Project description:Mechanochemistry is a versatile methodology that can be employed both for covalent bond formation in organic synthesis as well as a mediator to allow preparation novel colloidal dispersions for drug delivery. Herein, ball-milling was employed for the solid-state preparation of fluorescent hydrophobic hydantoins, followed by the unprecedented mechanochemically-mediated complexation of hydrophobic hydantoins within hydrophilic protein β-lactoglobulin (BLG) and BLG nanofibrils (BLGNFs). These hydantoin:protein materials were in turn incorporated into hydrogels. The effect of incorporation of hydantoins into proteins, as well as the effect of protein structure, on the release properties were then investigated. The conversion of BLG to BLGNFs led to a more sustained release demonstrating that heat treatment of BLG into BLGNFs could be employed to modify release properties. To the best of our knowledge, this is the first example where protein : hydantoin complexes were prepared by mechanochemical methodology and mechanochemistry was combined with self-assembly in order to prepare protein nanomaterials for drug-delivery applications. In addition, the use of the developed protein materials is not limited to delivery of drugs but can for example be employed as components of smart food (delivery of nutrients) or release systems of pesticides.
Project description:The next generation of nanowires that could advance the integration of functional nanosystems into synthetic applications from photocatalysis to optical devices need to demonstrate increased ability to promote electron transfer at their interfaces while ensuring optimum quantum confinement. Herein we used the biological recognition and the self-assembly properties of tubulin, a protein involved in building the filaments of cellular microtubules, to create stable, free standing and conductive sulfur-doped carbon nanodots-based conductive bio-hybrids. The physical and chemical properties (e.g., composition, morphology, diameter etc.) of such user-synthesized hybrids were investigated using atomic and spectroscopic techniques, while the electron transfer rate was estimated using peak currents formed during voltammetry scanning. Our results demonstrate the ability to create individually hybrid nanowires capable to reduce energy losses; such hybrids could possibly be used in the future for the advancement and implementation into nanometer-scale functional devices.
Project description:Hybrids between biopolymeric materials and low-cost conductive carbon-based materials are interesting materials for applications in electronics, potentially reducing the need for materials that generate environmentally harmful electronic waste. Herein we investigate a scalable ball-milling method to form graphene nanoplatelets (GNPs) by milling graphite flakes with aqueous dispersions of proteins or protein nanofibrils (PNFs). Aqueous GNP dispersions with high concentrations (up to 3.2 mg mL-1) are obtained under appropriate conditions. The PNFs/proteins help to exfoliate graphite and stabilize the resulting GNP dispersions by electrostatic repulsion. PNFs are prepared from hen egg white lysozyme (HEWL) and β-lactoglobulin (BLG). The GNP dispersions can be processed into free-standing films having an electrical conductivity of up to 110 S m-1. Alternatively, the GNP dispersions can be drop-cast on PET substrates, resulting in mechanically flexible films having an electrical conductivity of up to 65 S m-1. The drop-cast films are investigated regarding their thermoelectric properties, having Seebeck coefficients of about 50 μV K-1. By annealing drop-cast films and thus carbonizing residual PNFs, an increase of electrical conductivity, coupled with a modest decrease in Seebeck coefficient, is obtained resulting in materials displaying power factors of up to 4.6 μW m-1 K-2.
Project description:Fluorescence titration of methylene blue, rhodamine B and rhodamine 6G (R6G) by silver nanoparticle (AgNP) all resulted in an initial steep quenching curve followed with a sharp turn and a much flatter quenching curve. At the turn, there are about 200,000 dye molecules per a single AgNP, signifying self-assembly of approximately 36-layers of dye molecules on the surface of the AgNP to form a micelle-like structure. These fluorescence-quenching curves fit to a mathematical model with an exponential term due to molecular self-assembly on AgNP surface, or we termed it "self-assembly shielding effect", and a Stern-Volmer term (nanoparticle surface enhanced quenching). Such a "super-quenching" by AgNP can only be attributed to "pre-concentration" of the dye molecules on the nanoparticle surface that yields the formation of micelle-like self-assembly, resulting in great fluorescence quenching. Overall, the fluorescence quenching titration reveals three different types of interactions of dye molecules on AgNP surface: 1) self-assembly (methylene blue, rhodamine B and R6G), 2) absorption/tight interaction (tryptamine and fluorescein), and 3) loose interaction (eosin Y). We attribute the formation of micelle-like self-assembly of these three dye molecules on AgNP to their positive charge, possession of nitrogen atoms, and with relatively large and flat aromatic moieties.
Project description:Here, we report the controlled assembly of SWCNT-GFP hybrids employing DNA as a linker. Two distinct, enriched SWCNTs chiralities, (6,5), (7,6), and an unsorted SWCNT solution, were selectively functionalized with DNA and hybridized to a complementary GFPDNA conjugate. Atomic force microscopy images confirmed that GFP attachment occurred predominantly at the terminal ends of the nanotubes, as designed. The electronic coupling of the proteins to the nanotubes was confirmed via in-solution fluorescence spectroscopy, that revealed an increase in the emission intensity of GFP when linked to the CNTs.
