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Self-assembling amphiphilic cyanine dyes, such as C8S3, are promising candidates for energy storage and optoelectronic applications due to their efficient energy transport properties. C8S3 is known to self-assemble in water into double-walled J-aggregates. Thus far, the molecular self-assembly steps remain shrouded in mystery. Here, we employ a multiscale approach to unravel the first self-assembly step: dimerization. Our multiscale approach combines molecular dynamics simulations with quantum chemistry calculations to obtain a Frenkel exciton Hamiltonian, which we then use in spectral calculations to determine the absorption and two-dimensional electronic spectra of C8S3 monomer and dimer systems. We model these systems solvated in both water and methanol, validating our model with experiments in methanol solution. Our theoretical results predict a measurable anisotropy decay upon dimerization, which is experimentally confirmed. Our approach provides a tool for the experimental probing of dimerization. Moreover, molecular dynamics simulations reveal that the dimer conformation is characterized by the interaction between the hydrophobic aliphatic tails rather than the π–π stacking previously reported for other cyanine dyes. Our results pave the way for future research into the mechanism of molecular self-assembly in similar light-harvesting complexes, offering valuable insights for understanding and optimizing self-assembly processes for various (nano)technological applications. [ABSTRACT FROM AUTHOR]

Tert-butyl functional groups can modulate the self-assembly behavior of organic molecules on surfaces. However, the precise construction of supramolecular architectures through their controlled thermal removal remains a challenge. Herein, we precisely controlled the removal amount of tert-butyl groups in tetraazaperopyrene derivatives by stepwise annealing on Ag(111). The evolution of 4tBu-TAPP supramolecular self-assembly from the grid-like structure composed of 3tBu-TAPP through the honeycomb network formed by 2tBu-TAPP to the one-dimensional chain co-assembled by tBu-TAPP and TAPP was successfully realized. This series of supramolecular nanostructures were directly visualized by high resolution scanning tunneling microscopy. Tip manipulation and density functional theory calculations show that the formation of honeycomb network structure can be attributed to the van der Waals interactions, N–Ag–N coordination bonds, and weak C–H⋯N hydrogen bonds. Further addition of two tert-butyl groups (6tBu-TAPP) leads to a completely different assembly evolution, due to the fact that the additional tert-butyl groups affect the molecular adsorption behavior and ultimately induce desorption. This work can possibly be exploited in constructing stable and long-range ordered nanostructures in surface-assisted systems, which can also promote the development of nanostructures in functional molecular devices. [ABSTRACT FROM AUTHOR]

The semiconductor/insulator blends for organic field-effect transistors are a potential solution to improve the charge transport in the active layer by inducing phase separation in the blends. However, the technique is less investigated for long-chain conducting polymers such as Poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPPDTT), and lateral phase separation is generally reported due to the instability during solvent evaporation, which results in degraded device performance. Herein, we report how to tailor the dominant mechanism of phase separation in such blends and the molecular assembly of the polymer. For DPPDTT/PMMA blends, we found that for higher DPPDTT concentrations (more than 75%) where the vertical phase separation mechanism is dominant, PMMA assisted in the self-assembly of DPPDTT to form nanowires and micro-transport channels on top of PMMA. The formation of nanowires yielded 13 times higher mobility as compared to pristine devices. For blend ratios with DPPDTT ≤ 50%, both the competing mechanisms, vertical and lateral phase separation, are taking place. It resulted in somewhat lower charge carrier mobilities. Hence, our results show that by systematic tuning of the blend ratio, PMMA can act as an excellent binding material in long-chain polymers such as DPPDTT and produce vertically stratified and aligned structures to ensure high mobility devices. [ABSTRACT FROM AUTHOR]

Schiff base condensation of 2,6-dimethylaniline with 3-(3-formyl-4-hydroxybenzyl)-3-methylimidazolium chloride, 1, which contains an aldehyde and methylimidazole chloride, allowed the preparation of compound 2. Using the templating effect of zinc ions, an ionic metal complex 3 was obtained, which served as a precursor to a new class of organometallic supramolecular architectures. This was achieved through the self-assembly of the two molecular units of 4 in the presence of silver oxide. This coordination-driven self-assembly process facilitated the cofacial arrangement of two Schiff base linkers. Both compound 5 and gold(I) complex 6 were characterized using multinuclear NMR spectroscopy and ESI-MS spectrometry techniques. The anticancer potentials of compounds 5 and 6 were evaluated. The low IC50 value indicates that compound 5 can efficiently induce cell death in breast cancer cells. The IC50 values of complexes 5 and 6 are 1.63 μM and 16.76 μM, respectively. Further studies have also demonstrated that complex 5 can eliminate cancer cells by halting the cell cycle in the G2 phase, leading to apoptotic cell death. Additionally, cytotoxicity evaluation using an MCF-7-derived organoid platform confirmed the ability of compound 5 to eliminate cancer cells, especially within the central region of the model. [ABSTRACT FROM AUTHOR]

The document "Amphiphilic Molecules, Interfaces and Colloids" published in the journal "Molecules" explores the significance of colloids in various applications and everyday life. It delves into the role of amphiphilic molecules in self-assembly and the design of functional colloids. The research contributions in the document cover topics such as the fabrication of novel materials, the relationship between molecular structure and physicochemical properties, and the development of green surfactants. The studies presented in the document provide valuable insights into the interfacial behavior of molecules and their impact on colloidal systems, offering potential applications in drug delivery, catalysis, and other fields. [Extracted from the article]

