Noncovalent Conjugation of OVA323 to ELP Micelles Increases Immune Response.

Subunit vaccines would benefit from a safe particle-based adjuvant. Elastin-like polypeptide (ELP)-based micelles are interesting candidate adjuvants due to their well-defined size and easy modification with protein-based cargo. Coiled coils can facilitate noncovalent modifications, while potentially enhancing antigen delivery through interaction with cell membranes. ELP micelles comprise ELP diblock copolymers that self-assemble above a critical micelle temperature. In this study, an amphiphilic ELP was conjugated to peptide "K", which forms a heterodimeric coiled-coil complex with peptide "E". Self-assembled "covalent" micelles containing ELP-OVA323 (i.e., model antigen OVA323 conjugated to ELP), "coiled-coil" micelles containing ELP-K/E-OVA323 and "hybrid" micelles containing ELP-K and ELP-OVA323 were shown to be monodisperse and spherical. Dendritic cells (DCs) were exposed to all micelle compositions, and T-cell proliferation was investigated. The presence of ELP-K enhanced micelle uptake and subsequent DC maturation, resulting in enhanced CD4+ T-cell proliferation, which makes ELPs with coiled coil-associated antigens a promising vaccine platform.

Photoprocessing of cationic triazacoronene: dissociation characteristics of polycyclic aromatic nitrogen heterocycles in interstellar environments.

Polycyclic aromatic nitrogen heterocycles (PANHs) are present in various astronomical environments where they are subjected to intense radiation. Their photodissociation pathways give crucial insights into the cycle of matter in the universe, yet so far only the dissociation characteristics of few PANHs have been investigated. Moreover, most experiments use single photon techniques that only reveal the initial dissociation step, and are thus unsuited to replicate astronomical environments and timescales. In this work, we use the Instrument for the Photodynamics of PAHs (i-PoP) at the Laboratory for Astrophysics to simulate the interstellar photodissociation of a model PANH, cationic triazacoronene (TAC˙+, C21H9N3). Comparing the observed fragments to similar PAHs such as the isoelectronic coronene can give mechanistic insight into PAH dissociation. For coronene the major photodissociation products were found to be C9H+, C10+, and C11+. In contrast, fragmentation in TAC˙+ is initiated by up to three HCN losses often in combination with H- or H2 losses. In the lower mass region, the fragments show similarities to comparable PAHs like coronene, but for TAC˙+ the inclusion of nitrogen atoms into the ionic fragments in the form of e.g. (di)cyanopolyynes is also observed. These nitrogen-containing species may be important tracers of regions in interstellar space where interstellar PANHs are being photodissociated.

Macroscopic and Microscopic Wettability of Graphene.

Interactions between water and graphene can be probed on a macroscopic level through wettability by measuring the water contact angle and on a microscopic level through water desorption kinetic studies using surface science methods. The contact angle studies of graphene pinpointed the critical role of sample preparation and measurement conditions in assessing the wettability of graphene. So far, studies of water desorption from graphene under the conditions of ultrahigh vacuum provided superior control over the environment but disregarded the importance of sample preparation. Here, we systematically examined the effect of the morphology of the growth substrate and of the transfer process on the macroscopic and microscopic wettability of graphene. Remarkably, the macroscopic wetting transparency of graphene does not always translate into microscopic wetting transparency, particularly in the case of an atomically defined Cu(111) substrate. Additionally, subtle differences in the type of substrates significantly alter the interactions between graphene and the first monolayer of adsorbed water but have a negligible effect on the apparent macroscopic wettability. This work looks into the correlations between the wetting properties of graphene, both on the macroscopic and microscopic scales, and highlights the importance of sample preparation in understanding the surface chemistry of graphene.

Ultrasensitive Field-Effect Biosensors Enabled by the Unique Electronic Properties of Graphene.

