The core–shell architecture of biohybrid enzymes facilitates construction of multifunctional biofluids which display extremophilic traits in total absence of solvent.

A polymeric corona consisting of an alkyl-glycolic acid ethoxylate (C X EO Y ) surfactant offers a promising approach toward endowing proteins with thermotropic phase behavior and hyperthermal activity. Typically, preparation of protein–surfactant biohybrids is performed via chemical modification of acidic residues followed by electrostatic conjugation of an anionic surfactant to encapsulate single proteins. While this procedure has been applied to a broad range of proteins, modification of acidic residues may be detrimental to function for specific enzymes. Herein, we report on the one-pot preparation of biohybrids via covalent conjugation of surfactants to accessible lysine residues. We entrap the model enzyme hen egg-white lysozyme (HEWL) in a shell of carboxyl-functionalized C 12 EO 10 or C 12 EO 22 surfactants. With fewer surfactants, our covalent biohybrids display similar thermotropic phase behavior to their electrostatically conjugated analogues. Through a combination of small-angle X-ray scattering and circular dichroism spectroscopy, we find that both classes of biohybrids consist of a folded single-protein core decorated by surfactants. Whilst traditional biohybrids retain densely packed surfactant coronas, our biohybrids display a less dense and heterogeneously distributed surfactant coverage located opposite to the catalytic cleft of HEWL. In solution, this surfactant coating permits 7- or 3.5-fold improvements in activity retention for biohybrids containing C 12 EO 10 or C 12 EO 22 , respectively. The reported alternative pathway for biohybrid preparation offers a new horizon to expand upon the library of proteins for which functional biohybrid materials can be prepared. We also expect that an improved understanding of the distribution of tethered surfactants in the corona will be crucial for future structure–function investigations.

1395methyl compound was transferred from 0.01 A* hydrochloric acid, it exhibited much higher contact angles (Table I). Hydrolysis, catalyzed by the acid, probably generated a great number of hydroxyls which, by condensation with those in the glass surface, more firmly fixed the film.Of all the compounds discussed, those of the type (RjSiOL appear to be the least reactive however applied to the glass surface (Figure 9). A marked degree of orientation is not manifest initially as observed from contact angle measurements. Subsequent heating in the case of the dimethylsiloxane film, for example (Figure 5), soon results in a maximum value characteristic of the compound. Presumably, the heating has facilitated displacement of the adsorbed water molecules on the glass surface to allow highly intimate contact and probably chemical reaction with the siloxane in an oriented position. Films applied to glass using either halides or their hydrolysis products, after proper thermal treatment, are not removed by solvents which ordinarily dissolve such hydrolysis products. It is therefore not unreasonable to consider that chemical attachment plays an important part in either case. In the case of the organosilicon halides, orientation may be considered as prerequisite to the occurrence of a reaction. As a result, plates so treated immediately show the characteristics of oriented films.

Silica materials attract an increasing amount of interest in (fundamental) research, and find applications in, for example, sensing, catalysis, and drug delivery.A st he properties of these (nano)materials not only depend on their chemistry but also their size, shape,a nd surface area, the controllable synthesis of silica is essential for tailoringt he materials to specific applications. Advantageously,b ioinspired routes for silica production are environmentally friendly ands traightforward since the formation process is spontaneousa nd proceeds under mild conditions. These strategies mostly employ amine-bearing phosphorylated (bio)polymers. In this work, we expand this principle to supramolecular polymers based on the water-soluble cationic cyanine dye Pinacyanol acetate. Upon assembly in water, these dye molecules form large, polyaminated, supramolecular fibers.T he surfaces of these fibers can be used as ascaffold for the condensation of silicic acid. Controlo ver the ionic strength, dye concentration, and silicic acid saturation yielded silica fibers with ad iameter of 25 nm and as ingle, 4nmp ore. Unexpectedly,o ther unusual superstructures, namely,n ummulites and spherulites, are also observed depending on the ionic strength and dye concentration.T ransmission and scanning electronm icroscopy (TEM and SEM) showedt hat these superstructures are formed by aligned silica fibers. Close examination of the dye scaffold prior silicification using small-angle X-ray scattering (SAXS), and UV/Vis spectroscopy revealed minor influence of the ionic strength and dye concentration on the morphologyo ft he supramolecular scaffold.T otal internal reflection fluorescence (TIRF) during silicification unraveledt hat if the reaction is kept under static conditions, only silica fibers are obtained. Experiments performed on the dye scaffold and silica superstructures evidenced that the marked structurald iversity originates from the arrangemento fs ilica/dye fibers. Under these mild conditions, external force fields can profoundly influence the morphologyo ft he produced silica.

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