Hypothesis. Multi-walled tubular aggregates formed by hierarchical self-assembly of beta-cyclodextrin (β -CD) and sodium dodecylsulfate (SDS) hold a great potential as microcarriers. However, the underlying mechanism for this self-assembly is not well understood. To advance the application of these structures, it is essential to fine-tune the cavity size and comprehensively elucidate the energetic balance driving their formation: the bending modulus versus the microscopic line tension. Experiments. We investigated temperature-induced changes in the hierarchical tubular aggregates using synchrotron small-angle X-ray scattering across a broad concentration range. Detailed analysis of the scattering patterns enabled us to determine the structural parameters of the microtubes and to construct a phase diagram of the system. Findings. The microtubes grow from the outside in and melt from the inside out. We relate derived structural parameters to enthalpic changes driving the self-assembly process on the molecular level in terms of their bending modulus and microscopic line tension. We find that the conformation of the crystalline bilayer affects the saturation concentration, providing an example of a phenomenon we call conformational freezing point depression. Inspired by the colligative phenomenon of freezing point depression, well known from undergraduate physics, we model this system by including the membrane conformation, which can describe the energetics of this hierarchical system and give access to microscopic properties without free parameters.   [ABSTRACT FROM AUTHOR]

The Pt/TaON/GLC prepared by in-situ molecular self-assembly strategy exhibits higher ORR activity and durability, since Janus structural TaON/GLC dual-carrier presents a maximum synergy for the improvement in conductivity, O 2 adsorption and O O cleavage. [Display omitted] • Janus TaON/GLC dual-carrier is prepared via an in-situ self-assembly strategy. • The Janus structure provides strong metal-carrier and carrier-carrier interactions. • Pt/TaON/GLC exhibits higher ORR activity and durability compared to Pt/C. • TaON and GLC present the maximum synergies during ORR process. Developing carbon-supported Pt-based electrocatalysts with high activity and long-durability for the oxygen reduction reaction (ORR) is an enormous challenge for their commercial applications due to the corrosion of carbon supports in acid/alkaline solution at high potential. In this work, a Janus structural TaON/graphene-like carbon (GLC) was synthesized via an in-situ molecular selfassembly strategy, which was used as a dual-carrier for platinum (Pt). The as-obtained Pt/TaON/GLC presents high half-wave potential (0.94 V vs. RHE), excellent mass (1.48 A mg Pt -1) and specific (1.75 mA cm Pt -2) activities at 0.9 V, and superior long-term durability with a minimal loss (8.0 %) of mass activity after 10,000 cycles in alkaline solution, outperforming those of Pt/C and other catalysts. The structural characterizations and density functional theory (DFT) calculations indicate that the Pt/TaON/GLC catalyst exhibits the maximum synergies, including enhanced interfacial electron density, improved charge transfer, enhanced O 2 adsorption, and superimposed O O cleavage. This work shows a potential strategy for preparing the high-active and long-durable Pt-based electrocatalyst by synergism-promoted interface engineering. [ABSTRACT FROM AUTHOR]

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As a small-molecule gelator used as a stabilizer in gel emulsions, it has numerous advantages, such as low dosage, independence from phase ratios, and ease of control. In this study, a cholesterol derivative (CSA) was designed and synthesized to be used as a stabilizer for gel emulsions. Gelation experiments demonstrated that this small molecule could gelate various organic solvents, including linear alkanes, toluene, isoamyl alcohol, and acetone. Based on these gelation experiments, a series of gel emulsions were prepared with water as the dispersed phase and an organic solvent immiscible with water as the continuous phase. Finally, the gelation behavior of the gelator/water/toluene and gelator/water/cyclohexane systems was investigated, exploring the effects of different systems and varying water content within the same system on the structure and stability of the gel emulsions. Studies have shown that the gel emulsion prepared from the gelator/water/toluene system exhibits superior stability, likely due to the molecular self-assembly behavior of this cholesterol derivative exhibited in the water/toluene biphasic system. The research results provide a basis for using gel emulsions as templates to prepare porous materials and adjust their internal structure, ultimately laying a solid foundation for applying these porous materials in fields such as adsorption and catalysis. [ABSTRACT FROM AUTHOR]

The dynamic behaviour of metal‐ligand bonding cultivates stimuli‐mediated structural transformations in self‐assembled molecular architectures. The propensity of synthetically designed self‐assembled systems to interchange between higher‐order architectures is increased multi‐fold when the building blocks have higher conformational degrees of freedom. Herein, we report a new ligand, (2,7‐bis(di(pyridin‐4‐yl)amino)‐9H‐fluoren‐9‐one) (L), which, upon self‐assembly with a cis‐[(ethylene‐1,2‐diamine)Pd(NO3)2] acceptor (M), resulted in the formation of a M6L3 trifacial barrel (C1) in water. Interestingly, during crystallization, a rare M12L6 triangular orthobicupola architecture (C2) was generated along with C1. C2 could also be generated in solution via the application of several stimuli. C1 in aqueous media could stabilize one trans‐stilbene (tS) or cis‐stilbene (cS) molecule in its cavity, with a selectivity for the former from their mixture. Moreover, C1 acted as an effective host to prevent the otherwise facile photoisomerization of tS to cS inside its hydrophobic cavity under UV irradiation. Conversely, the visible‐light‐induced reverse isomerization of encapsulated cS to encapsulated tS could be achieved readily due to the better stabilization of tS within the cavity of C1 and its transparency to visible light. A multi‐functional system was therefore designed, which at the same time is stimuli‐responsive, shows isomer selectivity, and photo‐protects trans‐stilbene. [ABSTRACT FROM AUTHOR]

This study reports a method for enhancing the functions and properties of traditional organic macrocyclic hosts by fully encapsulating them within a large M9L6 cage to form host‐in‐host complexes. Within the cage host, the macrocyclic organic hosts with electron‐rich aromatic rings, such as cyclotriveratrylene and calix[8]arene, adopt specific orientations enhancing their inherent molecular recognition abilities. Due to the high crystallinity of the M9L6 cage, the guest encapsulation behavior of the host‐in‐host complexes can be observed by X‐ray structural analysis. [ABSTRACT FROM AUTHOR]

