin (TAX), Lentinus edodes mycelia polysaccharide (LMP), and β-casein (β-CN). β-CN and LMP spontaneously formed nanocomplexes by hydrogen bonds and van der Waals forces. The quenching constant and binding constant were (1.94 ± 0.02) × 1013 L mol−1 s−1 and (3.22 ± 0.17) × 105 L mol−1 at 298 K, respectively. The altered conformation of β-CN, resulting from the binding to LMP, affected the interaction with TAX. LMP significantly enhanced the binding affinity of TAX and β-CN, but did not change the static quenching binding mode. The binding constant for β-CN-TAX was (3.96 ± 0.09) × 1013 L mol−1, and that for the interaction between TAX and β-CN-LMP was (32.06 ± 0.05) × 1013 L mol−1. In summary, β-CN-LMP nanocomplexes have great potential as a nanocarrier for polyphenols, and this study provides a theoretical foundation for the rational design of non-covalent complexes involving LMP and β-CN, both in binary and ternary configurations.

Van der Waals Engineering of Charge Density Waves in One-Dimensional Nb6Te6 Nanowires.

One-dimensional (1D) systems have played a crucial role in the development of fundamental physics and practical applications. Recently, transition metal monochalcogenide (TMM) wires based on molybdenum (Mo) and tungsten (W) have emerged as promising platforms for investigating 1D physics in pure van der Waals (vdW) platforms. Here, we report on the bottom-up fabrication of Nb6Te6 wires down to the single-wire limit. The unique properties of Nb6Te6 single wire enable the realization of 1D charge density wave (CDW) phases in an isolated single TMM wire. Moreover, we revealed the appealing regulation of 1D CDW orders by van der Waals interactions at either the 1D-2D interface (i.e., rotation of a single wire along its wire axis) or the 1D-1D interface. Two rotation angles (30° and 0°) give rise to 3 × 1 and zigzag chain CDW morphologies, respectively, which exhibit pronounced differences in atomic displacement by a factor of 2. The interwire vdW coupling overwhelms its counterpart at the 1D-2D interface, thus locking the rotation angle (at 0°) as well as the interwire atomic registries. In contrast, interestingly, the phases of the charge oscillations are independent of the adjacent wires. The ability to tailor 1D charge orders provides a crucial addition to the toll set of vdW integrations beyond two-dimensional materials.

Particle Bounce Stick Behavior in the Rotating Frame of Reference

Abstract Particle deposition is a major damage mechanism for gas turbine components, especially in the secondary air system. Predicting the transport and deposition of ingested atmospheric contaminants is of great interest in component-level simulations. Bounce stick models predict deposition upon collision with a wall during Lagrangian particle tracking; they consider a range of physical phenomena, including van der Waals forces and plastic deformation. The effect of the rotating frame of reference on particle collision physics has thus far been neglected in the literature despite the significant centrifugal (CF) loads experienced by many components of interest for deposition studies, for example, turbine blades. The collision physics of the rotating frame are discussed here using low-order models and Monte Carlo style simulations. The present work aims to provide a conceptual framework for the inclusion of CF forces in collision physics. No significant effect was found on the rebound velocities of particles experiencing “worst case” CF forces. However, differences were observed in the sticking probability between concave and convex rotating surfaces, where the CF forces act in opposing directions to either push the particle into the surface or detach it. A force-based analogy of the popular critical velocity model was developed to study the phenomenon. It was used in a Monte Carlo style simulation of a rotor disk, finding that the variation of critical velocity due to CF forces was likely to bias deposition toward concave surfaces. The collision physics of the rotating frame were found to be unintuitive, with complex implications for modeling deposition in gas turbine components. However, they were consequential in determining the distribution of deposition through the system, hence should be included in particle deposition simulations in computational fluid dynamics (CFD).

Improved comprehensive adhesion performance of aggregate- recycled asphalt interface via incorporating steel slag

Steel slag, a typical industrial waste, reveals high alkalinity and abundant texture, endowing its excellent adhesion performance with asphalt and facilitating its implementation in recycled asphalt mixture. While few studies focused on the interaction mechanism and comprehensive adhesion performance of steel slag- recycled asphalt interface. Hence, this topic merits further exploration. In this study, the interface models of steel slag-asphalt were established and their interface parameters also were surveyed. And the comprehensive evaluation index of adhesion performance was explored by the improved radar chart. The experimental results elaborate that steel slag exhibits the larger surface energy of 46.69 mJ/m2 and higher percentage of dispersion component of 76.6 %. Recycled asphalt-steel slag demonstrates the greater adhesion work, the smaller exfoliated work and the larger adhesive destructive force than recycled asphalt-basalt, indicating its superior adhesion ability. Steel slag-asphalt molecule behaves the lower radial distribution function and larger interfacial bonding energy due to the dual provision of van der Waals force and electrostatic adsorption force. The exfoliated work in experiment and adhesion work in simulation presents a Pearson correlation coefficient of −0.683, resulting in their strong negative correlation. Steel slag-recycled asphalt interface with the higher comprehensive evaluation index of 0.9155 reveals the superior comprehensive adhesion performance than basalt- recycled asphalt.

Controlled growth of 3R phase niobium diselenide and its properties

Inversion symmetry broken 3R phase transition metal dichalcogenides (TMDs) show fascinating prospects in spintronics, valleytronics, and nonlinear optics. However, the controlled synthesis of 3R phase TMDs is still a great challenge. In this work, two-dimensional 3R-NbSe2 single crystals up to 0.2 mm were synthesized for the first time through chemical vapor deposition method by designing a space-confined system. The crystal size and morphology can be controlled by the location of the stacked substrates and the amount of the Nb2O5 precursor. Scanning transmission electron microscopy and Raman measurements reveal the NbSe2 exhibits a pure 3R stacking mode with relatively weak interlayer van der Waals interactions. Importantly, 3R-NbSe2 shows obvious second harmonic generation signal which intensity intensified as thickness increases. Density functional theory calculations and optical absorption demonstrate the coexistence of metallic and semiconducting optical properties of 3R-NbSe2. We designed a NbSe2/WS2/NbSe2 photodetector utilizing the metallicity of 3R-NbSe2, which shows good performance especially an ultrafast response (6–7 μs, 0.5 ms − 7.9 s for Au electrodes in literature). The proposed strategy and findings are of great significance for the growth of many other 3R-TMDs and applications of nonlinear optical and ultrafast devices.

Active Constituents with Tyrosinase Inhibitory Activities from Waste Tobacco Leaves.

One novel compound, (R)-3, 6-diethoxy-4-hydroxycyclohex-3-en-1-one (1) and thirteen known compounds were isolated from the waste tobacco leaves. The structures of two compounds (1-2) were confirmed and attributed firstly by the extensive spectroscopic data, including 1D/2D NMR, IR, HR-ESI-MS, CD, and ECD spectra. Notably, seven compounds (2, 3, 9, 10, 11, 12, and 13) exhibited better tyrosinase inhibitory activity than the positive control kojic acid. The binding modes of these compounds revealed that their structure formed strong hydrogen bonds and van der Waals forces with the active sites of tyrosinase. These results indicated that waste tobacco leaves are good resources for developing tyrosinase inhibitors.

