Spontaneous Self-assembly Process Research Articles

From Double-Stranded Helicates to Abiotic Double Helical Supramolecular Assemblies.

The folding of oligomeric strands is the method that nature has selected to generate ordered assemblies presenting spectacular functions. In the purpose to mimic these biomacro-molecules and extend their properties and functions, chemists make important efforts to prepare artificial secondary, tertiary, and even quarternary structures based on folded abiotic backbones. A large variety of oligomers and polymers, encoded with chemical informations, were designed, synthesized and characterized, and the establishment of non-covalent interactions lead to complex and functional supramolecular architectures resulting from a spontaneous self-assembly process. The association of comple-mentary molecular strands into double helical structures is a common structural pattern of nucleic acids and proteins, so the synthesis of bio-inspired double helices has emerged as an important subject. In recent years, a number of synthetic oligo-mers have been reported to form stable double helices and it was shown that the equilibrium between single and double helices can be controlled via different stimuli like the modification of the solvent or the temperature. This kind of structure presents highly interesting functions, such as molecular recognition within the cavity of double helices, and some other potential applications will emerge in the future.

Programmable In-Situ Co-Assembly of Organic Multi-Block Nanowires for Cascade Optical Waveguides.

Organic heterostructures (OHs) with multi-segments exhibit special optoelectronic properties compared with monomeric structures. Nevertheless, the synthesis of multi-block heterostructures remains challenging due to compatibility issues between segment parts, which restricts their application in optical waveguides and integrated optics. Herein, we demonstrate programmable in-situ co-assembly engineering, combining multi-step spontaneous self-assembly processes to promote the synthesis of multi-block heterostructures with a rational arrangement of three or more segments. The rational design of segments enables exciton manipulation and ensures optical waveguides and proper output among the multi-segment OHs. This work enables the controllable growth of segments within multi-block OHs, providing a pathway to construct complex OHs for the rational development of future optical applications.

Ion-Mediated Structural Discontinuities in Phospholipid Vesicles.

Despite intense research, methods for controlling soft matter's spontaneous self-assembly into well-defined layers remain a significant challenge. We observed ion-induced structural discontinuities of phospholipid vesicles that can be exploited for controlled self-assembly of soft materials, using DOPC and NaCl as a model system. The observations were made for the 0.25 wt % lipid concentration. We used dynamic light scattering, zeta-potential measurement, cryo-electron microscopy, small-angle X-ray, and small-angle neutron scattering to understand the reason for the discontinuities. For salt concentrations below 8 mM, we observed a decrease in the liposome diameter with increased NaCl concentration. Above 8 mM, we measured a discontinuity; the radius increases within a very narrow salt concentration range within less than 0.1 mM and then decreases for values greater than 8 mM. At 75 mM, the radius becomes constant until it grows again at around 500 mM. Microscopy and scattering experiments show a transition from unilamellar to bilamellar at 8 mM and to trilamellar at 75 mM. At 500 mM, we found a heterogeneous liposome system with many different bilayer numbers. All the experimental observations indicate that declining solvent quality and increasing osmotic pressure direct lipids to expel preferentially to the inner compartment. Upon reaching a critical concentration, excess lipids can form a new bilayer. This spontaneous self-assembly process causes simultaneous shrinkage of the aqueous core and expansion of the vesicle. This approach opens an intriguing path for controlling the self-assembly of bioinspired colloids.

Precise Regulation the Multiemission Based on Soft Double Salt for Information Encryption.

Manipulation of multiemissive luminophores is meaningful for exploring luminescent materials. Herein, we report a soft double salt assembly strategy that could result in well-organized nanostructures and different luminescence based on multiple weak intermolecular interactions thanks to the existence of electrostatic attraction between the anionic and cationic platinum(II) complexes. The cationic complexes B1 and B2 can coassemble with anionic complex A, respectively, and the emission switches from monomeric and excimeric emission to the triplet metal-metal-to-ligand charge transfer (3MMLCT) along with morphology changes from 0-dimensional (0-D) nanospheres to 3-dimensional (3-D) nanostructures. It is demonstrated that an isodesmic growth mechanism is adopted during the spontaneous self-assembly process, and the relative negative ΔG values make the anionic and cationic complex molecules prefer to form aggregates based on π-π stacking, Pt···Pt interactions, and electrostatic interactions. The coassembly strategy between anionic and cationic complexes endows them with multicolor luminescent and apparent color as optical materials for advanced information encryption.

