Marcin Libera

Direct synthesis of graphene from adsorbed organic solvent molecules over copper

The isolation of graphene by Novoselov et al. in 2004 ignited massive interest in this material. For graphene to succeed fully as a future material its controlled fabrication is required. While numerous routes have been and are being developed, chemical vapor deposition (CVD) is by far the most common approach. There is also interest in forming graphene directly from adsorbed molecules on a substrate. Few examples exist and those that do require multiple steps and rarely offer large graphene domains. In this work we demonstrate a remarkably simple route in which organic solvent precursor molecules are heated in a hydrogen rich atmosphere to directly form graphene over clean Cu foils. The single-step synthesis route has been studied systematically. The systematic studies not only highlight the importance of hydrogen radicals for this reaction, but also provide improved understanding of the role of hydrogen in the formation of graphene from hydrocarbon precursors (e.g. graphene fabrication from thermal CVD).

Silica-supported Au@hollow-SiO2 particles with outstanding catalytic activity prepared via block copolymer template approach

Catalytically active Au@hollow-SiO2 particles embedded in porous silica support (Au@hollow-SiO2@PSS) were prepared by using spherical micelles from poly(styrene)-block-poly(4-vinyl pyridine) block copolymer as a sacrificial template. Drastic increase of the shell porosity was observed after pyrolytic removal of polymeric template because the stretched poly(4-vinyl pyridine) chains interpenetrating with silica shell acted as an effective porogen. The embedding of Au@hollow-SiO2 particles in porous silica support prevented their fusion during pyrolysis. The catalytic activity of Au@hollow-SiO2@PSS was investigated using a model reaction of catalytic reduction of 4-nitrophenol and reductive degradation of Congo red azo-dye. Significantly, to the best of our knowledge, Au@hollow-SiO2@PSS catalyst shows the highest activity among analogous systems reported till now in literature. Such high activity was attributed to the presence of multiple pores within silica shell of Au@hollow-SiO2 particles and easy accessibility of reagents to the catalytically active sites of the ligand-free gold surface through the porous silica support.

Chimeric lipid/block copolymer nanovesicles: Physico-chemical and bio-compatibility evaluation

Chimeric systems are mixed nanovectors composed by different in nature materials and exhibit new functionalities and properties. The particular chimeric nanovectors, formed by the co-assembly of low and high molecular weight amphiphiles, have the potential to be utilized as drug delivery platforms. We have utilized two lipids, l-α-phosphatidylcholine, hydrogenated (Soy)(HSPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and a poly(oligoethylene glycol acrylate)-b-poly(lauryl acrylate) (POEGA-PLA) block copolymer, at different molar ratios, in aqueous media. Light scattering, differential scanning calorimetry (DSC) and imaging techniques (cryo-TEM, AFM) were employed in order to elucidate the structure and properties of the nanostructures, as well as the cooperativity between the components. DSC experiments showed considerable interaction of the block copolymer with the lipid bilayers and suggested an inhomogeneous distribution of the copolymer chains and lateral phase separation of the components. Vesicle formation was observed in most cases by cryo-TEM with a chimeric membrane exhibiting kinks, in accordance with DSC data. A series of biocompatibility experiments indicated good in vitro biological stability and low cytotoxicity in vivo of the novel nanocarriers. Finally, ibuprofen (IBU) was used as model drug in order to study the loading and the release properties of the prepared chimeric lipid/block copolymer vesicles.

Silver nanoparticles formed in bio- and chemical syntheses with biosurfactant as the stabilizing agent

ABSTRACT In this work, the comparison of the physical properties of silver nanoparticles (AgNPs) obtained via the reduction of silver nitrate (AgNO3) in biological and chemical (model) syntheses supplemented with the biosurfactant surfactin is described. In the studies, two strains of Bacillus subtilis (denoted T’1 and I’1a) were used. The biological synthesis of AgNPs was performed using supernatants obtained from cultures of bacteria growing on brewery effluents, molasses, and Luria–Bretani (LB) medium. In model experiments, ascorbic acid served as the reductant; surfactin acted as the stabilizing agent. The surfactin concentrations were adjusted to 5 and 30 mg/L, which corresponded to minimum and maximum surfactin concentrations as measured in the supernatants obtained from the B. subtilis cultures. The chemical synthesis was carried out at acidic as well as alkaline pH. Dynamic light scattering (DLS) revealed that in model and biological samples, single AgNPs were accompanied by aggregated structures. Transmission electron microscopy showed that the contribution of the aggregates in bacterial supernatants and in chemical synthesis is negligible under acidic conditions. However, in the alkaline environment, this contribution predominates. In the model experiments, smaller nanoparticles were formed with higher concentrations of surfactant. The presence of surfactin significantly increased the stability of AgNPs in both bio- and chemical syntheses. GRAPHICAL ABSTRACT

Amphiphilic core-shell nanoparticles with dimer fatty acid-based aliphatic polyester core and zwitterionic poly(sulfobetaine) shell for controlled delivery of curcumin