Porous molecularly imprinted beads for highly specific separation of 10-hydroxycamptothecine: An imprinted strategy based on modified cellulose hydrogel

10-hydroxycamptothecine (HCPT), known as a natural alkaloid with significant anti-cancer properties in Camptotheca acuminata, has valuable application prospects in health and medicine and has attracted worldwide attention especially in the field of cancer research. In this study, a porous cellulose hydrogel-based molecularly imprinted bead (PCH@MIBs) with high affinity and selectivity was prepared and served as novel fillers of solid phase extraction (SPE) for selectively separating HCPT. The combination of polydopamine (PDA) modified cellulose hydrogel and highly selective molecular imprinting technology enabled the efficient and targeted adsorption for template molecules. The mixture of nano-calcium carbonate and cellulose solution underwent a reaction with an acidic coagulation bath, which endowed the cellulose hydrogel beads with porous structures. Porous cellulose hydrogel beads were coated with a PDA layer, followed by the preparation of PCH@MIBs using HCPT as template molecules and acrylamide (AM) as functional monomers, resulting in hydrogel-based materials with specific adsorption cavities matched to HCPT. The PCH@MIBs exhibited excellent adsorption capacity (57.87 mg·g−1) and adsorption selectivity (IF = 3.75), as well as good reusability (5 of cycles). The PCH@MIBs were successfully used to separate HCPT from C. acuminata fruits, with an impressive adsorption capacity (0.0974 mg·g−1) and recovery of HCPT (91.27 %). Mechanism analysis demonstrated that the recognition of PCH@MIBs was primarily achieved through non-covalent interactions between AM and HCPT, specifically hydrogen bonds and Van der Waals forces. This work proposes a novel strategy for constructing porous cellulose-based molecularly imprinted hydrogel beads to specific capture targeted compound, which have broad potential for practical application.

Non-covalent interactions between large yellow croaker (Pseudosciaena crocea) roe protein isolates and curcumin: Implications for enhanced curcumin delivery

This study investigated the influence of heat treatment on the interaction of large yellow croaker (Pseudosciaena crocea) roe protein isolate (pcRPI) with curcumin (Cur), and heated pcRPI (HpcRPI)-Cur and pcRPI-Cur complexes were also prepared. Fourier transform infrared spectroscopy, fluorescence spectroscopy, and surface hydrophobicity analysis indicated that pcRPI and HpcRPI bind to Cur mainly by hydrogen bonds, van der Waals forces, and hydrophobic interactions, and compared with pcRPI, HpcRPI showed better binding effects with Cur. Molecular docking analysis also evaluated the binding site and the forces between vitellogenin, vitellogenin B and C in pcRPI and Cur. Furthermore, HpcRPI-Cur could form gels induced by glucono-δ-lactone (GDL), while pcRPI-Cur-GDL exhibited a fluid state. The HpcRPI-Cur-GDL gels showed great protective effects on Cur in the resistant gastrointestinal environment. These results indicated that heat treatment will improve the application of pcRPI as a functional material in the food field.

Effects of pH-varying thermal modification on sewage sludge: A focus on releasing nitrogen- and phosphorus-containing substances

Sewage sludge is promising for the recovery and utilisation of nutrient components, but its complex nature hinders the release of these components. The combination of pH and thermal modifications shows promise for the release of nutrient components from sludge. However, comprehensive studies on the full spectrum of pH levels and corresponding mechanisms of pH-varying thermal modification are lacking. In this study, the main nutrient components, physicochemical properties, molecular structure, and noncovalent interactions of sludge were comprehensively investigated through pH-varying thermal modification (within a pH range of 2.0 to 12.0 under the same thermal condition). The experimental results showed that the release of main organics, particularly nitrogen (N)-containing organics, was well-fitted, with a tick-like function (R2: 0.74–0.96). The thermal protons exhibited a notable accumulative mutagenic effect on the N-containing organics release, while the thermal hydroxyl ions had a more direct effect, as revealed by the changes in multivalent metals and molecular structures with the protonation–deprotonation of carboxyl groups. The driving force for the release of N-containing organics was identified as the fluctuation of electrostatic interactions at the solid–liquid interface of the sludge. However, the release of phosphorus (P)-containing substances exhibited a contrasting response to that of N-containing substances with varying pH, likely because the reaction sites of thermal protons and thermal hydroxyl ions for P-containing substances were different. Moreover, high concentrations of thermal protons and hydroxyl ions collapsed the Lifshitz–van der Waals interactions of sludge, resulting in a decrease in viscoelasticity and binding strength. These propositions were further confirmed through statistical analyses of the main indicators of the main nutrient components, physicochemical properties, and noncovalent interactions of sludge. These findings can provide a basis for optimising characteristic-specific methods to recovery nutrient components (N/P) from sludge.