Core-Shell Structured SiO2@NiFe LDH Composite for Broadband Electromagnetic Wave Absorption.

In this work, a novel core-shell structure material, NiFe layered double hydroxide (NiFe LDH) loaded on SiO2 microspheres (SiO2@NiFe LDH), was synthesized by a one-step hydrothermal method, and the spontaneous electrostatic self-assembly process. The morphology, structure, and microwave absorption properties of SiO2@NiFe LDH nanocomposites with different NiFe element ratios were systematically investigated. The results show that the sample of SiO2@NiFe LDH-3 nanocomposite has excellent microwave absorption properties. It exhibits broadband effective absorption bandwidth (RL < -10 dB) of 8.24 GHz (from 9.76 GHz to 18.0 GHz) and the reflection loss is -53.78 dB at the matched thickness of 6.95 mm. It is expected that this SiO2@NiFe-LDH core-shell structural material can be used as a promising non-precious, metal-based material microwave absorber to eliminate electromagnetic wave contamination.

Template-free assembly of 2D-electrolytes into nanofibres

The assembly of graphene-based materials into nanofibres is of intense technological interest for numerous applications ranging from tissue engineering and drug delivery to fuel cells and space elevators. We demonstrate a composite nanofibre synthesis process using functionalised graphene structures in liquid medium (two-dimensional [2D] electrolytes) as building blocks. The approach consists in simultaneous scrolling and reacting 2D electrolytes, leading to a dimensional reduction of 2D materials into one-dimensional nanostructures. The spontaneous self-assembly and cross-linking processes allow to produce nanofibres without the need of fibrillation techniques, such as wet-spinning or external templates.

Supramolecular Double Helices from Small C3-Symmetrical Molecules Aggregated in Water.

Supramolecular fibers in water, micrometers long and several nanometers in width, are among the most studied nanostructures for biomedical applications. These supramolecular polymers are formed through a spontaneous self-assembly process of small amphiphilic molecules by specific secondary interactions. Although many compounds do not possess a stereocenter, recent studies suggest the (co)existence of helical structures, albeit in racemic form. Here, we disclose a series of supramolecular (co)polymers based on water-soluble benzene-1,3,5-tricarboxamides (BTAs) that form double helices, fibers that were long thought to be chains of single molecules stacked in one dimension (1D). Detailed cryogenic transmission electron microscopy (cryo-TEM) studies and subsequent three-dimensional-volume reconstructions unveiled helical repeats, ranging from 15 to 30 nm. Most remarkable, the pitch can be tuned through the composition of the copolymers, where two different monomers with the same core but different peripheries are mixed in various ratios. Like in lipid bilayers, the hydrophobic shielding in the aggregates of these disc-shaped molecules is proposed to be best obtained by dimer formation, promoting supramolecular double helices. It is anticipated that many of the supramolecular polymers in water will have a thermodynamic stable structure, such as a double helix, although small structural changes can yield single stacks as well. Hence, it is essential to perform detailed analyses prior to sketching a molecular picture of these 1D fibers.