ABSTRACT Multifunctional nanocarriers are gaining increasing research interest as polymeric platforms for targeted drug delivery in cancer therapy and diagnosis. In this work, preparation and characterization of surfactant-free polyester nanoparticles (NPs) from a bio-based poly(butylene sebacate-co-butylene dilinoleate)s, poly(butylene sebacate) (PBSE)/poly(butylene dilinoleate) (PBDL), using nanoprecipitation, is reported. The polymeric nanoparticles (sizes narrowly distributed in a range less than 100 nm) were loaded with curcumin (CURC) with an encapsulation efficiency of 98% and drug loading (DL) content of 5–10% wtdrug/wtpolymer. The CURC-loaded nanoparticles were efficiently coated with a novel poly(sulfobetaine)-type zwitterionic polymer synthesized by nitroxide-mediated polymerization and postpolymerization functionalization step. Free and CURC formulated into noncoated and poly(sulfobetaine)-type zwitterionic polymer-coated nanoparticles were further investigated for cytotoxicity and antioxidant activity in a panel of human cell lines and rat liver microsomes, respectively. Formulated into coated NPs, CURC has superior cytotoxic and antioxidant activity versus the free drug and CURC incorporated in noncoated NPs. In addition, cell viability experiments of nonloaded nanoparticles, both coated and noncoated, demonstrated that developed nanoparticles are nontoxic, making them potentially suitable candidates for systemic passive targeting in cancer therapy, namely for treatment of solid tumors exhibiting high tumor accumulation of NPs due to enhanced permeability and retention effect. Polyzwitterion-coated nanoparticles exhibited slower drug release compared with the noncoated ones (half as much after 24 h) presumably due to the presence of the polymer shell around nanoparticles associated with a wider diffusion layer around the particles. GRAPHICAL ABSTRACT

Corrosion resistance of PLGA-coated biomaterials

The aim of the study was to determine the influence of PLGA bioresorbable polymer coating on corrosion resistance of metal biomaterial. Polymer coating deposited by immersion method was applied. Corrosion resistance of metal biomaterials (stainless steel, Ti6Al4V, Ti6Al7Nb) coated with PLGA polymer, after 90 days exposure to Ringers solution was tested. The amount of metal ions released to the solution was also investigated (inductively coupled plasma-atomic emission spectrometry (ICP-AES) method). The surface of the samples was observed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Degradation of PLGA was monitored with the use of the 1H NMR spectroscopy and GPC (Gel Permeation Chromatography). The studies were carried out for non-sterilized (NS) and sterilized (S) samples. Application of the polymer coating causes a reduction of release of metal ions to the solution. Depending on metal substrate different course of destruction of polymer layer was observed. After 90 days of incubation in Ringers solution polymer layer was highly degraded, however, the composition of copolymer (ratio of the comonomeric units in the chain) remained unchanged during the whole process, which suggests even degradation. The polymer layer reduced degradation kinetics of the metal substrate. Moreover, degradation process did not change surface morphology of metal substrate and did not disturb its integrity. The results obtained indicate that the applied polymer layer improves corrosion resistance of the alloys being investigated. Thus, the developed implants with bioresorbable coatings could be advantageous for medical applications.

Thermal properties and morphology changes in degradation process of poly(L-lactide-co-glycolide) matrices with risperidone

Determining thermal properties and morphology seems to be useful in the analysis of release and degradation processes form polymeric materials. Risperidone is available in the formulation of a long-acting injection based on poly(D,L-lactide-co-glycolide). Currently, alternative solutions are also offered, i.e., nano- and microparticles or implants, including copolymers of lactide and glycolide. The effect of risperidone content on the properties of poly(L-lactide-co-glycolide) matrices was determined. The study also involved an assessment of the changes during degradation. Risperidone free matrices and the matrices with risperidone were obtained by solvent casting. Thermal characteristics were tested by means of differential scanning calorimetry, and the morphology was evaluated using a scanning electron microscope. Risperidone did not change significantly semi-crystalline structure of poly(L-lactide-co-glycolide) matrices. The decrease in crystallization temperature and glass transition temperature during degradation was observed. Many pores and their deformation, the widening of pore area, cracks and slits because of degradation were observed. The analysis of thermal properties and morphology allowed us to explain degradation process. Matrices exhibited stable process of degradation, which may be advantageous for development of prolonged risperidone release systems.

Regulatory and risk assessment perspective for core-multishell nanocarriers

Abstract Core-multishell (CMS) nanocarriers (DendroSol) are innovative biocompatible excipients, which can be used to improve the dermal penetration of medicinal drug substances. The basis of CMS nanocarriers is a hyperbranched polyglycerol core surrounded by an amphiphilic shell. By varying chain lengths and charge density, the excipients can be adapted to different drug substances. As excipients within drugs, CMS nanocarriers are required to fulfill regulatory requirements, including 2015/C 95/02—an EU guideline on the formalized risk assessment for ascertaining the appropriate good manufacturing practice for excipients of medicinal products for human use. The risk assessment also considers the quality management system, as well as the source and intended use of the excipients. Specifically, CMS nanocarriers are well suited as excipients following a careful risk assessment.

Mixed lipid/polymer nanostructures: From advanced materials to drug delivery systems

The aim of this investigation was to study the alterations of the physicochemical characteristics of L-α-phosphatidylcholine, hydrogenated (Soy) (HSPC) and dipalmitoyl phosphatidyl choline (DPPC) liposomes, caused by the incorporation of a poly (oligoethylene glycol acrylate)-b-poly(lauryl acrylate) (POEGA-PLA) block copolymer at different molar ratios. We used Dynamic and Electrophoretic Light Scattering to determine the size and the ζ-potential; imaging techniques for investigate the structure and Static Light Scattering for quantifying the fractal morphology of the prepared nanosystems in situ. The size of mixed nanostructures became smaller with the incorporation of the block copolymer into the lipid membrane. The size of the prepared nanosystems ranged between 50-80nm. The fractal dimension (df) decreased significantly with the incorporation of block copolymer into liposomal bilayers. The morphology of DPPC:POEGA-PLA mixed nanostructures (with df equal to 1.8) is open (more loose). On the other hand, the morphology of HSPC: POEGA-PLA (with df equal to 2.1) is more compact and dense. The molar ratio of the POEGA-PLA did not alter the morphology of the mixed nanostructures, expect from HSPC:POEGA-PLA system. Finally, we studied the drug loading properties of the mixed nanostructures in order to examine their properties as advanced Drug Delivery nanosystems. Copyright