This review provides a critical overview of current developments on nanoelectronic biochemical sensors based on graphene. Composed of a single layer of conjugated carbon atoms, graphene has outstanding high carrier mobility and low intrinsic electrical noise, but a chemically inert surface. Surface functionalization is therefore crucial to unravel graphene sensitivity and selectivity for the detection of targeted analytes. To achieve optimal performance of graphene transistors for biochemical sensing, the tuning of the graphene surface properties via surface functionalization and passivation is highlighted, as well as the tuning of its electrical operation by utilizing multifrequency ambipolar configuration and a high frequency measurement scheme to overcome the Debye screening to achieve low noise and highly sensitive detection. Potential applications and prospectives of ultrasensitive graphene electronic biochemical sensors ranging from environmental monitoring and food safety, healthcare and medical diagnosis, to life science research, are presented as well.

Encapsulation of Graphene in the Hydrophobic Core of a Lipid Bilayer.

Theoretical simulations have predicted that a lipid bilayer forms a stable superstructure when a sheet of graphene is inserted in its hydrophobic core. We experimentally produced for the first time a lipid-graphene-lipid assembly by combining the Langmuir-Blodgett and the Langmuir-Schaefer methods. Graphene is sandwiched and remains flat within the hydrophobic core of the lipid bilayer. Using infrared spectroscopy, ellipsometry, and neutron reflectometry, we characterized the superstructure at every fabrication step. The hybrid superstructure is mechanically stable and graphene does not disturb the natural lipid bilayer structure.

Dynamic Tunneling Junctions at the Atomic Intersection of Two Twisted Graphene Edges.

The investigation of the transport properties of single molecules by flowing tunneling currents across extremely narrow gaps is relevant for challenges as diverse as the development of molecular electronics and sequencing of DNA. The achievement of well-defined electrode architectures remains a technical challenge, especially due to the necessity of high precision fabrication processes and the chemical instability of most bulk metals. Here, we illustrate a continuously adjustable tunneling junction between the edges of two twisted graphene sheets. The unique property of the graphene electrodes is that the sheets are rigidly supported all the way to the atomic edge. By analyzing the tunneling current characteristics, we also demonstrate that the spacing across the gap junction can be controllably adjusted. Finally, we demonstrate the transition from the tunneling regime to contact and the formation of an atomic-sized junction between the two edges of graphene.

Ultrasensitive Ethene Detector Based on a Graphene-Copper(I) Hybrid Material.

Ethene is a highly diffusive and relatively unreactive gas that induces aging responses in plants in concentrations as low as parts per billion. Monitoring concentrations of ethene is critically important for transport and storage of food crops, necessitating the development of a new generation of ultrasensitive detectors. Here we show that by functionalizing graphene with copper complexes biologically relevant concentrations of ethene and of the spoilage marker ethanol can be detected. Importantly, in addition these sensors provide us with important insights into the interactions between molecules, a key concept in chemistry. Chemically induced dipole fluctuations in molecules as they undergo a chemical reaction are harvested in an elegant way through subtle field effects in graphene. By exploiting changes in the dipole moments of molecules that occur upon a chemical reaction we are able to track the reaction and provide mechanistic insight that was, until now, out of reach.

Single molecule detection with graphene and other two-dimensional materials: nanopores and beyond.

Graphene and other two dimensional (2D) materials are currently integrated into nanoscaled devices that may - one day - sequence genomes. The challenge to solve is conceptually straightforward: cut a sheet out of a 2D material and use the edge of the sheet to scan an unfolded biomolecule from head to tail. As the scan proceeds - and because 2D materials are atomically thin - the information provided by the edge might be used to identify different segments - ideally single nucleotides - in the biomolecular strand. So far, the most efficient approach was to drill a nano-sized pore in the sheet and use this pore as a channel to guide and detect individual molecules by measuring the electrochemical ionic current. Nanoscaled gaps between two electrodes in 2D materials recently emerged as powerful alternatives to nanopores. This article reviews the current status and prospects of integrating 2D materials in nanopores, nanogaps and similar devices for single molecule biosensing applications. We discuss the pros and cons, the challenges, and the latest achievements in the field. To achieve high-throughput sequencing with 2D materials, interdisciplinary research is essential.

