Self-assembly Of Molecules Research Articles

Structural and electrical characterization of self-assembled Sb4 molecules on metal surfaces.

Antimonene is a promising two-dimensional material that is calculated to have a significant fundamental bandgap usable for advanced applications such as field-effect transistors, photoelectric devices, and the quantum-spin Hall state. Herein, we conducted a comprehensive investigation of self-assembled Sb4 islands on Au and Ag surfaces by scanning tunneling microscopy. The Sb4 molecules form α-phase and β-phase structures on Au and Ag surfaces, respectively, each exhibiting distinct island patterns. We simulated these structures using density functional theory calculations. Finally, we demonstrated the metallic band structure of Sb4 islands and observed the spatial and energy-dependent contributions of Sb4 molecules to the electronic states. This research enhances the understanding of the synthesis process of antimonene on metal surfaces and provides valuable insights for the industrial production of antimonene.

Impact of Self-Assembled Monolayer Structural Design on Perovskite Phase Regulation, Hole-Selective Contact, and Energy Loss in Inverted Perovskite Solar Cells

Recent studies have shown that self-assembled molecule (SAM)-based hole-selective contacts (HSCs) offer a promising solution to the challenges faced by perovskite solar cells (PVSCs), including minimal material consumption, scalable production, high interface stability, and the use of environmentally friendly solvents. In this study, the efficacy of two designs of SAMs (Cz and PA) as HSCs in inverted PVSCs was investigated by comparing them with the conventional MeO-2PACz (MeO) SAM. Surface analyses showed that the surface of PA is smoother than that of Cz, which helps to reduce interfacial defects. Subsequent perovskite deposition exhibited a reduced formation of the PbI2 phase, incidiating that its phase modulation ability is superior to that of MeO. Further analyses demonstrate the superior charge extraction ability of PA as a result of reduced interfacial defects and non-radiative recombination at the HSC/perovskite interface. By further coupling with phenethylammonium iodide (PEAI) surface passivation, both interfaces of the perovskite film were optimized and the inverted ((FAPbI3)0.85(MAPbBr3)0.15)0.95(CsPbI3)0.05 (bandgap = 1.62eV) PVSC achieves a high power conversion efficiency (PCE) of 23.3% and a very high open-circuit voltage of 1.227V due to the largely reduced energy loss. In addition, the PA PVSC exhibits enhanced long-term thermal stability at 85°C in a nitrogen atmosphere.

A self-assembly capsule-like solvation structure electrolyte for lithium metal batteries

The localized high-concentration electrolyte can be achieved by diluting a high-concentration electrolyte with an anti-solvent, which inherits the original solvation structural characteristics and reduces harmful interfacial reactions, resulting in an electrolyte with unique functions suitable for lithium metal batteries. Here, we design a localized high-concentration electrolyte with a capsule-like solvation structure and non-flammable properties to obtain stable-cycle and safe lithium metal batteries. The weak coordination and dipole-dipole interactions of fluorinated ether molecules promote the self-assembly of capsule-like solvated sheaths, encapsulating cations/anions and polar solvent molecules within the solvation sheath, which improves the oxidative stability of the electrolyte system and promotes the reduction of anions. A high-quality solid electrolyte layer was derived at the electrode interfaces, leading to rapid Li+ transport and dendrite-free lithium deposition. Consequently, a Coulombic efficiency of 99.7% is achieved, and the assembled Li||NCM811 battery exhibits a long cycle life of more than 400 cycles at 0.5C with a capacity retention of 83%. This work provides a promising approach for developing non-flammable electrolytes suitable for high-voltage lithium metal batteries.

Construction of myofibrillar protein-based Pickering emulsion for grass carp (Ctenopharyngodon idellus) based on interfacial self-assembly of spice aldehyde molecules: Mechanism and application of imine reaction-stabilized emulsion.