An adaptable Fe(II) tetrahedral cage, [Fe4L4][BF4]8 (L=tris(4‐(((E)‐pyridin‐2‐ylmethylene)amino)phenyl) phosphate), has been synthesised via self‐assembly. By modulating the orientation of its pendant P=O groups, the cage was found to be capable of encapsulating anionic, neutral, and cationic guests, which were confirmed in the solid state via single‐crystal X‐ray diffraction (SCXRD) and in solution by high‐resolution mass spectroscopy (HR‐MS), as well as by NMR (1H, 19F, 31P) studies where possible. [ABSTRACT FROM AUTHOR]

Biomacromolecules such as DNA, proteins, and lipids in nature are constructed by ‘bottom‐up’ assembly with diverse functions and structural ordered characteristics. Supramolecular assemblies have been employed to mimic the natural complexity by manipulating the subtle variations of functional groups. Nevertheless, the intricate design of the driving forces or sophisticated synthesis of molecular skeletons poses challenges in fabricating highly ordered assemblies. Natural phenolic molecules with anisotropic functional groups exhibit potential as versatile building blocks for a wide range of supramolecular crystalline materials with tailored assembly and controlled functionalities. The inherent and anisotropic phenolic groups engage in ordered assembly with various materials via directional covalent bonds (e. g., condensation and coordination) as well as multiple molecular interactions (e. g., hydrogen bonding and π–π interactions), leading to the formation of supramolecular crystalline materials with diverse functionalities. This Concept presents the assembly mechanisms of crystalline phenolic materials and their applications, showcasing the effective utilization of ordered assembly by natural phenolic building blocks. [ABSTRACT FROM AUTHOR]

Polymer fabrics are versatile materials used in various fields. Surface modification methods for hydrophobic polymer fibers have been developed to endow the materials with water wettability and functionality. Nevertheless, it remains a challenge to freely introduce functional groups to polymer fiber surfaces in a simple manner. Herein, we report the decoration of nonwoven fabric surfaces with azidated cello-oligosaccharide assemblies via molecular self-assembly. Cello-oligosaccharides with a terminal azido group were enzymatically synthesized and allowed to self-assemble in polyolefin, polyester, and vinylon nonwoven fabrics. It was found that the functional oligosaccharides formed bark-like assemblies on the nonwoven fiber surfaces, probably through heterogeneous nucleation. The hydrophilic oligosaccharide assemblies made the hydrophobic nonwoven surfaces water-wettable. Moreover, the azido group at oligosaccharide terminal was available for the post-functionalization of the modified nonwovens. In fact, an antigen was successfully conjugated to the modified nonwovens via the click chemistry. The antigen-conjugated nonwovens were useful for the specific and quantitative detection of a corresponding antibody. Our findings demonstrate the great potential of cello-oligosaccharide assembly for the functionalization of fabrics and other polymeric materials. IMPACT STATEMENT: This study developed a novel and simple method for modifying surfaces of polymer nonwoven fabrics based on the self-assembly of azidated cello-oligosaccharides to fabricate water-wettable and click-reactive functional materials. [ABSTRACT FROM AUTHOR]

Enantiospecific effects play an uprising role in chemistry and technical applications. Chiral molecular networks formed by self‐assembly processes at surfaces can be imaged by scanning probe microscopy (SPM). Low contrast and high noise in the topography map often interfere with the automatic image analysis using classical methods. The long SPM image acquisition times restrain Artificial Intelligence‐based methods requiring large training sets, leaving only tedious manual work, inducing human‐dependent errors and biased labeling. By generating realistic looking synthetic images, the acquisition of real datasets is avoided. Two state‐of‐the‐art object detection architectures are trained to localize and classify chiral unit‐cells in a regular molecular chiral network formed by self‐assembly of linear molecular bricks. The comparison of different architectures and datasets demonstrates that the training on purely synthetic data outperforms models trained using augmented datasets. A Faster R‐CNN model trained solely on synthetic data achieved an excellent mean average precision of 99% on real data. Hence this approach and the transfer to real data show high success, also highlighting the high robustness against experimental noise and different zoom levels across the full experimentally reasonable parameter range. The generalizability of this idea is demonstrated by achieving equally high performance on a different structure, too. [ABSTRACT FROM AUTHOR]

The bioavailability, release, and stability of pharmaceuticals under physicochemical conditions is the major cause of drug candidates failing during their clinical trials. Therefore, extensive efforts have been invested in the development of novel drug delivery systems that are able to transport drugs to a desired site and improve bioavailability. Hydrogels, and peptide hydrogels in particular, have been extensively investigated due to their excellent biocompatibility and biodegradability properties. However, peptide hydrogels often have weak mechanical strength, which limits their therapeutic efficacy. Therefore, a number of methods for improving their rheological properties have been established. This review will cover the broad area of drug delivery, focusing on the recent developments in this research field. We will discuss the variety of different types of nanocarrier drug delivery systems and then, more specifically, the significance and perspectives of peptide-based hydrogels. In particular, the interplay of intermolecular forces that govern the self-assembly of peptide hydrogels, progress made in understanding the distinct morphologies of hydrogels, and applications of non-canonical amino acids in hydrogel design will be discussed in more detail. [ABSTRACT FROM AUTHOR]