Spatiotemporal Control of Doxorubicin Delivery from "Stealth-Like" Prodrug Micelles.

In the treatment of cancer, targeting of anticancer drugs to the tumor microenvironment is highly desirable. Not only does this imply accurate tumor targeting but also minimal drug release en route to the tumor and maximal drug release once there. Here we describe high-loading, "stealth-like" doxorubicin micelles as a pro-drug delivery system, which upon light activation, leads to burst-like doxorbicin release. Through this approach, we show precise spatiotemporal control of doxorubicin delivery to cells in vitro.

Chemistry at the Edge of Graphene.

The selective functionalization of graphene edges is driven by the chemical reactivity of its carbon atoms. The chemical reactivity of an edge, as an interruption of the honeycomb lattice of graphene, differs from the relative inertness of the basal plane. In fact, the unsaturation of the pz orbitals and the break of the π conjugation on an edge increase the energy of the electrons at the edge sites, leading to specific chemical reactivity and electronic properties. Given the relevance of the chemistry at the edges in many aspects of graphene, the present Review investigates the processes and mechanisms that drive the chemical functionalization of graphene at the edges. Emphasis is given to the selective chemical functionalization of graphene edges from theoretical and experimental perspectives, with a particular focus on the characterization tools available to investigate the chemistry of graphene at the edge.

Controlled, reversible, and nondestructive generation of uniaxial extreme strains (>10%) in graphene.

Theoretical calculations have predicted that extreme strains (>10%) in graphene would result in novel applications. However, up to now the highest reported strain reached ∼1.3%. Here, we demonstrate uniaxial strains >10% by pulling graphene using a tensile-MEMS. To prevent it from slipping away it was locally clamped with epoxy using a femtopipette. The results were analyzed using Raman spectroscopy and optical tracking. Furthermore, analysis proved the process to be reversible and nondestructive for the graphene.

Highly strained graphene samples of varying thickness and comparison of their behaviour.

Mechanically straining graphene opens the possibility to exploit new properties linked to the stressed lattice of this two-dimensional material. In particular, theoretical analyses have forecast that straining graphene by more than 10% is a requirement for many novel applications that have not yet been experimentally demonstrated. Recently, we reported having achieved 12.5% strain in a trilayer graphene sample (3LG) in a controlled, reversible and non-destructive way. In this paper, we explore our method by straining samples of varying thicknesses and comparing their behavior, where strains of 14% and 11% were achieved for monolayer and four-layer graphene (4LG), respectively. For the analysis, optical tracking and the correspondent Raman spectra were taken. While doing so, we observed slippage between two layers in a bilayer sample of which one layer was clamped on one side only. The obtained results when stretching different samples to extreme strains demonstrated the exceptional elasticity of graphene, which might be essential for practical applications. Hysteretic effects observed in the partially clamped layer hints at small energy losses during slippage. This may shed new light on the superlubricity property of graphene that has been reported in the literature.

Covalent Benzenesulfonic Functionalization of a Graphene Nanopore for Enhanced and Selective Proton Transport.

A fundamental understanding of proton transport through graphene nanopores, defects, and vacancies is essential for advancing two-dimensional proton exchange membranes (PEMs). This study employs ReaxFF molecular dynamics, metadynamics, and density functional theory to investigate the enhanced proton transport through a graphene nanopore. Covalently functionalizing the nanopore with a benzenesulfonic group yields consistent improvements in proton permeability, with a lower activation barrier (≈0.15 eV) and increased proton selectivity over sodium cations. The benzenesulfonic functionality acts as a dynamic proton shuttle, establishing a favorable hydrogen-bonding network and an efficient proton transport channel. The model reveals an optimal balance between proton permeability and selectivity, which is essential for effective proton exchange membranes. Notably, the benzenesulfonic-functionalized graphene nanopore system achieves a theoretically estimated proton diffusion coefficient comparable to or higher than the current state-of-the-art PEM, Nafion. Ergo, the benzenesulfonic functionalization of graphene nanopores, firmly holds promise for future graphene-based membrane development in energy conversion devices.