The purpose of this research is to investigate multiple structural spice aldehydes (cinnamaldehyde (CA), citronellal (CN), and melonal (MA)) interact with myofibrillar protein in grass carp (GCMP) and the effects of interfacial interactions on stability properties of Pickering emulsion. It was demonstrated that the functional characteristics of interfacial protein might be greatly improved by the complexation of spice aldehydes with protein particles at the water-oil interface. The fluorescence quenching and molecular docking results revealed that the binding mode of spice aldehyde is primarily dominated by hydrophobic interactions, yet there are hydrogen bonding interactions exist in special structure. When comparing multiple structure aldehyde, CA has a greater binding affinity than CN and MA, as well as the most binding sites at different temperatures. Among them, the interaction of CA and GCMP is enhanced by forming hydrogen bonds through π-bonds owing to its special aromatic ring structure. The O/W structure was further stabilized by the formation of conjugated and unconjugated imines of interfacial protein with spice aldehydes. This work provides a theoretical basis for the interaction and development of protein particles with spice aldehyde in Pickering emulsion stabilization and novel ideas for the application of low value aquatic protein for high quality.

Hexagonal liquid crystals as emerging quasi solid-state electrolytes for aqueous lithium-ion batteries

The increasing market demand ranging from portable electronics to electric vehicles drives the advancement of lithium-ion batteries. However, traditional liquid electrolytes used in LIBs are plagued by issues such as leakage, vaporization, and the degradation of active materials, which compromise performance and pose safety risks. To address these challenges, herein, the liquid-crystalline electrolytes with hexagonal phase were designed based on the self-assembly of amphiphilic molecules, which exhibit both high ionic conductivity and a high Li+ transference number. The hexagonal liquid crystal structure reconfigures the Li+ solvation structure and provides a transport pathway for the Li+ structural diffusion, facilitating the efficient transport of Li+ and contributing to the high ionic conductivity. Furthermore, the ordered arrangement of amphiphilic anion significantly restricts anion diffusion, resulting in an exceptionally high Li+ transference number of 0.92. Additionally, when utilizing NaV3O8 (NVO) as the anode and LiMn2O4 (LMO) as the cathode, the resultant full cell delivers impressive rate performance and stable cycling performance. This work highlights the potential of lyotropic liquid crystals in the development of high-performance quasi solid-state electrolytes for aqueous lithium-ion batteries and beyond.

In-situ isomerization and reversible self-assembly of photoresponsive polymeric colloidal molecules enabled by ON and OFF light control

Photocatalytic colloids enable light-triggered nonequilibrium interactions and are emerging as key components for the self-assembly of colloidal molecules (CMs) out of equilibrium. However, the material choices have largely been limited to inorganic substances and the potential for reconfiguring structures through dynamic light control remains underexplored, despite light being a convenient handle for tuning nonequilibrium interactions. Here, we introduce photoresponsive N,O-containing covalent organic polymer (NOCOP) colloids, which display multi-wavelength triggered fluorescence and switchable diffusiophoretic interactions with the addition of triethanolamine. Our system can form various flexible structures, including ABn-type molecules and linear chains. By varying the relative sizes of active to passive colloids, we significantly increase the structural diversity of A2B2-type molecules. Most importantly, we demonstrate in-situ transitions between different isomeric configurations and the reversible assembly of various structures, enabled by on-demand light ON and OFF control of diffusiophoretic interactions. Our work introduces a new photoresponsive colloidal system and a novel strategy for constructing and reconfiguring colloidal assemblies, with promising applications in microrobotics, optical devices, and smart materials.

Substrate as the primer of relay-race spin-driven self-assembly of chiral molecules

The molecules of chiral N-trifluoroacetylated α-aminoalcohols can self-assemble and form long and thin fiber-like supramolecular structures (strings). The strings effectively grow on the surface of the substrate and the amount of them, as well as their morphology, depend on the properties of the substrate. In particular, self-assembly was not observed on the electroconductive substrates, such as some metals (copper and aluminum) and graphite. The strings were found on the surface of titanium due to the peculiarities of the titanium oxide’s properties. The strings usually emanate from some nucleation zones, where the growth was initiated and then proceeded spontaneously outside these areas. We supposed the relay-race scheme of the transfer of spin polarization, which describes the mechanics and thermodynamics of the observed self-assembly process. The scheme implies the preliminary orientation of two molecules, their mutual polarization accompanied by spin-polarization, and finally the binding of the molecules. We also suppose this mechanism can play a significant role in various self-assembly processes in living cells.

Ordered Mesoporous Magnetic Ceramics from Single-Source Self-Assembled Ferrocene-Functionalized Giant Molecules

Ordered Mesoporous Magnetic Ceramics from Single-Source Self-Assembled Ferrocene-Functionalized Giant Molecules

Quantification of the Surface Coverage of Gold Nanoparticles with Mercaptosulfonates Using Isothermal Titration Calorimetry (ITC).

This manuscript presents a comprehensive study on the quantification of modifier molecules adsorbed on gold nanoparticles (AuNPs) using two complementary techniques Ellman's method (UV-vis spectroscopy) and isothermal titration calorimetry (ITC). In this paper, we compare the feasibility of using the ITC technique and Ellman's method to study the interactions of mercaptosulfonate compounds (sodium mercaptoethanesulfonate, MES, and sodium mercaptoundecanesulfonate, MUS) with the surface of AuNPs of various sizes. The thermodynamic functions of the attachment of mercaptosulfonates to AuNPs were determined, revealing a linear relationship between the number of adsorbed molecules and the surface area of the nanoparticles. The amount of MES and MUS determined by Ellman's method (7 and 11 molecules per square nm, respectively) is more than twice that measured by the ITC technique (3 and 4 molecules per square nm, respectively). The slight differences in the adsorption of MES and MUS on the gold surface are due to differences in the carbon chain length of the ligand molecules. In the case of MES, the formation of the Au-S bond is the dominant stage of the adsorption process, whereas for MUS, the ordering process and self-assembly of molecules on the gold surface are dominant.

Photo-Triggered ROS-Responsive Supramolecular Nanoprodrugs for Targeted and Synergistic Chemo/Photodynamic/Gas Therapy.

Photo-triggered ROS-responsive supramolecular nanoprodrugs (BNN6@GBTC NPs) are constructed via supramolecular self-assembly of amphiphilic prodrug molecule (GBTC) and NO donor (BNN6). BNN6@GBTC NPs possess good stability, ROS responsiveness, and selective HepG2 cells targetability via overexpressed galactose receptors on the cell membrane. When BNN6@GBTC NPs are taken up by HepG2 cells, they can generate ROS upon light irradiation, which can not only be used for photodynamic therapy, but also cleave the thioketal linkage to release camptothecin for chemotherapy. Meanwhile, BNN6 triggering release NO for gas therapy. BNN6@GBTC NPs enable targeted and synergistic chemo/photodynamic/gas therapy, which results in reduced damage to normal cells and enhanced anti-cancer efficacy in vitro. This work provides a novel approach for the design of nanoprodrugs based on supramolecular self-assembly to achieve the multimodal synergistic anti-cancer therapy.

Configurational Isomerization-Induced Orientation Switching: Non-Fused Ring Dipodal Phosphonic Acids as Hole-Extraction Layers for Efficient Organic Solar Cells.

Phosphonic acid (PA) self-assembled molecules have recently emerged as efficient hole-extraction layers (HELs) for organic solar cells (OSCs). However, the structural effects of PAs on their self-assembly behaviors on indium tin oxide (ITO) and thus photovoltaic performance remain obscure. Herein, we present a novel class of PAs, namely "non-fused ring dipodal phosphonic acids" (NFR-DPAs), featuring simple and malleable non-fused ring backbones and dipodal phosphonic acid anchoring groups. The efficacy of configurational isomerism in modulating the photoelectronic properties and switching molecular orientation of PAs atop electrodes results in distinct substrate surface energy and electronic characteristics. The NFR-DPA with linear (C2h symmetry) and brominated backbone exhibits favorable face-on orientation and enhanced work function modification capability compared to its angular (C2v symmetry) and non-brominated counterparts. This makes it versatile HELs in mitigating interfacial resistance for energy barrier-free hole collection, and affording optimal active layer morphology, which results in an impressive efficiency of 19.11 % with a low voltage loss of 0.52 V for binary OSC devices and an excellent efficiency of 19.66 % for ternary OSC devices. This study presents a new dimension to design PA-based HELs for high-performance OSCs.

Replenishing Cation-π Interactions for the Fabrication of Mesoporous Levodopa Nanoformulations for Parkinson Remission.

Directly assembling drugs into mesoporous nanoformulations will be greatly favored due to the combination of enhanced drug delivery efficiency and mesostructure-enabled nanobio interactions. However, such an approach is hindered due to the lack of understanding of polymer nanoparticles' formation mechanism, especially the relationship between polymerization, self-assembly, and the nucleation process. Here, by investigating the levodopa and dopamine polymerization process, we identify π-cation interaction as pivotal in the self-assembly and nucleation control of dopa molecules. Thus, through manipulation of the π-cation interaction, we present the direct assembly of a commercial drug, levodopa, into mesoporous nanoformulations. The synthesized nanospheres, approximately 200 nm in diameter, exhibit uniform mesopores of around 8 nm. These nanoformulations, abundant in mesopores, enhance chiral phenylalanine interaction with α-synuclein (Syn), curbing aggregation, safeguarding neurons, and alleviating Parkinson's pathology. When combating α-synuclein, the nanoformulation achieved ∼100% inhibition of protein aggregation and sustained neuron viability up to 300%. We believe that this study may advance mesoscale self-assembly knowledge, guiding future nanopharmaceutical developments.

Self-Assembly of Cyclic-Bending Collagen Fibrils by Polyimide Films.

The cyclic-bending morphologies of the fibrils formed by the self-assembly of type I collagen (Col) are closely related to the mechanisms of various diseases. Therefore, studies that allow the self-assembly of Col molecules to form cyclic-bending fibrils in vitro are vitally important. In this study, we successfully achieved the cyclic-bending shapes (specifically, a regular hexagonal shape) of Col molecules by controlling the steric structures of polyimide (PI) molecular chains through the film formation process. Specifically, when a single layer of PI film was baked, the PI molecular chains within the film bent in the direction parallel to the substrate surface plane. Repeating the layering and baking processes resulted in 3D structures of the PI molecular chains, which were oriented in the direction perpendicular to the substrate surface plane. This three-dimensional bending would result from the PI molecular chain interactions between the upper and lower layers. When the Col molecules were reacted on these film surfaces, they recognized the structures of the PI molecular chains and self-assembled to form cyclic-bending Col fibrils. Especially, in PI films subjected to three cycles of layering and baking, hemicircular-shaped Col fibrils were observed to be regularly arrayed. Additionally, these regularly cyclic-bending fibrils were aligned in the uniaxial direction through a uniaxial rubbing treatment of the PI films. This successful research is significant both as a method for controlling the morphologies of Col fibrils and as a study that explores the biomedical implications of Col fibril cyclic-bending in the living body.