Background: Lipid vesicles, especially those utilizing biocompatible materials like chitosan (CHIT), hold significant promise for enhancing the stability and release characteristics of drugs such as indomethacin (IND), effectively overcoming the drawbacks associated with conventional drug formulations. Objectives: This study seeks to develop and characterize novel lipid vesicles composed of phosphatidylcholine and CHIT that encapsulate indomethacin (IND-ves), as well as to evaluate their in vitro hemocompatibility. Methods: The systems encapsulating IND were prepared using a molecular droplet self-assembly technique, involving the dissolution of lipids, cholesterol, and indomethacin in ethanol, followed by sonication and the gradual incorporation of a CHIT solution to form stable vesicular structures. The vesicles were characterized in terms of size, morphology, Zeta potential, and encapsulation efficiency and the profile release of drug was assessd. In vitro hemocompatibility was evaluated by measuring erythrocyte lysis and quantifying hemolysis rates. Results: The IND-ves exhibited an entrapment efficiency of 85%, with vesicles averaging 317.6 nm in size, and a Zeta potential of 24 mV, indicating good stability in suspension. In vitro release kinetics demonstrated an extended release profile of IND from the vesicles over 8 h, contrasting with the immediate release observed from plain drug solutions. The hemocompatibility assessment revealed that IND-ves exhibited minimal hemolysis, comparable to control groups, indicating good compatibility with erythrocytes. Conclusions: IND-ves provide a promising approach for modified indomethacin delivery, enhancing stability and hemocompatibility. These findings suggest their potential for effective NSAID delivery, with further in vivo studies required to explore clinical applications. [ABSTRACT FROM AUTHOR]

Self-assembly and molecular spectroscopy are widely used in protein research. However, studies underreported the interaction of rice glutelin (RG) and egg white protein (EWP) under pH-cycle treatments, which had differences between initial and final environment. Herein, the possible interaction mechanism of RG-EWP self-assembly behavior was demonstrated by spectroscopy or other characterization methods under different conditions and proportions. Fourier transform infrared, circular dichroism, intrinsic fluorescence, and UV absorption spectroscopic methods showed changes in the secondary and tertiary structures of RG or RG-EWP. Results also revealed the degree of protein folding and exposure status of aromatic amino acid residues. The nonignorable surface hydrophobic and electrostatic interactions were observed by ζ-potentials and surface hydrophobicity. The electrophoretic analysis showed increased 48 kDa subunits. The high solubility (over 92%) of RG-EWP was discovered as potential functionality at total ratio of 90% and 50% RG. This study improved the asymmetric pH-cycle theoretical mechanism and widened RG-EWP application. [ABSTRACT FROM AUTHOR]

Uncovering slow collective variables (CVs) of self-assembly dynamics is important to elucidate its numerous kinetic assembly pathways and drive the design of novel structures for advanced materials through the bottom-up approach. However, identifying the CVs for self-assembly presents several challenges. First, self-assembly systems often consist of identical monomers, and the feature representations should be invariant to permutations and rotational symmetries. Physical coordinates, such as aggregate size, lack high-resolution detail, while common geometric coordinates like pairwise distances are hindered by the permutation and rotational symmetry challenges. Second, self-assembly is usually a downhill process, and the trajectories often suffer from insufficient sampling of backward transitions that correspond to the dissociation of self-assembled structures. Popular dimensionality reduction methods, such as time-structure independent component analysis, impose detailed balance constraints, potentially obscuring the true dynamics of self-assembly. In this work, we employ GraphVAMPnets, which combines graph neural networks with a variational approach for Markovian process (VAMP) theory to identify the slow CVs of the self-assembly processes. First, GraphVAMPnets bears the advantages of graph neural networks, in which the graph embeddings can represent self-assembly structures in high-resolution while being invariant to permutations and rotational symmetries. Second, it is built upon VAMP theory, which studies Markov processes without forcing detailed balance constraints, which addresses the out-of-equilibrium challenge in the self-assembly process. We demonstrate GraphVAMPnets for identifying slow CVs of self-assembly kinetics in two systems: the aggregation of two hydrophobic molecules and the self-assembly of patchy particles. We expect that our GraphVAMPnets can be widely applied to molecular self-assembly. [ABSTRACT FROM AUTHOR]

This work focused on the template-free synthesis of uniform hydrangea-shaped hollow carbon nitride microspheres (HHCN) in an intermolecular assembly process, featuring open pores with application in efficient photodegradation of 6PPD-Q, an emerging pollutant for the first time. The prepared HHCN also shows prominent performance for treating the refractory pollutants such as staphylococcus aureus and antibiotic residues. [Display omitted] • Ordered hydrangea-shaped hollow g-C 3 N 4 microsphere was prepared by template-free ultrasound-assisted intermolecular assembly. • Unique structure and O, Cl co-doping optimize light harvesting and charge separation. • 90 % of 6PPD-Q was efficiently degraded on HHCN within 60 min for the first time. • Enhanced photocatalytic activities on bacteria disinfection and antibiotic degradation are observed. • DFT calculation is used to uncover band structure and reaction mechanism. 6PPD-quinone (6PPD-Q) as a derivative of the rubber antioxidant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), is attracting intensive attention due to the significant hazard to ecosystems. However, the effective management of this type of contaminant has been scarcely reported. Hydrangea-like hollow O, Cl-codoped graphite-phase carbon nitride microspheres (HHCN), featuring open pores were readily prepared by molecular self-assembly and utilized to address 6PPD-Q in an aqueous system for the first time. More than 90 % of 6PPD-Q is efficiently photodegraded within 1 h on the as-prepared HHCN, which is 2.5 times more than that on bulk g-C 3 N 4. Moreover, the as-synthesized HHCN demonstrates prominent photocatalytic activities for the degradation of doxycycline and tetracycline and the inactivation of Staphylococcus aureus (S. aureus) in an aqueous environment. The distinct hydrangea-like hollow structure imparts a large surface area and an abundance of active sites. In addition, the inclusion of Cl-3 p orbitals also contributes to a reduction in the bandgap (2.01 eV) and facilitates carrier separation and transport. These combined characteristics synergistically enhance the remarkable photocatalytic performance of HHCN, which induces a more than 2 times higher degradation rate than bulk g-C 3 N 4. This work offers a prospective route for template-free designing porous functional materials with improved properties and efficiently treating emerging pollutants such as 6PPD-Q, pathogenic bacteria, and antibiotic residues. [ABSTRACT FROM AUTHOR]