A study on novel dual-functional photothermal material for high-efficient solar energy harvesting and storage

The solar-heat storage efficiency of devices based on phase change materials (PCMs) is limited due to the light absorption and internal heat transfer within the PCMs, unclear thermal conductivity-enhancement mechanism within nanocomposite PCMs, and uncontrollable photothermal-interface modulation. Therefore, a novel controllable strategy was proposed in this study to fabricate dual-functional photothermal storage three-dimensional (3D) phase change blocks (PCBs) with higher thermal conductivity (27.98 W/m·K) and spectral absorption (98.03 %) compared to those of most previously reported PCM-based devices. The as-synthesized PCBs contained millimeter-sized graphite plates with horizontal Van der Waals bonds and oriented micro/nanoscale graphite nanosheets. The structural properties of thin PCM layers between the PCB sheets have synergistically reduced the internal interfacial thermal resistance of the PCBs. Laser-controllable induction was used to fabricate integrated biomimetic-forest 3D optical absorbers on the high thermal conductivity interface of the PCBs, which significantly reduced the thermal resistance of the optical-thermal interface. The resulting 3D-PCBs, integrated with thermoelectric generators, powered portable electronic devices, expanding the applications of traditional PCM heat-storage devices. Therefore, this study will guide the future design of high-performance solar-thermal storage PCMs with a wide range of practical applications.

The potential of MOFs embedded in banana cellulose materials for application in dialysis

The accumulation of uremic toxins in the human body presents a fatal issue that leads to the development of chronic kidney disease. The effective removal of these toxins from the bloodstream is crucial for enhancing the efficacy of hemodialysis and improving the survival rate. A comprehensive understanding of the interactions between an adsorbent and the uremic toxins is vital in the development of efficient materials for the elimination of these hazardous compounds. In this study, we investigate the adsorption behavior of various toxins, namely cresol sulfate, and creatinine, using banana cellulose and its modified form with MOFs, namely Ni-BTC, Cu-BTC, and Co-BTC. The adsorption behavior is characterized using the Langmuir and Freundlich models. The analysis reveals that the Langmuir model provides a better fit to the isotherm data compared to the Freundlich model. Furthermore, the adsorption kinetics data indicate that both banana cellulose and its modified form with MOFs adhere to the pseudo-second-order rate models rather than the pseudo-first-order model. The capacities for adsorption of cresol sulfate by banana cellulose, Ni-BTC@cellulose, Cu-BTC@cellulose, and Co-BTC@cellulose were measured to be 115, 402, 509, and 577 mg/g, respectively. Conversely, the capacities for adsorption of creatinine were found to be 166, 514, 605, and 704 mg/g, respectively. The underlying mechanism of adsorption is contingent upon the van der Waals interactions and π–π interactions. Furthermore, even after undergoing five cycles, the removal efficiency for cresol sulfate and creatinine remained at 88 % and 85 %, respectively. These findings demonstrate the renderability of MOFs@cellulose. The antimicrobial activity of the prepared MOFs was recorded for all MOFs composites against tested pathogenic microbes. Additionally, the MOFs@cellulose exhibited a satisfactory level of blood compatibility. Consequently, these exceptional MOFs@cellulose present a promising opportunity for reducing costs associated with clinical hemodialysis.