Role of Vacancy Defects and Nitrogen Dopants for the Reduction of Oxygen on Graphene.

Disentangling the roles of nitrogen dopants and vacancy defects (VG) in metal-free carbon catalysts for the oxygen reduction reaction (ORR) ideally requires studying both the dopants and defects separately. Here, we systematically introduced nitrogen dopants and VGs via plasma treatment into the basal plane of monolayer graphene as a model carbon catalyst to investigate their specific roles in ORR catalysis. An increased defect density including dopants is positively associated with boosted ORR activity. Nitrogen dopants are responsible for an improved current via a 2e- pathway generating hydroperoxide, while VGs result in enhanced kinetics and water production. We therefore infer that VGs in graphene are responsible for the improved ORR kinetics, while nitrogen dopants majorly influence the selectivity of ORR reaction products. The nitrogen dopants without VGs lead to a higher overpotential compared with the pristine graphene. Instead of the attribution of the ORR active site to only nitrogen species in carbon materials, the improved ORR activity in nitrogen-doped carbon materials should be attributed to the active sites constituted of VGs, oxygen dopants, and nitrogen dopants. Through this work, we provide important insights into the intertwined roles of nitrogen and VGs as well as oxygen dopants in nitrogen-doped metal-free catalysts for a more efficient ORR.

Proton-selective coating enables fast-kinetics high-mass-loading cathodes for sustainable zinc batteries.

The pressing demand for sustainable energy storage solutions has spurred the burgeoning development of aqueous zinc batteries. However, kinetics-sluggish Zn2+ as the dominant charge carriers in cathodes leads to suboptimal charge-storage capacity and durability of aqueous zinc batteries. Here, we discover that an ultrathin two-dimensional polyimine membrane, featured by dual ion-transport nanochannels and rich proton-conduction groups, facilitates rapid and selective proton passing. Subsequently, a distinctive electrochemistry transition shifting from sluggish Zn2+-dominated to fast-kinetics H+-dominated Faradic reactions is achieved for high-mass-loading cathodes by using the polyimine membrane as an interfacial coating. Notably, the NaV3O8·1.5H2O cathode (10 mg cm-2) with this interfacial coating exhibits an ultrahigh areal capacity of 4.5 mAh cm-2 and a state-of-the-art energy density of 33.8 Wh m-2, along with apparently enhanced cycling stability. Additionally, we showcase the applicability of the interfacial proton-selective coating to different cathodes and aqueous electrolytes, validating its universality for developing reliable aqueous batteries.

Size-controlled polyelectrolyte complexes: direct measurement of the balance of forces involved in the triggered collapse of layer-by-layer assembled nanocapsules.

Polyelectrolyte multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) were assembled on 13 nm gold nanoparticles and characterized by Transmission Electron Microscopy and Atomic Force Microscopy. The direct measurement of the interactions at the molecular level using a Surface Force Apparatus revealed that the colloidal stability of such coated particles in aqueous media is brought about concomitantly by electrostatic and steric repulsive interactions. The cyanide induced dissolution of the gold cores yields either hollow nanocapsules or collapsed nanospheres, two species which are very difficult to distinguish. In contrast to the established micron sized hollow capsules, the dissolution of the nanosized gold cores may induce a substantial swelling of the polyelectrolyte complex into the central void as induced by the temporary local increase of the ionic strength. At least three layer pairs are required to maintain the structural integrity of the polyelectrolyte shells to yield hollow nanospheres. At about three layer pairs, thin nanocapsules are mechanically compressible and may collapse on themselves following mechanical stimulation to form even smaller spherical polyelectrolyte complex particles that retain the small polydispersity of the gold cores. Thus, the templating of polyelectrolyte shells around, e.g., gold nanoparticles followed by the dissolution of the respective cores constitutes a new method for the synthesis of extremely small polyelectrolyte complex particles with very low polydispersity.

Energetics and Kinetics of Hydrogen Electrosorption on a Graphene-Covered Pt(111) Electrode.

