Potential applications of graphene

Potential graphene applications include lightweight, thin, and flexible electric/photonics circuits, solar cells, and various medical, chemical and industrial processes enhanced or enabled by the use of new graphene materials. In 2008, graphene produced by exfoliation was one of the most expensive materials on Earth, with a sample the area of a cross section of a human hair costing more than

1,000 as of April 2008 (about

100,000,000/cm2). Since then, exfoliation procedures have been scaled up, and now companies sell graphene in large quantities. The price of epitaxial graphene on silicon carbide is dominated by the substrate price, which was approximately

100/cm2 as of 2009. There is now a new method of making graphene out of gum trees that can lower the cost to up to

0.50 per gram as of 2019. Hong and his team in South Korea pioneered the synthesis of large-scale graphene films using chemical vapour deposition (CVD) on thin nickel layers, which triggered research on practical app

Chiral Cyclic Alkyl Amino Carbene (CAAC) Transition-Metal Complexes: Synthesis, Structural Analysis, and Evaluation in Asymmetric Catalysis

Adrien Jules Louis Madron Du Vigné

Despite recent advances in the field of cyclic alkyl amino carbenes (CAACs) including a few complementary synthetic strategies affording CAACs with various substitution patterns, the application potential of chiral CAACs to efficiently catalyze asymmetric organometallic transformations remains largely underdeveloped. Herein, we describe a convenient and robust route that incorporates common chiral primary amine allowing access of a broad range of chiral CAACs precursors. The corresponding transition-metal complexes with Cu, Au, Ru, Rh, Ir, and Pd were obtained in a straightforward manner. The steric parameters of the complexes were comprehensively collected by X-ray single-crystal analysis to serve as a source of information for further ligand design. The preliminary application potential of the copper CAAC complexes was tested in asymmetric conjugate borylation of an alpha,beta-unsaturated ester providing 89:11 er, thus illustrating the potential of chiral CAACs in asymmetric catalysis.

AMER CHEMICAL SOC2022

Peptide-Polymer Conjugates for Therapeutic Applications

Ana Maria Raduta

Over the last ten years the attention of the pharmaceutical industry has shifted away from small molecules to focus on new biologics such as antibodies, proteins and therapeutic peptides. Herein, peptides have emerged as a particularly interesting category that fills a niche between small molecule chemicals and the larger proteins. Although they have great potential for drug development, their use is still limited due to their intrinsic low systemic stability, rapid renal elimination and poor membrane permeability. Various formulations have been developed to take advantage of their therapeutic properties, one of the most promising strategies being chemical conjugation to a polymer. Peptide-polymer conjugates are hybrid materials that consist of one or more synthetic polymers covalently attached to one or more peptide fragments. The aim of this thesis was to provide an insight into the requirements for the design of peptide-polymer conjugates for therapy. Chapter 1 illustrates the state of the art in the development of peptides for therapeutic applications, exemplifies the different architectures and structures of peptide-polymer conjugates and discusses ongoing efforts to improve and diversify the range and applications of these conjugates. Chapter 2 describes a novel synthetic strategy to prepare PHPMA based peptide-polymer conjugates via thiol chemistry starting from poly(pentafluorophenyl methacrylate). By varying the feed composition, the extent of side chain modification could be controlled. Further modification of the reactive copolymer scaffolds led to the site specific attachment of model peptides. This method was used to synthesize stable as well as pH and redox sensitive peptide-polymer conjugates and the release of the peptide from the polymer backbone was studied in acidic and redox conditions. In Chapter 3, the aim was to construct a peptide-polymer conjugate that could serve to promote intracellular delivery and drug release but also play a role in the intracellular trafficking of the drug. To this end, coiled coil peptides E3/K3 was attached to a PHPMA polymer backbone and was used to facilitate release from the backbone at acidic pH and further endosomal escape. Initially, the membrane lytic properties of E3/K3 and three newly designed E3/K3X motifs on model membranes were investigated as a function of pH. Secondly, the potential application of E3/K3 peptide-polymer conjugate for cytoplasmic delivery was evaluated in vitro. Chapter 4 explores the synthesis and in vitro therapeutic activity of synthetic peptide-polymer conjugates focusing on the inhibition of an oncogenic transcription factor (AP-1). To this end, AFosW peptide, a peptide binder that can interfere with AP-1 formation was attached to a polymer backbone via a redox or pH sensitive linker using a strategy developed in Chapter 2. Fluorescent microscopy and flow cytometry provided an insight into the cellular uptake of these conjugates. Their ability to interfere with AP-1 formation in vitro was quantified. Chapter 5 describes the synthesis of a second generation of peptide-polymer conjugates for AP-1 inhibition that along the FosW dominant negative peptide also incorporates a motif that facilitates endosomal escape and a nuclear localization sequence. To investigate the potential application for therapy, the conjugates were evaluated and compared with regard to their ability to inhibit AP-1 formation in living cells.

EPFL2015

Phase Gradient Estimation Techniques in Fringe Analysis

Rajshekhar Gannavarpu

The thesis introduces novel techniques in the field of fringe analysis for direct estimation of phase gradients or derivatives. A pseudo Wigner-Ville distribution based method is proposed to reliably estimate the phase derivatives from a single fringe pattern. The method's ability for estimating rapidly varying phase derivatives is enhanced by developing an adaptive windowing technique. Further, the two-dimensional extension of the method is presented to handle fringe patterns with severe noise. In addition, a generalized approach is described to enable direct estimation of arbitrary order phase derivatives. Subsequently, methods based on digital holographic moiré and multi-component polynomial phase formulation are introduced to measure the in-plane and out-of-plane displacements and their derivatives for a deformed object in digital holographic interferometry. These methods permit the simultaneous estimation of multiple phases and their derivatives without the need of multiple fringe patterns and complex experimental configurations, which is hitherto not possible with the current state-of-the-art fringe analysis methods. The major advantages of the developed techniques are the ability to directly estimate phase derivatives without relying on complex unwrapping, filtering and numerical differentiation operations, high computational efficiency and strong robustness against noise. In addition, the requirement of a single fringe pattern makes these techniques less error-prone in the presence of vibrations and external disturbances and enhances their applicability for dynamic measurements. Further, the developed techniques offer a potential solution to the challenging problem of simultaneous multi-dimensional deformation analysis in digital holographic interferometry. The reliable performance of these techniques is validated by numerical simulation and their practical applicability is demonstrated in digital holographic interferometry and fringe projection for slope and curvature measurement, defect detection, surface slope evolution studies and measurement of in-plane and out-of-plane displacements and their derivatives. These techniques offer substantial advancements in fringe analysis and exhibit significant application potential in areas such as non-destructive testing, biomechanics, reliability analysis, material characterization and experimental mechanics.

EPFL2012