Carotenoids are increasingly used as naturally occurring food colorants. For application as beverage colorants, fat-soluble carotenoids are formulated into dispersion systems via nanoparticle (NP) formation. In recent years, the antioxidant properties of carotenoids have gained immense recognition for their preventive health benefits, thereby highlighting further interest in their development as functional food ingredients. Although functional carotenoids in dispersion-based formulations are desirable, knowledge regarding the structural and optical properties of NPs of carotenoids other than those of β-carotene, and methods to efficiently produce and compare NPs of various carotenoids, remain scarce. In this study, NPs of β-carotene, lycopene, astaxanthin, and lutein were prepared using a simple reprecipitation method, with a focus on understanding the variations in the molecular self-assembly influenced by the quality of solvent used during reprecipitation. This study presents the novel finding that the terminal groups of carotenoids significantly affect the intermolecular interactions, thereby altering the structural and optical properties of the resulting NPs. Our findings are expected to contribute to the development of new technologies for controlling the color of carotenoids based on the crystal structure of the NPs. [ABSTRACT FROM AUTHOR]

Two new structural motifs within the class of heteroleptic PdnAnBn assemblies, namely syn‐cis‐Pd3A3B3 bowls and bowl‐ (syn) or saddle‐ (anti) shaped cis‐Pd4A4B4 rings are introduced. All of the ten examples share a common longer fluorenone‐based bis‐monodentate ligand, equipped with meta‐pyridine donor groups. The ring size (3‐ vs. 4‐membered) and conformational preference (bowl vs. saddle) are controlled by the choice of the shorter ligand. These carry para‐pyridine donors, different aromatic backbones (benzene, thiophene or selenophene) and either no or small or bulky endohedral substituents, serving to control the nuclearity of the heteroleptic rings through different effects (ligand angle, charge distribution or backbone bulk). Moreover, the luminescence of the fluorenone ligand is conserved in the formed architectures. Emission intensity as well as host–guest properties vary depending on the inward‐pointing functions. All Pd3A3B3 assemblies are shown to bind chiral guest BINOL bis‐sulfonate which imparts its chirality to the entire host–guest complex. This results in a guest‐induced circular dichroism (CD) and circularly polarized luminescence (CPL) with dissymmetry factor glum up to 10−3. [ABSTRACT FROM AUTHOR]

Supramolecular gels are unique materials formed through the self-assembly of molecular building blocks, typically low molecular weight gelators (LMWGs), driven by non-covalent interactions. The process of crystallization within supramolecular gels has broadened the scope of the traditional gel-phase crystallization technique offering the possibility of obtaining crystals of higher quality and size. The broad structural diversity of LMWGs allows crystallization in multiple organic and aqueous solvents, favouring screening and optimization processes and the possibility to search for novel polymorphic forms. These supramolecular gels have been used for the crystallization of inorganic, small organic compounds of pharmaceutical interest, and proteins. Results have shown that these gels are not only able to produce crystals of high quality but also to influence polymorphism and physicochemical properties of the crystals, giving rise to crystals with potential new bio- and technological applications. Thus, understanding the principles of crystallization in supramolecular gels is essential for tailoring their properties and applications, ranging from drug delivery systems to composite crystals with tunable stability properties. In this review, we summarize the use of LMWG-based supramolecular gels as media to grow single crystals of a broad range of compounds. [ABSTRACT FROM AUTHOR]

Giant tetrahedral molecules have sparked significant interest in the past decade due to their unique and diverse supramolecular nanostructures. The longer and bulkier peripheral substituents create deep molecular concavities and thus contribute to the different self‐assembly behaviors compared to the conventional small tetrahedral molecules. In this study, a molecular giant tetrahedra, TetraNDI, was synthesized to investigate the important roles of the molecular concavities in the self‐assembly mechanism. Single‐crystal structural characterizations indicate that the TetraNDI takes its trigonal concavities to form 1D supramolecular columns, and its tetragonal concavities to reach close inter‐columnar packing. The difficulty in occupying the concavities leads to the path‐dependent phase behaviors of the giant tetrahedra. It is also found that the remaining molecular concavities in the supramolecular scaffolds affect the CO2 affinity of TetraNDI. With an understanding of the packing principles of molecular giant tetrahedra, the structure‐property relationships could be better evaluated in the future and might broaden the horizon of porous materials. [ABSTRACT FROM AUTHOR]

Type 2 diabetes mellitus (T2DM) is the most prevalent metabolic disorder worldwide. There have been tremendous efforts to find a safe and prolonged effective therapy for its treatment. Peptide hormones, from certain organisms in the human body, as the pharmaceutical agents, have shown outstanding profiles of efficacy and safety in plasma glucose regulation. Their therapeutic promises have undergone intensive investigations via examining their physicochemical and pharmacokinetic properties. Their major drawback is their short half-life in vivo. To address this challenge, researchers have recently started to apply the state-of-the-art molecular self-assembly on peptide hormones to form nanofibrillar structures, as a smart nanotherapeutic drug delivery technique, to tremendously enhance their prolonged bioactivity in vivo. This revolutionary therapeutic approach would significantly improve patient compliance. First, this review provides a comprehensive summary on the pathophysiology of T2DM, various efforts to treat this chronic disorder, and the limitations and drawbacks of these treatment approaches. Next, this review lays out detailed insights on various aspects of peptide self-assembly: adverse effects, potential applications in nanobiotechnology, thermodynamics and kinetics of the process, as well as the molecular structures of the self-assembled configurations. Furthermore, this review elucidates the recent efforts on applying reversible human-derived peptide self-assembly to generate highly organized smart nanostructured drug formulations known as nanofibrils to regulate and prolong the bioactivity of the human gut hormone peptides in vivo to treat T2DM. Finally, this review highlights the future research directions to advance the knowledge on the state-of-the-art peptide self-assembly process to apply the revolutionary smart nanotherapeutics for treatment of chronic disorders such as T2DM with highly improved patient compliance. [ABSTRACT FROM AUTHOR]

