Effect of Polymer Porosity on Aqueous Self‐ H ealing Encapsulation of Proteins in PLGA Microspheres

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102254/1/mabi201300323.pd

First Jump of Microgel: Actuation Speed Enhancement by Elastic Instability

Swelling-induced snap-buckling in a 3D micro hydrogel device, inspired by the insect-trapping action of Venus flytrap, makes it possible to generate astonishingly fast actuation. We demonstrate that elastic energy is effectively stored and quickly released from the device by incorporating elastic instability. Utilizing its rapid actuation speed, the device can even jump by itself upon wetting.Comment: 4 pages, 3 figure

An optically activated cantilever using photomechanical effects in dye-doped polymer fibers

We report on what we believe is the first demonstration of an optically activated cantilever due to photomechanical effects in a dye-doped polymer optical fiber. The fiber is observed to bend when light is launched off-axis. The displacement angle monotonically increases as a function of the distance between the illumination point and the fiber axis, and is consistent with differential light-induced length changes. The photothermal and photo-reorientation mechanisms, each with its own distinct response time, are proposed to explain the observed time dependence. The measured degree of bending is consistent with a model that we have proposed which includes coupling between photoisomerization and heating. Most importantly, we have discovered that at high light intensity, a cooperative release of stress results in cis-to-trans isomerization that yields a large and abrupt length change.Comment: 13 pages, 16 figure

Water-Blown Polyurethane Foams Showing a Reversible Shape-Memory Effect

Water-blown polyurethane (PU) foams are of enormous technological interest as they are widely applied in various fields, i.e., consumer goods, medicine, automotive or aerospace industries. The discovery of the one-way shape-memory effect in PU foams provided a fresh impetus for extensive investigations on porous polymeric actuators over the past decades. High expansion ratios during the shape-recovery are of special interest when big volume changes are required, for example to fill an aneurysm during micro-invasive surgery or save space during transportation. However, the need to program the foams before each operation cycle could be a drawback impeding the entry of shape- memory polymeric (SMP) foams to our daily life. Here, we showed that a reversible shape-memory effect (rSME) is achievable for polyurethane water- blown semicrystalline foams. We selected commercially available crystallizable poly(ε-caprolactone)-diols of different molecular weight for foams synthesis, followed by investigations of morphology, thermal, thermomechanical and shape- memory properties of obtained compositions. Densities of synthesized foams varied from 110 to 180 kg∙m−3, while peak melting temperatures were composition-dependent and changed from 36 to 47 °C, while the melting temperature interval was around 15 K. All semicrystalline foams exhibited excellent one-way SME with shape-fixity ratios slightly above 100% and shape- recovery ratios from the second cycle of 99%. The composition with broad distribution of molecular weights of poly(ε-caprolactone)-diols exhibited an rSME of about 12% upon cyclic heating and cooling from Tlow = 10 °C and Thigh = 47 °C. We anticipate that our experimental study opens a field of systematic investigation of rSMEs in porous polymeric materials on macro and micro scale and extend the application of water-blown polyurethane foams to, e.g., protective covers with zero thermal expansion or even cushions adjustable to a certain body shape. View Full-Tex

Shape-memory properties of magnetically active triple-shape nanocomposites based on a grafted polymer network with two crystallizable switching segments

Thermo-sensitive shape-memory polymers (SMP), which are capable of memorizing two or more different shapes, have generated significant research and technological interest. A triple-shape effect (TSE) of SMP can be activated e.g. by increasing the environmental temperature (Tenv), whereby two switching temperatures (Tsw) have to be exceeded to enable the subsequent shape changes from shape (A) to shape (B) and finally the original shape (C). In this work, we explored the thermally and magnetically initiated shape-memory properties of triple-shape nanocomposites with various compositions and particle contents using different shape-memory creation procedures (SMCP). The nanocomposites were prepared by the incorporation of magnetite nanoparticles into a multiphase polymer network matrix with grafted polymer network architecture containing crystallizable poly(ethylene glycol) (PEG) side chains and poly(ε-caprolactone) (PCL) crosslinks named CLEGC. Excellent triple-shape properties were achieved for nanocomposites with high PEG weight fraction when two-step programming procedures were applied. In contrast, single-step programming resulted in dual-shape properties for all investigated materials as here the temporary shape (A) was predominantly fixed by PCL crystallites

Thermomechanical properties and shape-memory behavior of bisphenol a diacrylate-based shape-memory polymers