Electrochemical surface science: Self-assembly of Porphyrin molecules at single crystal metal electrodes

A detailed understanding of properties and processes at surfaces and interfaces requires at least two types of most basic information, chemical composition and –distribution as well as structure. While surface science in ultrahigh vacuum is blessed with a plethora of high sensitivity and highest spatial and temporal resolution due to the free accessibility of the surfaces by any kind of probe beams, investigations of solid surfaces under ambient conditions, i.e. in contact with gases or liquids, were for a long time restricted to the use of integral photon-based reflection-, absorption-, emission-, and diffraction methods. This “methodological gap” between UHV surface science and environmental interface research became immediately, at least partially, closed after the realization of the scanning tunneling microscope (STM) and following variants of proximity probes (SPM). The full applicability of this class of methods also under ambient conditions opened the door to structure information of solid-liquid interfaces of comparable resolution as in UHV at room temperature, a “quantum leap” for the understanding of e.g. interfacial electrochemistry. This, in turn, highlighted the need of reliable determination of the chemical composition and distribution at solid-liquid interfaces and pushed the development of in situ X-ray photoelectron spectroscopy (XPS).The availability of both techniques, in situ SPM and in situ XPS closes the former methodological gap between the research in UHV and under ambient conditions. In particular, interfacial electrochemistry, being primarily interested in chemical processes at electrode/electrolyte interfaces benefits decisively of this development.In this article, as an example, we present systematic in situ STM measurements and results on the interactions and self-assembly of porphyrins at anion modified metal/electrolyte interfaces, an important class of molecules for the functionalization of surfaces for various applications. Atomically and sub-molecularly resolved potentiostatic and potentiodynamic in situ STM images of such molecular layers are nowadays standard and wait for an in-depth theoretical analysis.

Tailoring the π-conjugation in self-assembled hole-selective molecules for perovskite photovoltaics

Tailoring the π-conjugation in self-assembled hole-selective molecules for perovskite photovoltaics

Responsive Supramolecular Nanomicelles Formed through Self-Assembly of Acyclic Cucurbit[n]uril for Targeted Drug Delivery to Cancer Cells.

The supramolecular drug delivery systems (SDDSs) based on host-guest recognition through noncovalent interactions, capable of responsive behavior and dynamic switching to external stimuli, have attracted considerable attention in cancer therapy. In this study, a targeted dual-functional drug delivery system was designed and synthesized. A hydrophilic macrocyclic host molecule (acyclic cucurbit[n]uril ACB) was modified with folic acid (FA) as a targeting ligand. The guest molecule consists of a disulfide bond attached to adamantane (DA) and cannabidiol (CBD) at both ends of the response element of glutathione. Recognition and self-assembly of host and guest molecules successfully functionalize supramolecular nanomicelles (SNMs), targeting cancer cells and releasing drugs in a high glutathione environment. The interactions between host and guest molecules were investigated by using nuclear magnetic resonance (NMR), fluorescence titration, Fourier-transform infrared spectroscopy (FT-IR), and thermal analysis (TGA). Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the nanostructure of the SNMs. Experimentation with 5,5'-dithiobis (2-nitrobenzoic acid) (DTNB) demonstrated the responsiveness of SNMs to glutathione (GSH). In vitro cytotoxicity assays demonstrated that SNMs had a greater targeting efficacy for four types of cancer cells (HeLa, HCT-116, A549, and HepG2) compared to normal 293T cells. Cellular uptake studies revealed that HeLa cells more readily absorbed SNMs, leading to their accumulation in the tumor cell cytoplasm. Fluorescence colocalization assays verified that SNMs efficiently accumulated in organelles related to energy metabolism and signaling, including mitochondria and the endoplasmic reticulum, affecting cellular metabolic death. Both flow cytometry and confocal nuclear staining assays confirmed that SNMs effectively induced apoptosis over time, ultimately resulting in the death of cancer cells. These findings demonstrate that SNMs exhibit excellent targeting ability, responsiveness, high bioavailability, and stability, suggesting significant potential in drug delivery applications.

Asymmetric Modification of Carbazole Based Self-Assembled Monolayers by Hybrid Strategy for Inverted Perovskite Solar Cells.