A strategy for the screening and optimization of an artificial esterase is presented that utilizes the self‐assembly of amphiphilic molecules. Unlike conventional approaches that rely on the attachment of key functional groups onto molecular scaffolds or surfaces, the modular assembly of amphiphiles allows a large number of catalytic combinations to be investigated with minimal synthetic effort. In this study, iterative combinatorial screens led to an optimized esterase comprising amphiphiles that act as a nucleophilic catalyst, an oxyanion hole and a metal ion chelator. Cooperativity is observed between the functional headgroups of the amphiphiles, an effect that is diminished when co‐assembled with non‐functionalized surfactants. Assessment of the catalytic efficiency (kcat/KM) of our optimized catalysts against recently reported artificial esterases shows comparable efficiency, indicating that efficient catalysis is possible with dynamic self‐assembled systems despite the absence of pre‐defined rigid binding pockets. [ABSTRACT FROM AUTHOR]

Complexation of Pd(II) with a designer unsymmetrical bis‐monodentate ligand (2 : 4 ratio) yielded a specific Pd2L4 type “single‐cavity discrete coordination cage” (SCDCC), from a pool of 4 isomeric structures. The observed selctivity is attributed to inherent orientational preference of the ligand strands around the metal centers. Crafting a short coordinating arm at either ends of the bis‐monodentate ligand (i.e the longer‐arm) produced a pair of unsymmetrical isomeric tris‐monodentate ligands; whereas crafting the same short‐arm at both ends of the ligand gives an unsymmetrical tetrakis‐monodentate ligand. Complexation of Pd(II) with either of the isomeric tris‐monodenate ligands (3 : 4 ratio) resulted in corresponding low‐symmetry “multi‐cavity discrete coordination cage” MCDCC having two conjoined cavities, though the inherent relative orientational preference of the longer arms is not achievable in these cages. The enforced orientation is sustained by “Neighbouring Cage Participation” (NCP). However, one‐pot combination of Pd(II), with a mixture of isomeric tris‐monodentate ligands in 3 : 2 : 2 ratio produced an integratively self‐sorted mixed‐ligated MCDCC from a pool of 31 structures. Also, mixing Pd(II) with the tetrakis‐monodentate ligand produced a MCDCC having three conjoined cavities. The inherent orientational preference of longer‐arm of the ligand strands is retained in the mixed‐ligated double‐cavity and the homo‐ligated triple cavity cages. [ABSTRACT FROM AUTHOR]

Living cells regulate the dynamics of developmental events through interconnected signaling systems that activate and deactivate inert precursors. This suggests that similarly, synthetic biomaterials could be designed to develop over time by using chemical reaction networks to regulate the availability of assembling components. Here we demonstrate how the sequential activation or deactivation of distinct DNA building blocks can be modularly coordinated to form distinct populations of self-assembling polymers using a transcriptional signaling cascade of synthetic genes. Our building blocks are DNA tiles that polymerize into nanotubes, and whose assembly can be controlled by RNA molecules produced by synthetic genes that target the tile interaction domains. To achieve different RNA production rates, we use a strategy based on promoter "nicking" and strand displacement. By changing the way the genes are cascaded and the RNA levels, we demonstrate that we can obtain spatially and temporally different outcomes in nanotube assembly, including random DNA polymers, block polymers, and as well as distinct autonomous formation and dissolution of distinct polymer populations. Our work demonstrates a way to construct autonomous supramolecular materials whose properties depend on the timing of molecular instructions for self-assembly, and can be immediately extended to a variety of other nucleic acid circuits and assemblies. DNA and RNA are the ideal building blocks to construct dynamic but programmable biomolecular materials. Here, the authors develop a modular system which allows the temporal control of filamentous DNA assemblies using cascaded gene networks. [ABSTRACT FROM AUTHOR]

Multivalency is a fundamental principle in nature that leads to high‐affinity intermolecular recognition through multiple cooperative interactions that overcome the weak binding of individual constituents. For example, multivalency plays a critical role in lectin‐carbohydrate interactions that participate in many essential biological processes. Designing high‐affinity multivalent glycoconjugates that engage lectins results in systems with the potential to disrupt these biological processes, offering promising applications in therapeutic design and bioengineering. Here, a versatile and tunable synthetic platform for the synthesis of metallosupramolecular glycoassemblies is presented that leverages subcomponent self‐assembly, which employs metal ion templates to generate complex supramolecular architectures from simple precursors in one pot. Through ligand design, this approach provides precise control over molecular parameters such as size, shape, flexibility, valency, and charge, which afforded a diverse family of well‐defined hybrid glyconanoassemblies. Evaluation of these complexes as multivalent binders to Concanavalin A (Con A) by isothermal titration calorimetry (ITC) demonstrates the optimal saccharide tether length and the effect of electrostatics on protein affinity, revealing insights into the impact of synthetic design on molecular recognition. The presented studies offer an enhanced understanding of structure‐function relationships governing lectin‐saccharide interactions at the molecular level and guide a systematic approach towards optimizing glyconanoassembly binding parameters. [ABSTRACT FROM AUTHOR]

Supramolecular polymers, as a type of dynamic polymers, are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry, whose development has greatly promoted the prosperity of new materials. Notably, molecular weight is one of the most important parameters of supramolecular polymers, which affects the physical/chemical properties and processing applications of materials. Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers. In this review, we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers, including (1) the molecular weight distinction corresponding to variable fluorescence colors, (2) matching different molecular weights with different fluorescence lifetime, (3) transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers. Besides, we also discuss the limitations of current methods for characterizing supramolecular polymers. We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers. [ABSTRACT FROM AUTHOR]