Project description:Dendronized helix bundle assemblies combine the sequence diversity and folding properties of proteins with the tailored physical properties of dendrimers. Assembly of peptide-dendron hybrids into ?-helical bundles encapsulates the helix bundle motif in a dendritic sheath that will allow the functional, protein-like domain to be transplanted to nonbiological environments. A bioorthogonal graft-to synthetic strategy for preparing helix bundle-forming peptide-dendron hybrids is described herein for hybrids 1a, 1b, and 2. Titration experiments monitored by circular dichroism spectroscopy support our self-assembly model for how the peptide-dendron hybrids self-assemble into ?-helical bundles with the dendrons on outside of the bundle.
Project description:In many physiological situations, BAR proteins reshape membranes with pre-existing curvature (templates), contributing to essential cellular processes. However, the mechanism and the biological implications of this reshaping process remain unclear. Here we show, both experimentally and through modelling, that BAR proteins reshape low curvature membrane templates through a mechanochemical phase transition. This phenomenon depends on initial template shape and involves the co-existence and progressive transition between distinct local states in terms of molecular organization (protein arrangement and density) and membrane shape (template size and spherical versus cylindrical curvature). Further, we demonstrate in cells that this phenomenon enables a mechanotransduction mode, in which cellular stretch leads to the mechanical formation of membrane templates, which are then reshaped into tubules by BAR proteins. Our results demonstrate the interplay between membrane mechanics and BAR protein molecular organization, integrating curvature sensing and generation in a comprehensive framework with implications for cell mechanical responses.
Project description:Supramolecular self-assembly is an excellent tool for controlling the optical and electronic properties of chromophore-based molecular systems. Herein, we demonstrate how differential self-assembly affects mechanoresponsive luminescence of fluorene-benzothiadiazole-based fluorophores. We have synthesized two donor-acceptor-donor-type conjugated oligomers consisting of fluorene as the donor and benzothiadiazole as the acceptor. For facile self-assembly, both molecules are end-functionalized with hydrogen-bonding amide groups. Differential self-assembly was induced by attaching alkyl chains of different lengths onto the fluorene moiety: hexyl (FB-C6) and dodecyl (FB-C12). The molecules self-assemble to form well-defined nanostructures in nonpolar solvents and solvent mixtures. Although their optical properties in solution are not affected by the alkyl chain length, significant effects were observed in the self-assembled state, particularly in the excitation energy migration properties. As a result, remarkable differences were observed in the mechanochromic luminescence properties of the molecules. A precise structure-property correlation is made using UV-visible absorption and fluorescence spectroscopy, time-correlated single-photon counting analysis, scanning electron microscopy, and X-ray diffraction spectroscopy.
Project description:A bis(squaraine) dye equipped with alkyl and oligoethyleneglycol chains was synthesized by connecting two dicyanomethylene substituted squaraine dyes with a phenylene spacer unit. The aggregation behavior of this bis(squaraine) was investigated in non-polar toluene/tetrachloroethane (98:2) solvent mixture, which revealed competing cooperative self-assembly pathways into two supramolecular polymorphs with entirely different packing structures and UV/Vis/NIR absorption properties. The self-assembly pathway can be controlled by the cooling rate from a heated solution of the monomers. For both polymorphs, quasi-equilibrium conditions between monomers and the respective aggregates can be established to derive thermodynamic parameters and insights into the self-assembly mechanisms. AFM measurements revealed a nanosheet structure with a height of 2 nm for the thermodynamically more stable polymorph and a tubular nanorod structure with a helical pitch of 13 nm and a diameter of 5 nm for the kinetically favored polymorph. Together with wide angle X-ray scattering measurements, packing models were derived: the thermodynamic polymorph consists of brick-work type nanosheets that exhibit red-shifted absorption bands as typical for J-aggregates, while the nanorod polymorph consists of eight supramolecular polymer strands of the bis(squaraine) intertwined to form a chimney-type tubular structure. The absorption of this aggregate covers a large spectral range from 550 to 875 nm, which cannot be rationalized by the conventional exciton theory. By applying the Essential States Model and considering intermolecular charge transfer, the aggregate spectrum was adequately reproduced, revealing that the broad absorption spectrum is due to pronounced donor-acceptor overlap within the bis(squaraine) nanorods. The latter is also responsible for the pronounced bathochromic shift observed for the nanosheet structure as a result of the slip-stacked arranged squaraine chromophores.
Project description:Two new tridentate(NNO)-bidentate(NN) compartmental ligands, HL(5) and HL(6), are synthesized from pyridine and benzimidazole synthons. They react in aqueous solution under physiological conditions with Zn(II), Ln(III), or a mixture thereof, to yield complexes of different stoichiometries, 1:3, 2:2, 2:3, 1:1:3, the speciation of which is established by UV-visible titrations and ESI mass spectrometry. Photophysical studies of the Eu(III)-containing solutions in Tris-HCl 0.1 M (pH = 7.4) show that lanthanide luminescence arises from a unique N6O3 coordination site with pseudo D 3 symmetry. Relevant parameters such as crystal field splitting, lifetime, radiative lifetime, and intrinsic quantum yield perfectly match those reported for dinuclear 4f-4f helicates in which the Eu(III) ion has the same coordination environment.