Facile synthesis of FeCo layered double oxide/raspberry-like carbon microspheres with hierarchical structure for electromagnetic wave absorption

Transition metal compositions (Fe, Co and Ni) have always been promising candidates for electromagnetic wave (EMW) absorbers. In this study, the FeCo layered double hydroxide (LDH) supported on raspberry-like carbon spheres (RCs) was synthesized by a simple hydrothermal method and the spontaneous electrostatic self-assembly process. The surface FeCo-LDH is then transformed into FeCo layered double oxide (LDO) with different compositions after calcination treatment (650 °C and 700 °C), forming a typical hierarchical structure. The sample calcined at 700 °C exhibited an ultra-wide effective absorption bandwidth (fe) (RL < −10 dB) of 7.4 GHz (from 10.6 to 18.0 GHz) at the matched thickness of 2.2 mm. The remarkable EM wave absorption properties are attributed to the strong interface polarization due to the various phase boundaries in LDO shell as well as sufficient heterointerfaces between LDO shell and RCs. It should be emphasized that LDH is rarely used for EMW absorption, and the use of LDH positively charged characteristics to fabricate hierarchical materials is a meaningful attempt and confirms the potential of LDH in EMW absorbing materials.

In search of a primitive signaling code

Cells must have preceded by simpler chemical systems (protocells) that had the capacity of a spontaneous self-assembly process and the ability to confine chemical reaction networks together with a form of information. The presence of lipid molecules in the early Earth conditions is sufficient to ensure the occurrence of spontaneous self-assembly processes, not defined by genetic information, but related to their chemical amphiphilic nature. Ribozymes are plausible molecules for early life, being the first small polynucleotides made up of random oligomers or formed by non-enzymatic template copying. Compartmentalization represents a strategy for the evolution of ribozymes; the attachment of ribozymes to surfaces, such as formed by lipid micellar aggregates may be particular relevant if the surface itself catalyzes RNA polymerization.It is conceivable that the transition from pre-biotic molecular aggregates to cellular life required the coevolution of the RNA world, capable of synthesizing specific, instead of statistical proteins, and of the Lipid world, with a transition from micellar aggregates to semipermeable vesicles. Small molecules available in the prebiotic inventory might promote RNA stability and the evolution of hydrophobic micellar aggregates into membrane-delimited vesicles. The transition from ribozymes catalyzing the assembly of statistical polypeptides to the synthesis of proteins, required the appearance of the genetic code; the transition from hydrophobic platforms favoring the stability of ribozymes and of nascent polypeptides to the selective transport of reagents through a membrane, required the appearance of the signal transduction code.A further integration between the RNA and Lipid worlds can be advanced, taking into account the emerging roles of phospholipid aggregates not only in ensuring stability to ribozymes by compartmentalization, but also in a crucial step of evolution through natural selection mechanisms, based on signal transduction pathways that convert environmental changes into biochemical responses that could vary according to the context. Here I present evidences on the presence of traces of the evolution of a signal transduction system in extant cells, which utilize a phosphoinositide signaling system located both at nucleoplasmic level as well as at the plasma membrane, based on the very same molecules but responding to different rules. The model herewith proposed is based on the following assumptions on the biomolecules of extant organisms: i) amphiphils can be converted into structured aggregates by hydrophobic forces thus giving rise to functional platforms for the interaction of other biomolecules and to their compartmentalization; ii) fundamental biochemical pathways, including protein synthesis, can be sustained by natural ribozymes of ancient origin; iii) ribozymes and nucleotide-derived coenzymes could have existed long before protein enzymes emerged; iv) signaling molecules, both derived from phospholipids and from RNAs could have guided the evolution of complex metabolic processes before the emergence of proteins.

Self-Assembly of Artificial Sweetener Aspartame Yields Amyloid-like Cytotoxic Nanostructures.