The rational design of artificial supramolecular structures with specific properties and functions hinges the comprehensive understanding of the coordination and noncovalent interactions driving self‐assembly. Herein, the self‐assembly of supramolecular systems through octahedral coordination between Ni(II) ions and a flexible tripeptide was theoretically investigated using quantum chemical calculations. These calculations utilized the B3LYP functional with the polarizable continuum model. Our results indicate that tridentate sites have a greater propensity for coordination, and that the presence of chloride anions and conformational shifts enhance bidentate and monodentate coordination. Insights into the effect of counter anions on the stability of octahedral coordination and the prerequisites for self‐assembly were gained by determining the stable conformation and potential reaction pathways of the tripeptide before and after adding chloride anions through an efficient automated conformational search. The formation of intramolecular hydrogen bonding interactions during the conformational changes was also studied using model calculations. Possible processes for initial self‐assembly of tripeptide were proposed. This study enhances the fundamental understanding of the conformational behavior of building blocks during supramolecular formation and advance the potential for constructing future bioinspired complexes. [ABSTRACT FROM AUTHOR]

Knots containing metal atoms as part of their continuous strand backbone are termed as metallaknots. While several metallaknots have been synthesized through one-pot self-assembly, the designed synthesis of metallaknots by controlling the arrangement of entanglements and strands connectivity remains unexplored. Here, we report the synthesis of metallaknots composed with Au(I)-bis(acetylide) linkages and templated by Cu(I) ions. Varying the ratio of the building blocks results in the switchable formation of two trefoil knots with different stoichiometries and symmetries (C2 or D3) and an entangled metalla-complex. While the entangled complex formed serendipitously, the strand ends can be subsequently linked through coordinative closure to generate a 41 metallaknot in a highly designable fashion. The comparable structural characteristics of resulting metalla-complexes allow us to probe the correlations between their topologies and photophysical properties, showing the backbone rigidity of knots endows complexes with excellent phosphorescent properties. This strategy, in conjunction with the coordinative closure approach, provides a straightforward route for the formation of highly phosphorescent metallaknots that were previously challenging to access. [ABSTRACT FROM AUTHOR]

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host‐guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal‐ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one‐pot method when only one type of coordinated motif exists due to its poor metal‐ion selectivity. Herein, we propose an effective intramolecular cation‐π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn2Cu4L34 by the one‐pot self‐assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following a clear self‐assembly mechanism in which only thermodynamic dimers ZnL12 and Cu2L22 were constructed with model ligands L1, L2, Zn(II) and Cu(II) with perfect self‐sorting and an ultra‐high metal‐selectivity feature. The successful construction of the heterometallic supramolecule Zn2Cu4L34, in which the definite sequence of metal ions Zn(II) and Cu(II) is encoded in the one‐pot method, will offer a novel approach to precisely construct heterometallic architectures. [ABSTRACT FROM AUTHOR]

A yet‐outstanding supramolecular chemistry challenge is isolation of novel varieties of stacked complexes with finely‐tuned donor‐acceptor bonding and optoelectronic properties, as herein reported for binary adducts comprising two different cyclic trinuclear complexes (CTC@CTC'). Most previous attempts focused only on 1–2 factors among metal/ligand/substituent combinations, resulting in heterobimetallic complexes. Instead, here we show that, when all 3 factors are carefully considered, a broadened variety of CTC@CTC' stacked pairs with intuitively‐enhanced intertrimer coordinate‐covalent bonding strength and ligand‐ligand/metal‐ligand dispersion are attained (dM–M' 2.868(2) Å; ΔE>50 kcal/mol, an order of magnitude higher than aurophilic/metallophilic interactions). Significantly, CTC@CTC' pairs remain intact/strongly‐bound even in solution (Keq 4.67×105 L/mol via NMR/UV‐vis titrations), and the gas phase (mass spectrometry revealing molecular peaks for the entire CTC@CTC' units in sublimed samples), rather than simple co‐crystal formation. Photo‐/electro‐luminescence studies unravel metal‐centered phosphorescence useful for novel all metal‐organic light‐emitting diodes (MOLEDs) optoelectronic device concepts. This work manifests systematic design of supramolecular bonding and multi‐faceted spectral properties of pure metal‐organic macrometallacyclic donor/acceptor (inorganic/inorganic) stacks with remarkably‐rich optoelectronic properties akin to well‐established organic/organic and organic/inorganic analogues. [ABSTRACT FROM AUTHOR]

The design of novel energetic compounds constitutes a pivotal research direction within the field of energetic materials. However, exploring the intricate relationship between their molecular structure and properties, in order to uncover their potential applications, remains a challenging endeavor. Therefore, employing multi-molecule assembly techniques to modulate the structure and performance of energetic materials holds immense significance. This approach enables the creation of a new generation of energetic materials, fueling research and development efforts in this field. In this study, a series of coordination compounds are synthesized by utilizing tetranitroethide (TNE) as an anion, which possesses a high nitrogen and oxygen content. The synthesis involves the synergistic modification between metal ions and small molecule ligands. Characterization of the obtained compounds is carried out using various techniques, including single crystal X-ray diffraction, IR spectroscopy, elemental analysis, and simultaneous TG–DSC analysis. Additionally, the energy of formation for these compounds is calculated using bomb calorimetry, based on the heat of combustion. The detonation performances of the compounds are determined through calculations using the EXPLO 5 software, and their sensitivities to external stimuli are evaluated. [ABSTRACT FROM AUTHOR]

