Cornelia Rosu

Progress in silica polypeptide composite colloidal hybrids: from silica cores to fuzzy shells

Core–shell particles have attracted increased interest in the past two decades. The properties of these composite materials are a symbiosis between the core and shell features which neither can exhibit separately. Polypeptide composite particles (PCPs) are a newly expanding field of hybrid materials with potential future impact in a broad variety of applications. In this review, we present an overview about the progress made on designing PCPs. Past and present limitations in the fabrication of the cores and shells alone will be outlined. A special emphasis will be placed on the future challenges directed to design better materials by expanding the architectural repertoire which will benefit their functionality and their range of applications. The review also presents possible future trends and challenges in engineering polypeptide-based materials as platforms for targeted applications.

Sculpting the internal architecture of fluorescent silica particles via a template-free approach.

Particles with an open, porous structure can be used to deliver payloads. It is often of interest to detect such particles in tissue or materials, which is facilitated by addition of dye. A straightforward approach leading to fluorescent, porous silica particles is described. The particles are etched with 3mM aqueous sodium hydroxide, taking advantage of the etching rate difference between normal silica and an interior band of silica that contains covalently attached dye. No additional steps, such as dye labeling or thermal annealing, are required. Etching modeled the internal structure of the fluorescent silica particles by creating meso/macropores and voids, as reflected by nitrogen absorption measurements. In order to investigate whether a polymer shell influences etching, certain composite particles are top-coated with poly(l-lysine) representing neutral or positive charged surfaces under typical pH conditions in living systems. The polypeptide-coated fluorescent silica cores exhibit the same porous morphology as uncoated homologs. The polypeptide topcoat does little to alter the permeation by the etching agent. Preservation of size during etching, confirmed by dynamic light scattering, transmission electron microscopy and small-angle X-ray scattering, simplifies the use of these template-free porous fluorescent particles as platforms for drug encapsulation, drug carriers and in vivo imaging.

Synthesis and Characterization of Complex Mixtures Consisting of Cyclic and Linear Polyamides from Ethyl Bis-Ketal Galactarates

Bis-ketal-protected diethyl galactarate was condensed with different diamines to prepare sugar-based polyamides. Ketal-protected polyamides, which are soluble in organic solvents, were deprotected with 90% trifluoroacetic acid to yield water insoluble materials. FTIR, NMR, GPC, MALDI-TOF, ESI and TGA techniques were used to characterize the structure and the properties of these biodegradable materials. D-galactaric acid-based polyamides are complex mixtures of cyclic and linear structures. High molecular weight linear polymer formation was limited by competitive cyclization reactions. The percentage of cyclization was highly dependent on the nature of the diamine used. Polycondensation with linear aliphatic diamines favored the formation of macrocycles, identified by MALDI-TOF and ESI.

Polypeptide-Coated Silica Particles Dispersed in Lyotropic Liquid Crystals of the Same Polypeptide

When a particle is introduced into a liquid crystal (LC), it distorts the LC director field, leading to new arrangements of the particles. This phenomenon is ordinarily studied using >100 nm particles and ∼2 nm mesogens. Usually the particle surface and mesogens are chemically distinct, which adds an enthalpic effect, even though the more interesting interactions are entropic. To raise the structures to the visible regime, while minimizing chemical differences between the particle surface and mesogen, silica particles coated with an α-helical polypeptide have been prepared and dispersed in lyotropic polypeptide LCs. The polypeptide is poly(γ-stearyl-α,l-glutamate) or PSLG. To make the particles easy to manipulate and easy to find, the silica core included superparamagnetic magnetite (Fe3O4) and covalently attached dye. Two methods were used to place polypeptides on these magnetic, fluorescent particles: a multistep grafting-to approach in which whole polypeptides were attached and a one-pot grafting-from approach in which the polymerization of the monomers was initiated from the particle surface. These approaches resulted in sparse and dense surface coverages, respectively. The influence of surface curvature and polypeptide molecular weight on the design of sparsely covered particles was investigated using the grafting-to approach. The aggregated grafting-from particles when freshly dispersed in a PSLG/solvent matrix disrupted the orientation of the characteristic cholesteric LC (ChLC) phase directors. In time, the hybrid particles were expelled from some domains, enabling the return of the familiar helical twist of the cholesteric mesophase. The sparsely coated grafting-to hybrid particles when inserted in the PSLG/solvent matrix assembled into stable islet-like formations that could not be disrupted even by an external magnetic field. The bulk particles aligned in chains that were easily manipulated by a magnetic field. These results indicate that polypeptide ChLCs can control and facilitate colloidal assembly of particles with matching surfaces.

Polypeptide Composite Particle-Assisted Organization of π-Conjugated Polymers into Highly Crystalline “Coffee Stains”

We demonstrate that homopolypeptides covalently tethered to anisotropically shaped silica particles induce crystalline ordering of representative semiconducting polymers. Films drop-cast from chloroform dispersions of poly(γ-stearyl-l-glutamate) (PSLG) composite particles and poly(3-hexythiophene) (P3HT) led to highly ordered crystalline structures of P3HT. Hydrophobic-hydrophobic interactions between the alkyl side chains of P3HT and PSLG were the main driving force for P3HT chain ordering into the crystalline assemblies. It was found that the orientation of rigid P3HT fibrils on the substrate adopted the directionality of the evaporating front. Regardless of the PSLG-coated particle dimensions used, the drop-cast films displayed patterns that were shaped by the coffee ring and Marangoni effects. PSLG-coated particles of high axial ratio (4.2) were more efficient in enhancing the electronic performance of P3HT than low axial ratio (2.6) homologues. Devices fabricated from the ordered assemblies displayed improved charge-carrier transport performance when compared to devices fabricated from P3HT alone. These results suggest that PSLG can favorably mediate the organization of semiconducting polymers.

Poly(colloid)s: “Polymerization” of Poly(l-tyrosine)-silica Composite Particles through the Photoinduced Cross-Linking of Unmodified Proteins Method

Photoinduced cross-linking of unmodified proteins, PICUP, was extended to core-shell silica-polypeptide composite particles to produce poly(colloid)s. Silica particles coated with poly(l-tyrosine), PTYR-SiO2, served as the monomer units. The PICUP reaction accomplished the formation of dityrosil linkages between the tyrosine units by illumination of photo-oxidizing ruthenium(II) bipyridyl catalyst under physiological conditions. The PICUP method was compared with an enzymatic route intermediated by horseradish peroxidase as catalyst. The PTYR-SiO2 particles feature high PTYR content in the shell, which facilitated the formation of heavily cross-linked but unstructured aggregates. After magnetic alignment of superparamagnetic PTYR-SiO2-cobalt composite particles, only the PICUP approach enabled the preparation of isolated chain-like poly(colloid)s. The cross-linking products were confirmed by FTIR. The native secondary structure of poly(l-tyrosine) is preserved in these poly(colloid)s. Because the PICUP reaction does not require the modification of the polypeptide structure, the cross-linked PTYR will retain its characteristic functions as a poly(amino acid). The PICUP method opens the door to a variety of PTYR-based poly(colloid) architectures.

Sugar-Based Polyamides: Self-Organization in Strong Polar Organic Solvents

Periodic patterns resembling spirals were observed to form spontaneously upon unassisted cooling of d-glucaric acid- and d-galactaric acid-based polyamide solutions in N-methyl-N-morpholine oxide (NMMO) monohydrate. Similar observations were made in d-galactaric acid-based polyamide/ionic liquid (IL) solutions. The morphologies were investigated by optical, polarized light and confocal microscopy assays to reveal pattern details. Differential scanning calorimetry was used to monitor solution thermal behavior. Small- and wide-angle X-ray scattering data reflected the complex and heterogeneous nature of the self-organized patterns. Factors such as concentration and temperature were found to influence spiral dimensions and geometry. The distance between rings followed a first-order exponential decay as a function of polymer concentration. Fourier-Transform Infrared Microspectroscopy analysis of spirals pointed to H-bonding between the solvent and the pendant hydroxyl groups of the glucose units from the polymer backbone. Tests on self-organization into spirals of ketal-protected d-galactaric acid polyamides in NMMO monohydrate confirmed the importance of the monosaccharides pendant free hydroxyl groups on the formation of these patterns. Rheology performed on d-galactaric-based polyamides at high concentration in NMMO monohydrate solution revealed the optimum conditions necessary to process these materials as fibers by spinning. The self-organization of these sugar-based polyamides mimics certain biological materials.