Recent reports have revealed the intrinsic propensity of single aromatic metabolites to undergo self-assembly and form nanostructures of amyloid nature. Hence, identifying whether aspartame, a universally consumed artificial sweetener, is inherently aggregation prone becomes an important area of investigation. Although the reports on aspartame-linked side effects describe a multitude of metabolic disorders, the mechanistic understanding of such destructive effects is largely mysterious. Since aromaticity, an aggregation-promoting factor, is intrinsic to aspartame's chemistry, it is important to know whether aspartame can undergo self-association and if such a property can predispose any cytotoxicity to biological systems. Our study finds that aspartame molecules, under mimicked physiological conditions, undergo a spontaneous self-assembly process yielding regular β-sheet-like cytotoxic nanofibrils of amyloid nature. The resultant aspartame fibrils were found to trigger amyloid cross-seeding and become a toxic aggregation trap for globular proteins, Aβ peptides, and aromatic metabolites that convert native structures to β-sheet-like fibrils. Aspartame fibrils were also found to induce hemolysis, causing DNA damage resulting in both apoptosis and necrosis-mediated cell death. Specific spatial arrangement between aspartame molecules is predicted to form a regular amyloid-like architecture with a sticky exterior that is capable of promoting viable H-bonds, electrostatic interactions, and hydrophobic contacts with biomolecules, leading to the onset of protein aggregation and cell death. Results reveal that the aspartame molecule is inherently amyloidogenic, and the self-assembly of aspartame becomes a toxic trap for proteins and cells, exposing the bitter side of such a ubiquitously used artificial sweetener.

Self-Assembled Chiral Nanoparticle Superstructures and Identification of Their Collective Optical Activity from Ligand Asymmetry.

The spontaneous self-assembly of chiral nanoparticles (NPs) into stationary fabrication has garnered great interest in technique investigation and science advancement due to its expected apparent properties via orderly collective behaviors. However, this kind of characterization of assembled nanoparticles superstructure (NPS) is rarely reported and is distinguished with monodispersed chiral NPs. In this work, we used l-cysteine (Cys) as the chiral molecule in the form of functional surfactant, which had capped CdS/CdTe NPs and was treated as a linkage bridge for constructing orderly assembled NPS. Among the circular dichrosim (CD) phenomenon, Cys ligands exhibit related changes in CD absorption, while whole-molecule solution was used for treatment in different pH-controlling procedures. Synthesized chiral NPs are organized into ordered rod-shaped NPS during the spontaneous self-assembly process, and the CD response of NPS is monitored in different cultivating times; it showed a persuasive response appears in sum frequency generation (SFG) spectroscopy. Both experimental works and theory calculation convey that the ordered stacking of chiral stabilizer and the chirality of NPS, which are identified from chiral molecular status and their collective optical activity, originated from ligand asymmetry.

Effect of solvents on the self-assembly of long chain alkylphosphonic acids on indium tin oxide surface - In situ studies on the adsorption kinetics and electron transfer process

The spontaneous self-assembly process of phosphonic acids (PAs) onto indium tin oxide (ITO) surface has been studied in this work. We have carried out in situ adsorption kinetics studies of phosphonic acids in ethanol as a solvent using electrochemical impedance spectroscopy (EIS). Further, the effect of different solvents like ethanol, water, toluene and hexane on the structural integrity of the alkylphosphonic acid (CH3 (CH2)n PO3H2, n=15,17) thin films on ITO surface has been investigated by using [Fe(CN)6]3‐/4‐ as a redox probe. From the study of formation kinetics, it is concluded that molecular self-assembly process follows two adsorption steps, a fast first step followed by a slower second step. The results of cyclic voltammetric (CV) and impedance measurements show that phosphonic acids form a highly impermeable surface film on ITO when polar solvents like ethanol and water are used.

Governing the Inhibition of Reconstituted Collagen Type I Assemblies Mediated Through Noncovalent Forces of (±)-α Lipoic Acid.

Type I collagen is a fibrous protein, which is highly biocompatible and biodegradable and exhibits low immunogenicity with its unique feature of undergoing a spontaneous self-assembly process. However, the excessive accumulation of collagen may lead to a condition known as fibrosis in vertebrates. Recently, saturated fatty acids have gained much attention as biomedical and therapeutic agents. Therefore, drawing inspiration from the biological and structural tunability of these fatty acids, this work aims to inhibit the self-assembly of type I collagen using (±)-α-lipoic acid (ALA). Reconstituted collagen and its blends with (±)-ALA under physiological conditions were subjected to fibril growth kinetics measurements, which exhibited the decrease in the rate of fibrillogenesis ( t1/2) with an increase in the concentration of ALA. Variations in the viscoelasticity of collagen and ALA blend with respect to rate and frequency showed significant changes. Further, the frequency shifts of different functional groups via FT-IR (ATR) and the morphological changes associated with fibril inhibition were visualized using a cryoscanning electron microscope. Molecular dynamics simulation of the collagen-like peptide with the (±)-ALA molecule at different molar ratios proved that (±)-ALA had a strong potential to bind at various sites of collagen mediated by conventional secondary or noncovalent forces. Thus, the protein-small molecule interaction dominates the forces prevailing between protein-protein binding, leading to the inhibition of the self-assembly process. Such inhibitory effects by a fatty acid may unfold newer avenues for development of targeted and sustainable drug delivery systems for fibrotic diseases.