Based on the principle of molecular design and self-assembly, a novel rare earth based arsenotungstate was obtained by introducing rare earth LaⅢ ions into the lacunary polyoxotungstates clusters with vacancy structure by one-pot method with Na2 WO4 ·2H2 O, NaAsO2 and LaCl3 ·6H2 O as the main materials. The structure and composition of this complex was confirmed by single-crystal X-ray diffraction, X-ray powder diffraction (PXRD), infrared spectroscopy (IR) and so on. The single crystal X-ray diffraction results show that the complex is in the monoclinic system, C2/c space group, and with the cell parameters of a =3.595 56(14) nm, b =1.222 48(4) nm, c =2.247 34(9) nm, β = 117.117 0(10)°, V =8.792 3(6) nm3, Z =4. The molecular formula of this compound is [(CH3)2 NH2]8 H3. 56 [{LaO(H2 O)2 }{WO(H2 O)}{W0. 24 (H2 O)2 } {AsW9 O33 }2]. And the polyoxoanion [{LaO(H2 O)2 }{WO(H2 O)}{W0. 24 (H2 O)2 }{AsW9 O33 }2]11. 56 - shows a novel sandwich type structure, which can be simply described as two trilacunary Keggin type{AsW9 O33 } units are linked by a {LaO(H2 O)2 } segment, a {WO(H2 O)} segment and a {W0. 24 (H2 O)2 } segment. Catalytic degradation property of this compound for Rhodamine-B was further inverstigated. The results demonstrate that the compound shows good photocatalytic activity under the condition of 300 W Hg lamp irradiation, and the degradation efficiency reaches to 74%. [ABSTRACT FROM AUTHOR]

Nature uses various chiral and unsymmetric building blocks to form substantial and complex supramolecular assemblies. In contrast, the majority of organic ligands used in metallosupramolecular chemistry are symmetric and achiral. Here we extend the group of unsymmetric chiral bile acids used as a scaffold for organic bispyridyl ligands by employing chenodeoxycholic acid (CDCA), an epimer of the previously used ursodeoxycholic acid (UDCA). The epimerism, flexibility, and bulkiness of the ligands leads to large structural differences in coordination products upon reaction with Pd(NO3)2. The UDCA‐bispyridyl ligand self‐assembles quantitatively into a single crown‐like Pd3L6 complex, whereas the CDCA ligand provides a mixture of coordination complexes of general formula PdnL2n, i.e., Pd2L4, Pd3L6, Pd4L8, Pd5L10, and even Pd6L12 containing an impressive 120 chiral centers. The coordination products were studied by a combination of analytical methods, with ion‐mobility mass spectrometry (IM‐MS) providing valuable details on their structure and allowed an effective separation of m/z 1461 to individual signals according to the arrival time distribution, thereby revealing four different ions of [Pd3L6(NO3)3]3+, [Pd4L8(NO3)4]4+, [Pd5L10(NO3)5]5+, and [Pd6L12(NO3)6]6+. The structures of all the complexes were modelled using DFT calculations. Finally, the challenges and conclusions in determining the specific structural identity of these unsymmetric species are discussed. [ABSTRACT FROM AUTHOR]

Surfactant molecules are known to self-assemble into micellar structures due to their amphiphilic nature of interactions with the solvent molecules. This ubiquitous phenomenon has been largely understood through the qualitative description of forces that govern these events. However, computational models that provide an accurate quantitative characterization of the process of micelle formation are still limited. In this study, we develop a coarse-grained computational model for Polysorbate 80 surfactant molecules that captures the phenomenon of aggregation at concentrations ranging from 0.1 % to 10 % in water. Here, we use a dissipative particle dynamics scheme to describe the interactions between the coarse-grained beads in the system. This computational model is able to reproduce the characteristics of micelle formation with increasing surfactant concentration. Our results demonstrate that despite loss in the degrees of freedom, the coarse-grained model predicts the structural and transport properties of the surfactant system with sufficient accuracy. The presented coarse-grained modeling technique offers a new window to uncover the molecular mechanisms of self-organization in the biophysical systems over a wide range of lengths and time scales. [ABSTRACT FROM AUTHOR]

"Chemistry - A European Journal Turns 30" reflects on the history and evolution of the journal since its launch in 1995. The journal has been a cornerstone of Chemistry Europe, covering diverse topics in chemistry over the years. In its 30th year, Chemistry - A European Journal remains committed to excellence, innovation, and representing modern chemistry, with plans to celebrate its anniversary with a symposium in Strasbourg. [Extracted from the article]

The Spindle Assembly Abnormal Protein 6 (SAS-6) forms dimers, which then self-assemble into rings that are critical for the nine-fold symmetry of the centriole organelle. It has recently been shown experimentally that the self-assembly of SAS-6 rings is strongly facilitated on a surface, shifting the reaction equilibrium by four orders of magnitude compared to the bulk. Moreover, a fraction of non-canonical symmetries (i.e., different from nine) was observed. In order to understand which aspects of the system are relevant to ensure efficient self-assembly and selection of the nine-fold symmetry, we have performed Brownian dynamics computer simulation with patchy particles and then compared our results with the experimental ones. Adsorption onto the surface was simulated by a grand canonical Monte Carlo procedure and random sequential adsorption kinetics. Furthermore, self-assembly was described by Langevin equations with hydrodynamic mobility matrices. We find that as long as the interaction energies are weak, the assembly kinetics can be described well by coagulation-fragmentation equations in the reaction-limited approximation. By contrast, larger interaction energies lead to kinetic trapping and diffusion-limited assembly. We find that the selection of nine-fold symmetry requires a small value for the angular interaction range. These predictions are confirmed by the experimentally observed reaction constant and angle fluctuations. Overall, our simulations suggest that the SAS-6 system works at the crossover between a relatively weak binding energy that avoids kinetic trapping and a small angular range that favors the nine-fold symmetry. [ABSTRACT FROM AUTHOR]