A novel loofah-like chitosan/alginate composite aerogels prepared for efficient removal of perchlorate: Experimental and DFT study

Perchlorate, an emerging contaminant in drinking water, has attracted global attention. In this study, a novel loofah-like porous chitosan/alginate composite aerogel (CTS/SA-m) was fabricated using ionotropic pregelation and freeze-dried technology to effectively adsorb perchlorate. The performance, isotherms, thermodynamics, and kinetics of perchlorate adsorption by CTS/SA-m were systematically discussed. The results showed that the loofah-like CTS/SA-m with high hydrophilicity exhibited excellent adsorption properties. Over 95 % of the removal rate in 10 min can be achieved, with initial concentration of perchlorate and CTS/SA-m dosage of 10 mg/L and 2 g/L, respectively. And 70.15 mg/g of equilibrium adsorption capacity of perchlorate could be reached at pH 5 and 298 K. pH had little effect on the removal rate of perchlorate, the removal rate surpassed 85 % over a wide pH range of 3.0–11.0. Multilayer adsorption (MLA), intraparticle diffusion (IPD), and adsorption on the active site (AOAS) models were employed to discuss the adsorption mechanism of perchlorate. It was confirmed that double-layer chemisorption played a dominant role. Density functional theory (DFT) analysis of binding energy revealed the effect of functional groups on the ClO4− adsorption strength in the order of –NH3+ > –COOH > –NH2 > –OH. Furthermore, electrostatic potential and the independent gradient model confirmed that electrostatic interactions, hydrogen bonding, and van der Waals forces contributed to the highly efficient adsorption of perchlorate. These findings have a vital promoting effect on perchlorate removal technology in water treatment. Moreover, the loofah-like CTS/SA-m aerogel material, exhibiting outstanding performance, shows great potential in effectively in trapping perchlorate anions from aquatic systems.

Freeze-sonication delamination method of high crystalline-quality MXene with high yield

MXene has attracted broad attention for its unique physicochemical properties and has flourished in many research areas. Since MXene obtained by high crystalline-quality MAX phase has excellent stability and properties, the etching of high crystalline-quality MAX phase and delamination into monolayer will become an inevitable trend. However, the delamination of the high crystalline-quality MXene is significantly more challenging than conventional MXene because of the more vital van der Waals forces of the more regular interlayer structure. Here, we propose a freeze-sonication delamination (FSD) strategy that can solve the difficult problem of efficiently exfoliation of high crystalline-quality MXene. The principle is to utilize the synergistic effect of ultrasound and ionic intercalation to allow a large number of water molecules to penetrate into the interlayer, which results in volume expansion, and then ultrasound to obtain monolayer MXene in a frozen state. This method not only increases the yield of high crystalline-quality monolayer MXene but also prevents the size reduction and the nanosheet destruction. The yield of monolayer MXene reached 74.2 % with a concentration of 19.8 mg/mL after six FSD cycles (the time of ultrasound treatment is 5 min after per freeze). Meanwhile, under the protection of ice, the obtained monolayer MXene has a larger size with more complete nanosheets than ultrasound-delaminated MXene. Supercapacitors made of high crystalline-quality MXene exhibits excellent gravimetric capacitance of 261.1 F/g and satisfactory cycling stability.

Effect of surface functional groups of polystyrene micro/nano plastics on the release of NOM from flocs during the aging process

Currently, the hidden risk of microplastics in the coagulation process has attracted much attention. However, previous studies aimed at improving the removal efficiency of microplastics and ignored the importance of interactions between microplastics and natural organic matter (NOM). This study investigated how polystyrene micro/nano particles impact the release of NOM during the aging of flocs formed by aluminum-based coagulants Al13 and AlCl3. The results elucidated that nano-particles with small particle sizes and agglomerative states are more likely to interact with coagulants. After 7 years of floc aging, the DOC content of the nano system decreased by more than 40%, while the micron system did not change significantly. During coagulation, the benzene rings in polystyrene particles form complexes with electrophilic aluminum ions through π-bonding, creating new Al-O bonds. NOM tends to adsorb at micro/nano plastic interfaces due to hydrophobic interactions and conformational entropy. In the aging process, the structure of PS-Al13 or PS-AlCl3 flocs and the functional groups on the surface of micro/nano plastics control the absorption and release of organic matter through hydrophobic, van der Waals forces, hydration, and polymer bridging. In the system with the addition of nano plastics, several DBPs such as TCAA, DCAA, TBM, DBCM and nitrosamines were reduced by more than 50%. The reaction order of different morphological structures and surface functional groups of microplastics to Al13 and AlCl3 systems is aromatic C-H > C-OH > C-O > NH2 > aromatic CC > aliphatic C-H and C-O>H-CO> NH2 >C-OH> aliphatic C-H. The results provided a new sight to explore the effect of micro/nano plastics on the release of NOM during flocs aging.

Silica-supported ionic liquid for efficient gaseous arsenic oxide removal through hydrogen bonding

The emission of highly-toxic gaseous As2O3 (As2O3 (g)) from nonferrous metal smelting poses environmental concerns. In this study, we prepared an adsorbent (SMIL-X) by loading an ionic liquid (IL) ([HOEtMI]NTf2) into MCM-41 through an impregnation–evaporation process and then applied it to adsorb As2O3 (g). SMIL-20% exhibited an As2O3 (g) adsorption capacity of 35.48 mg/g at 400 °C, which was 490% times higher than that of neat MCM-41. Characterization of SMIL-X indicated that the IL was mainly supported on MCM-41 through O–H…O bonds formed between the hydroxyl groups (–OH) and the silanol groups (Si–OH) and the O–H…F bonds formed between the C–F groups and the Si–OH groups. The hydrogen bonds significantly contributed to the adsorption of As2O3 (g), with –NH and –OH groups forming hydrogen bonds with As–O species (i.e., N–H…O and O–H…O). This showed superior performance to traditional adsorbents that rely on van der Waals forces and chemisorption. Moreover, after exposure to high concentrations of SO2, the adsorption capacities remained at 76% of their initial values, demonstrating some sulfur resistance. This study presents an excellent adsorbent for the purification of As2O3 (g) and shows promising application potential for treating flue gas emitted by nonferrous metal smelting processes.

Synthesis and crystal structures of 5,17-dibromo-26,28-dihydroxy-25,27-dipropynyloxycalix[4]arene, 5,17-dibromo-26,28-dipropoxy-25,27-dipropynyloxycalix[4]arene and 25,27-bis(2-azidoethoxy)-5,17-dibromo-26,28-dihydroxycalix[4]arene

The calixarenes, 5,17-dibromo-26,28-dihydroxy-25,27-dipropynyloxycalix[4]arene (C34H26Br2O4, 1), 5,17-dibromo-26,28-dipropoxy-25,27-dipropynyloxycalix[4]arene (C40H38Br2O4, 2) and 25,27-bis(2-azidoethoxy)-5,17-dibromo-26,28-dihydroxycalix[4]arene (C32H28Br2N6O4, 3) possess a pinched cone molecular shape for 1 and 3, and a 1,3-alternate shape for compound 2. In calixarenes 1 and 3, the cone conformations are additionally stabilized by intramolecular O—H...O hydrogen bonds, while in calixarene 2 intramolecular Br...Br interactions consolidate the 1,3-alternate molecular conformation. The dense crystal packing of the cone dialkyne 1 is a consequence of π–π, C—H...π and C—H...O interactions. In the crystal of the diazide 3, there are large channels extending parallel to the c axis, which are filled by highly disordered CH2Cl2 solvent molecules. Their contribution to the intensity data was removed by the SQUEEZE procedure that showed an accessible void volume of 585 Å3 where there is room for 4.5 CH2Cl2 solvent molecules per unit cell. Rigid molecules of the 1,3-alternate calixarene 2 form a columnar head-to-tail packing parallel to [010] via van der Waals interactions, and the resulting columns are held together by weak C—H...π contacts.

Revealing the Improved Binding Interaction of Plant Alkaloid Harmaline with Human Hemoglobin in Molecular Crowding Condition.

Harmaline and harmine are two structurally similar β-carboline alkaloids with several therapeutic activities, such as anti-inflammatory, antioxidant, neuroprotective, nephroprotective, antidiabetic, and antitumor activities. It has been previously reported that the interaction between harmaline and hemoglobin (Hb) is weak in buffer media compared to harmine. Crowding agents induce a molecular crowding environment in the ex vivo condition, which is almost similar to the intracellular environment. In this present study, we have investigated the nature of the interactions of harmaline and harmine with Hb by increasing the percentage of the crowding agent in buffer solution. The results of the UV-vis and fluorescence spectroscopy analysis have showed that with an increasing proportion of crowding agents, the interaction between harmaline and Hb is steadily improving in comparison to harmine. It has been found that the binding constant of Hb-harmaline reaches 6.82 × 105 M-1 in the 40% polyethylene glycol 200-mediated crowding condition, indicating high affinity compared to very low interaction in buffer media. Steady-state fluorescence anisotropy along with fluorescence lifetime measurements further revealed that the rotational movement of harmaline is maximally restricted by Hb in high crowding environments. Stoichiometry results represent that Hb and harmaline interacts in a 1:1 ratio in different percentages of the crowding agent. The circular dichroism spectroscopic results predict stronger interaction of harmaline with Hb (secondary structure alterations) in a higher crowding environment. From the melting study, it was found that the reactions between Hb and harmaline in crowding environments are endothermic (ΔH > 0) and disordering (ΔS > 0) in nature, indicating that hydrogen bonding and van der Waals interactions are the main interacting forces between Hb and harmaline. Harmaline molecules are more reactive in molecular crowding conditions than in normal buffer condition. This study represents that the interaction between harmaline and Hb is stronger compared to the structurally similar harmine in a molecular crowding environment, which may enlighten the drug discovery process in cell-mimicking conditions.

Topological phase transition in compressed van der Waals superlattice heterostructure BiTeCl/HfTe2

Abstract Based on first-principles calculation, we investigate electronic band structures and topological properties of heterostructure BiTeCl/HfTe2 under c direction strain. In the primitive structure, this material undergoes phase transition from insulator with narrow indirect gap to metal by strong spin-orbital coupling. When strain effect is considered, band inversion at time-reversal invariant point Z is responsible for topological phase transition. These nontrivial topologies are caused by two different types of band crossing. The observable topological surface states in (110) surface also support that this material experiences topological phase transition twice. The layered heterostructure with van der Waals force provides us a new desirable platform to control topological phase transition and construct topological superconductors.

Effect of Hydrogen Bonding and Chirality in Star-Shaped Molecules with Peripheral Triphenylamines: Liquid Crystal Semiconductors and Gels.

Organic semiconductors with well-defined architectures pose a suitable alternative to amorphous silicon-based inorganic semiconductors. Encouraged by the development of organic semiconductors based on columnar liquid crystals, herein, we report on a family of C3-symmetric star-shaped mesogens based on triphenylamine (TPA), a functional unit with strong electron donor character. Highly stable columnar phases with high hole mobility values were obtained out of this nonplanar functional unit, and this was achieved by using flexible amide spacers to join the TPA units to a tris(triazolyl)triazine (T) star-shaped core, allowing the formation of intermolecular hydrogen bonds. The presence of hydrogen bonds results in a stabilization of the columnar architectures either in bulk or in the presence of solvents by reinforcing π-stacking and van der Waals interactions, as deduced by Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) studies. Furthermore, the introduction of a stereogenic center in the flexible spacer prompts the formation of chiral aggregates in the liquid crystal state and in the organogel formed in 1-octanol, as demonstrated by circular dichroism spectroscopy.