PCPP-Adjuvanted Respiratory Syncytial Virus (RSV) sF Subunit Vaccine: Self-Assembled Supramolecular Complexes Enable Enhanced Immunogenicity and Protection.

PCPP, a well-defined polyphosphazene macromolecule, has been studied as an immunoadjuvant for a soluble form of the postfusion glycoprotein of respiratory syncytial virus (RSV sF), which is an attractive vaccine candidate for inducing RSV-specific immunity in mice and humans. We demonstrate that RSV sF-PCPP formulations induce high neutralization titers to RSV comparable to alum formulations even at a low PCPP dose and protect animals against viral challenge both in the lung and in the upper respiratory tract. PCPP formulations were also characterized by Th1-biased responses, compared to Th2-biased responses that are more typical for RSV sF alone or RSV sF-alum formulations, suggesting an inherent immunostimulating activity of the polyphosphazene adjuvant. We defined these immunologically active RSV sF-PCPP formulations as self-assembled water-soluble protein-polymer complexes with distinct physicochemical parameters. The secondary structure and antigenicity of the protein in the complex were fully preserved during the spontaneous aqueous self-assembly process. These findings further advance the concept of polyphosphazene immunoadjuvants as unique dual-functionality adjuvants integrating delivery and immunostimulating modalities in one water-soluble molecule.

Self-transport and self-alignment of microchips using microscopic rain.

Alignment of microchips with receptors is an important process step in the construction of integrated micro- and nanosystems for emerging technologies, and facilitating alignment by spontaneous self-assembly processes is highly desired. Previously, capillary self-alignment of microchips driven by surface tension effects on patterned surfaces has been reported, where it was essential for microchips to have sufficient overlap with receptor sites. Here we demonstrate for the first time capillary self-transport and self-alignment of microchips, where microchips are initially placed outside the corresponding receptor sites and can be self-transported by capillary force to the receptor sites followed by self-alignment. The surface consists of hydrophilic silicon receptor sites surrounded by superhydrophobic black silicon. Rain-induced microscopic droplets are used to form the meniscus for the self-transport and self-alignment. The boundary conditions for the self-transport have been explored by modeling and confirmed experimentally. The maximum permitted gap between a microchip and a receptor site is determined by the volume of the liquid and by the wetting contrast between receptor site and substrate. Microscopic rain applied on hydrophilic-superhydrophobic patterned surfaces greatly improves the capability, reliability and error-tolerance of the process, avoiding the need for accurate initial placement of microchips, and thereby greatly simplifying the alignment process.

ChemInform Abstract: From 1 → 3 Dendritic Designs to Fractal Supramacromolecular Constructs: Understanding the Pathway to the Sierpinski gasket

AbstractReview: 76 refs.

From 1 → 3 dendritic designs to fractal supramacromolecular constructs: understanding the pathway to the Sierpiński gasket.