The Angstrom-scale space between graphene and its substrate provides an attractive playground for scientific exploration and can lead to breakthrough applications. Here, we report the energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode using electrochemical experiments, in situ spectroscopy, and density functional theory calculations. The graphene overlayer influences the hydrogen adsorption on Pt(111) by shielding the ions from the interface and weakening the Pt-H bond energy. Analysis of the proton permeation resistance with controlled graphene defect density proves that the domain boundary defects and point defects are the pathways for proton permeation in the graphene layer, in agreement with density functional theory (DFT) calculations of the lowest energy proton permeation pathways. Although graphene blocks the interaction of anions with the Pt(111) surfaces, anions do adsorb near the defects: the rate constant for hydrogen permeation is sensitively dependent on anion identity and concentration.

A Lock-and-Kill Anticancer Photoactivated Chemotherapy Agent†.

Photosubstitutionally active ruthenium complexes show high potential as prodrugs for the photoactivated chemotherapy (PACT) treatment of tumors. One of the problems in PACT is that the localization of the ruthenium compound is hard to trace. Here, a ruthenium PACT prodrug, [Ru(3)(biq)(STF-31)](PF6 )2 (where 3 = 3-(([2,2':6',2″-ter- pyridin]-4'-yloxy)propyl-4-(pyren-1-yl)butanoate) and biq = 2,2'-biquinoline), has been prepared, in which a pyrene tracker is attached via an ester bond. The proximity between the fluorophore and the ruthenium center leads to fluorescence quenching. Upon intracellular hydrolysis of the ester linkage, however, the fluorescence of the pyrene moiety is recovered, thus demonstrating prodrug cellular uptake. Further light irradiation of this molecule liberates by photosubstitution STF-31, a known cytotoxic nicotinamide phosphoribosyltransferase (NAMPT) inhibitor, as well as singlet oxygen via excitation of the free pyrene chromophore. The dark and light cytotoxicity of the prodrug, embedded in liposomes, as well as the appearance of blue emission upon uptake, were evaluated in A375 human skin melanoma cells. The cytotoxicity of the liposome-embedded prodrug was indeed increased by light irradiation. This work realizes an in vitro proof-of-concept of the lock-and-kill principle, which may ultimately be used to design strategies aimed at knowing where and when light irradiation should be realized in vivo.

Effect of surfactant hydrophobicity on the pathway for unfolding of ubiquitin.

This paper describes the interaction between ubiquitin (UBI) and three sodium n-alkyl sulfates (SC(n)S) that have the same charge (Z = -1) but different hydrophobicity (n = 10, 12, or 14). Increasing the hydrophobicity of the n-alkyl sulfate resulted in (i) an increase in the number of distinct intermediates (that is, complexes of UBI and surfactant) that form along the pathway of unfolding, (ii) a decrease in the minimum concentrations of surfactant at which intermediates begin to form (i.e., a more negative ΔG(binding) of surfactant for UBI), and (iii) an increase in the number of surfactant molecules bound to UBI in each intermediate or complex. These results demonstrate that small changes in the hydrophobicity of a surfactant can significantly alter the binding interactions with a folded or unfolded cytosolic protein.

Atomic-scale electron-beam sculpting of near-defect-free graphene nanostructures.

In order to harvest the many promising properties of graphene in (electronic) applications, a technique is required to cut, shape, or sculpt the material on the nanoscale without inducing damage to its atomic structure, as this drastically influences the electronic properties of the nanostructure. Here, we reveal a temperature-dependent self-repair mechanism that allows near-damage-free atomic-scale sculpting of graphene using a focused electron beam. We demonstrate that by sculpting at temperatures above 600 °C, an intrinsic self-repair mechanism keeps the graphene in a single-crystalline state during cutting, even though the electron beam induces considerable damage. Self-repair is mediated by mobile carbon ad-atoms that constantly repair the defects caused by the electron beam. Our technique allows reproducible fabrication and simultaneous imaging of single-crystalline free-standing nanoribbons, nanotubes, nanopores, and single carbon chains.