Carbazole-based self-assembled molecules (SAMs) are widely applied in inverted perovskite solar cells (iPSCs) due to their unique molecular properties. However, the symmetrical structure of the carbazole-based SAMs makes it difficult to finely regulate their performance, which impedes the further enhancement of the efficiency and stability of iPSCs. This work demonstrates that by constructing an asymmetric carbazole core, 9H-thieno[2',3' : 4,5]thieno[3,2-b]indole) (TTID), the key properties of SAM molecules can be effectively regulated. It has been confirmed that the hybrid thieno[2,3-b]thiophene unit of this asymmetric core governs the energy level, the surface wettability, and the defect passivation capability of the SAMs, while the substituent of core has a greater impact on the molecular dipole and device stability. The synergistic effects from thieno[2,3-b]thiophene and fluorine lead to the KF-derived iPSC demonstrating a certified power conversion efficiency (PCE) of 25.17 % and excellent operational stability. This hybrid design concept offers a promising approach for the further structural modification of SAMs in iPSCs.

Growth of anthracene microcrystals by the micro-space sublimation method and their photophysical properties

Anthracene and its derivatives are widely utilized in optoelectronic devices due to their unique properties. Generally, single-crystal structures can avoid non-radiative recombination, enhance carrier mobility, and ultimately improve device performance. In this work, anthracene microcrystals were prepared using the micro-space sublimation method. Through real-time in-situ observation, the crystallization dynamics of anthracene molecules were revealed. Unlike traditional vacuum evaporation deposition technique, the close proximity of the substrate to the source facilitates the self-assembly of anthracene molecules into an ordered crystal structure. Six peaks can be observed in the photoluminescence spectrum, corresponding to various lowest excited state decay processes. The fluorescence intensity at the peak of 423 nm decreases significantly with increasing temperature. The reason for this is the relatively high exciton binding energy, which makes excitons more stable and easier to form. The lattice vibrations induced by increased temperature were found to affect the transport and separation of excitons. Time-resolved fluorescence spectroscopy imaging revealed that a relatively uniform distribution of fluorescence lifetimes in the anthracene microcrystals, indicating high crystallization quality. This work provides valuable insights for controlling the morphology and investigating the photophysical properties of organic semiconductors.

New Molecularly Flexible Self-Assembling Benzothiadiazole Derivatives: Mesomorphism And DFT Investigations

In the present study, we have synthesized symmetric/unsymmetrical BTD embedded self-assembling molecules and investigated for their mesomorphic properties. Two symmetrical series (BTDK-(2-18) and BTDC-(4-18)) comprises benzothiadiazole moiety as a central core unit which is connected to two different systematically varied end-groups, alkoxy ester and alkoxy coumaryl unit connected through ether and imine linkages. On the other hand, the asymmetric molecules have an alkoxy chalconyl unit at one end and a formyl group at the other. It was observed that, the mesomorphism is completely depends on the molecular flexibility. New molecules revealed mesomorphic behaviour with N (nematic), SmA (smectic-A) and SmC (smectic-C) mesophase with high thermal stability and greater range. Changes in mesogenic units (alkoxy ester & alkoxy coumaryl unit) and the impact of altering the alkoxy chain at both ends have been investigated. Interesting evaluation has been carried out on the molecular flexibility which resulted in different mesomorphic behaviour of molecules under study. Furthermore, the experimentally established values of the mesophase thermal stability (Tc) and mesophase temperature ranges (ΔTSmA, ΔTSmC, and ΔTN), as well as the type of the mesophase, were related to the calculated quantum chemical parameters (Frontier molecular orbitals (FMOs), Aspect Ratio, Polarizability, dipole moment, molecular and electrostatic potential (MEP)) that were obtained by using the DFT method of the investigated compounds.

Regulating phase homogeneity by self-assembled molecules for enhanced efficiency and stability of inverted perovskite solar cells

Regulating phase homogeneity by self-assembled molecules for enhanced efficiency and stability of inverted perovskite solar cells