The iterative synthetic protocols used for dendrimer construction were developed based on the desire to easily craft highly branched macromolecules with ideally an exact mass and tailored functionality. Inspired by arboreal design and precursors of the utilitarian macromolecules known as dendrimers today, our first examples employed predesigned, 1 → 3 or 1 → (1 + 2) C-branched, building blocks. Physical characteristics of the dendrimers, including their globular shapes, excellent solubility, and demonstrated aggregation, revealed the inherent supramolecular potential. The architecture that is characteristic of dendritic materials also exhibits obvious fractal qualities based on self-similar, repetitive, branched frameworks. Thus, both the fractal design and supramolecular aspects of these constructs are suggestive of a larger field of fractal materials that incorporate repeating geometries and are derived by complementary building block recognition and assembly. Use of 〈terpyridine-M(2+)-terpyridine〉 connectivity for the sides and tuned directed organic vertices has opened the door to other types of novel materials. This approach also circumvents the nonideality of dendrimers, since the heteroleptic, one-step, spontaneous self-assembly process facilitates quantitative outcomes.

Enantioselective determination of representative profens in wastewater by a single-step sample treatment and chiral liquid chromatography–tandem mass spectrometry

This manuscript describes, for the first time, the simultaneous enantioselective determination of ibuprofen, naproxen and ketoprofen in wastewater based on liquid chromatography tandem mass spectrometry (LC–MS/MS). The method uses a single-step sample treatment based on microextraction with a supramolecular solvent made up of hexagonal inverted aggregates of decanoic acid, formed in situ in the wastewater sample through a spontaneous self-assembly process. Microextraction of profens was optimized and the analytical method validated. Isotopically labeled internal standards were used to compensate for both matrix interferences and recoveries. Apparent recoveries for the six enantiomers in influent and effluent wastewater samples were in the interval 97–103%. Low method detection limits (MDLs) were obtained (0.5–1.2ngL–1) as a result of the high concentration factors achieved in the microextraction process (i.e. actual concentration factors 469–736). No analyte derivatization or evaporation of extracts, as it is required with GC–MS, was necessary. Relative standard deviations for enantiomers in wastewater were always below 8%. The method was applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in influents and effluents from three wastewater treatment plants. All the values found for profen enantiomers were consistent with those previously reported and confirmed again the suitability of using the enantiomeric fraction of ibuprofen as an indicator of the discharge of untreated or poorly treated wastewaters. Both the analytical and operational features of this method make it applicable to the assessment of the enantiomeric fate of profens in the environment.

Designing in vitro strategies and in vivo models for Alzheimer's disease - promises & challenges.

Protein folding is a spontaneous self-assembly process, which occurs in the biological system. Understanding this complex process not only helps in deciphering the mechanism involved in protein misfolding diseases but also helps in modeling in vitro and in vivo systems for testing the therapeutic strategies developed for the disease. Among the protein misfolding diseases, much emphasis has been given to Alzheimer's disease because of its prevalence among elderly individuals and propensity to cause external damage to neurons, an effective cure for which is yet to be designed. Though amyloid fibrils are the major cause of neurotoxicity in Alzheimer's disease, their mechanism of self-assembly during pathological conditions is still under active investigation. This review aims to understand the basic mechanism of amyloid fibril formation and how it can be characterized in different stages by various techniques. With this information, it is possible to design both in vitro and in vivo systems, which not only serves as model systems for understanding the mechanism of amyloid fibril formation but also helps to test new therapeutic strategies against the disease. This review also highlights the pros and cons of currently available in vitro and in vivo systems, which can aid the readers to select a suitable system for their further studies.

Role of hydrophobicity on self-assembly by peptide amphiphiles via molecular dynamics simulations.

Using a novel coarse-grained model, large-scale molecular dynamics simulations were performed to examine self-assembly of 800 peptide amphiphiles (sequence palmitoyl-V3A3E3). Under suitable physiological conditions, these molecules readily assemble into nanofibers leading to hydrogel construction as observed in experiments. Our simulations capture this spontaneous self-assembly process, including formation of secondary structure, to identify morphological transitions of distinctive nanostructures. As the hydrophobic interaction is increased, progression from open networks of secondary structures toward closed cylindrical nanostructures containing either β-sheets or random coils are observed. Moreover, temperature effects are also determined to play an important role in regulating formation of secondary structures within those nanostructures. These understandings of the molecular interactions involved and the role of environmental factors on hydrogel formation provide useful insight for development of innovative smart biomaterials for biomedical applications.