A series of acrylate-based shape-memory materials are synthesized from bisphenol A diacrylate monomers as crosslinking agents. Networks are synthesized by keeping constant the content of bisphenol A-based crosslinking agent and systematically varying the content ratio of different monofunctional chain builder monomers. The implications of the structure of bisphenol A-based monomers and the chemical structure and content of monofunctional monomers on thermomechanical properties are discussed. Thermomechanical properties are analyzed using dynamic mechanical analyses and mechanical properties are studied at room temperature and at the onset of the glass transition temperature. Shape-memory performances under isothermal and transient temperature conditions are also carried out. Tensile tests show excellent values of stress at break up to 45 and 15 MPa at room and high temperature, respectively. The measurements show excellent shape recovery and shape fixity ratios, ˜95% and 97%, respectively. These materials also show very high recovery velocities under transient temperature conditions, up to 24% min-1, and very short recovery times, up to 1.5 s, under isothermal conditions in a water bath. The results confirm that networks synthesized from bisphenol A crosslinkers are promising shape-memory materials.Postprint (author's final draft

What is "system": the information-theoretic arguments

The problem of "what is 'system'?" is in the very foundations of modern quantum mechanics. Here, we point out the interest in this topic in the information-theoretic context. E.g., we point out the possibility to manipulate a pair of mutually non-interacting, non-entangled systems to employ entanglement of the newly defined '(sub)systems' consisting the one and the same composite system. Given the different divisions of a composite system into "subsystems", the Hamiltonian of the system may perform in general non-equivalent quantum computations. Redefinition of "subsystems" of a composite system may be regarded as a method for avoiding decoherence in the quantum hardware. In principle, all the notions refer to a composite system as simple as the hydrogen atom.Comment: 13 pages, no figure

RGD constructs with physical anchor groups as polymer co-electrospinnable cell adhesives

The tissue integration of synthetic polymers can be promoted by displaying RGD peptides at the biointerface with the objective of enhancing colonization of the material by endogenous cells. A firm but flexible attachment of the peptide to the polymer matrix, still allowing interaction with receptors, is therefore of interest. Here, the covalent coupling of flexible physical anchor groups, allowing for temporary immobilization on polymeric surfaces via hydrophobic or dipole–dipole interactions, to a RGD peptide was investigated. For this purpose, a stearate or an oligo(ethylene glycol) (OEG) was attached to GRGDS in 51–69% yield. The obtained RGD linker constructs were characterized by NMR, IR and MALDI-ToF mass spectrometry, revealing that the commercially available OEG and stearate linkers are in fact mixtures of similar compounds. The RGD linker constructs were co-electrospun with poly(p-dioxanone) (PPDO). After electrospinning, nitrogen could be detected on the surface of the PPDO fibers by X-ray photoelectron spectroscopy. The nitrogen content exceeded the calculated value for the homogeneous material mixture suggesting a pronounced presentation of the peptide on the fiber surface. Increasing amounts of RGD linker constructs in the electrospinning solution did not lead to a detection of an increased amount of peptide on the scaffold surface, suggesting inhomogeneous distribution of the peptide on the PPDO fiber surface. Human adipose-derived stem cells cultured on the patches showed similar viability as when cultured on PPDO containing pristine RGD. The fully characterized RGD linker constructs could serve as valuable tools for the further development of tissue-integrating polymeric scaffolds

Insights from Multimodal Preclinical Imaging in Immunocompetent Nude Mice

Hydrogels based on gelatin have evolved as promising multifunctional biomaterials. Gelatin is crosslinked with lysine diisocyanate ethyl ester (LDI) and the molar ratio of gelatin and LDI in the starting material mixture determines elastic properties of the resulting hydrogel. In order to investigate the clinical potential of these biopolymers, hydrogels with different ratios of gelatin and diisocyanate (3-fold (G10_LNCO3) and 8-fold (G10_LNCO8) molar excess of isocyanate groups) were subcutaneously implanted in mice (uni- or bilateral implantation). Degradation and biomaterial-tissue- interaction were investigated in vivo (MRI, optical imaging, PET) and ex vivo (autoradiography, histology, serum analysis). Multimodal imaging revealed that the number of covalent net points correlates well with degradation time, which allows for targeted modification of hydrogels based on properties of the tissue to be replaced. Importantly, the degradation time was also dependent on the number of implants per animal. Despite local mechanisms of tissue remodeling no adverse tissue responses could be observed neither locally nor systemically. Finally, this preclinical investigation in immunocompetent mice clearly demonstrated a complete restoration of the original healthy tissue

Multivalent grafting of hyperbranched oligo- and polyglycerols shielding rough membranes to mediate hemocompatibility

Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo- and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials