We provide evidence of low-temperature hydrogen evolution and possible hydrogen trapping in an anthracite coal derivative, formed via reactive ball milling with cyclohexene. No molecular hydrogen is added to the process. Raman-active molecular hydrogen vibrations are apparent in samples at atmospheric conditions (300 K, 1 bar) for samples prepared 1 year previously and stored in ambient air. Hydrogen evolves slowly at room temperature and is accelerated upon sample heating, with a first increase in hydrogen evolution occurring at approximately 60 degrees C. Subsequent chemical modification leads to the observation of crystalline carbons, including nanocrystalline diamond surrounded by graphene ribbons, other sp2-sp3 transition regions, purely graphitic regions, and a previously unidentified crystalline carbon form surrounded by amorphous carbon. The combined evidence for hydrogen trapping and carbon crystallization suggests hydrogen-induced crystallization of the amorphous carbon materials, as metastable hydrogenated carbons formed via the high-energy milling process rearrange into more thermodynamically stable carbon forms and molecular hydrogen.

Graphite nanofibers (GNFs) were doped with platinum in an attempt to activate the materials for moderate temperature hydrogen adsorption. Characterization of the 1% Pt/GNF sample indicates well-dispersed, metallic platinum particles ranging from 2 to 5 nm in diameter. At 27 °C and 20 bar, the hydrogen uptake of 1% Pt/GNF was less than 0.1 wt % and showed no increase relative to the GNF precursor within experimental detection limits. To explore this apparent anomaly, a stochastic Monte Carlo simulation was used to analyze the hydrogen spillover process for idealized two-dimensional surfaces with two surface types with interfacial mass transfer from the first to the second surface site. The model suggests interfacial mass transfer may not improve overall surface coverage when the rates of adsorption and desorption to the support are comparable. Dimensionless groupings are introduced to the stochastic simulation to explore the conditions in which interfacial transfer will lead to significant surface coverage from a catalytically active surface to a previously inert surface. The implications for hydrogen storage are discussed.

No abstract

In this work, biocompatible and degradable biohybrid microgels based on chitosan and dextran were synthesized for drug delivery applications. Two kinds of bio-based building blocks, alkyne-modified chitosan and azide-modified dextran, were used to fabricate microgels via single-step cross-linking in water-in-oil emulsions. The cross-linking was initiated in the presence of copper­(II) without the use of any extra cross-linkers. A series of pH-responsive and degradable microgels were successfully synthesized by varying the degree of cross-links. The microgels were characterized using 1H NMR and FTIR spectroscopy which proved the successful cross-linking of alkyne-modified chitosan and azide-modified dextran by copper­(II)-mediated click reaction. The obtained microgels exhibit polyampholyte character and can carry positive or negative charges in aqueous solutions at different pH values. Biodegradability of microgels was shown at pH 9 or in the presence of Dextranase due to the hydrolysis of carbonate esters in the microgels or 1,6-α-glucosidic linkages in dextran structure, respectively. Furthermore, the microgels could encapsulate vancomycin hydrochloride (VM), an antibiotic, with a high loading of approximately 93.67% via electrostatic interactions. The payload could be released in the presence of Dextranase or under an alkaline environment, making the microgels potential candidates for drug delivery, such as colon-specific drug release.

In this work, we synthesized electroactive and degradable microgels based on biomacromolecular building blocks, which enable the controlled release of therapeutic drugs.

Due to its biocompatibility, electrical conductivity, and tissue‐like elasticity, poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) constitutes a highly promising material regarding the fabrication of smart cell culture substrates. However, until now, high‐throughput synthesis of pure PEDOT:PSS geometries was restricted to flat sheets and fibers. In this publication, the first microfluidic process for the synthesis of spherical, highly porous, pure PEDOT:PSS particles of adjustable material properties is presented. The particles are synthesized by the generation of PEDOT:PSS emulsion droplets within a 1‐octanol continuous phase and their subsequent coagulation and partial crystallization in an isopropanol (IPA)/sulfuric acid (SA) bath. The process allows to tailor central particle characteristics such as crystallinity, particle diameter, pore size as well as electrochemical and mechanical properties by simply adjusting the IPA:SA ratio during droplet coagulation. To demonstrate the applicability of PEDOT:PSS particles as potential cell culture substrate, cultivations of L929 mouse fibroblast cells and MRC‐5 human fibroblast cells are conducted. Both cell lines present exponential growth on PEDOT:PSS particles and reach confluency with cell viabilities above 95 vol.% on culture day 9. Single cell analysis could moreover reveal that mechanotransduction and cell infiltration can be controlled by the adjustment of particle crystallinity.

Alveolar‐capillary basement membrane (BM) is ultra‐thin (<2 µm) extracellular matrix that maintains integral epithelial‐endothelial cell layers. In vitro reconstructions of alveolar‐capillary barrier supported on synthetic scaffolds closely resembling the fibrous and ultra‐thin natural BM are essential in mimicking the lung pathophysiology. Although BM topology and dimensions are well known to significantly influence cellular behavior, conventionally used BM mimics fail to recreate this natural niche. To overcome this, electrospun ultra‐thin 2 µm poly(caprolactone) (PCL) nanofibrous mesh is used to establish an alveolar‐capillary barrier model of lung endothelial/epithelial cells. Transepithelial electrical resistance (TEER) and permeability studies reveal integral tight junctions and improved mass transport through the highly porous PCL meshes compared to conventional dense membranes with etched pores. The chemotaxis of neutrophils is shown across the barrier in presence of inflammatory response that is naturally impeded in confined regions. Conventional requirement of 3 µm or larger pore size can lead to barrier disruption due to epithelial/endothelial cell invasion. Despite high porosity, the interconnected BM mimic prevents barrier disruption and allows neutrophil transmigration, thereby demonstrating the physiological relevance of the thin nanofibrous meshes. It is envisioned that these bipolar cultured barriers would contribute to an organ‐level in vitro model for pathological disease, environmental pollutants, and nanotoxicology.

Advancements in the field of tissue engineering have led to the elucidation of physical and chemical characteristics of physiological basement membranes (BM) as specialized forms of the extracellular matrix. Efforts to recapitulate the intricate structure and biological composition of the BM have encountered various advancements due to its impact on cell fate, function, and regulation. More attention has been paid to synthesizing biocompatible and biofunctional fibrillar scaffolds that closely mimic the natural BM. Specific modifications in biomimetic BM have paved the way for the development of in vitro models like alveolar-capillary barrier, airway models, skin, blood-brain barrier, kidney barrier, and metastatic models, which can be used for personalized drug screening, understanding physiological and pathological pathways, and tissue implants. In this Review, we focus on the structure, composition, and functions of in vivo BM and the ongoing efforts to mimic it synthetically. Light has been shed on the advantages and limitations of various forms of biomimetic BM scaffolds including porous polymeric membranes, hydrogels, and electrospun membranes This Review further elaborates and justifies the significance of BM mimics in tissue engineering, in particular in the development of in vitro organ model systems.