Alloy nanoparticles are important in many fields, including catalysis, plasmonics, and electronics, due to the chemical and physical properties that arise from the interactions between their ...components. Typically, alloy nanoparticles are made by solution-based synthesis; however, scanning-probe-based methods offer the ability to make and position such structures on surfaces with nanometer-scale resolution. In particular, scanning probe block copolymer lithography (SPBCL), which combines elements of block copolymer lithography with scanning probe techniques, allows one to synthesize nanoparticles with control over particle diameter in the 2–50 nm range. Thus far, single-element structures have been studied in detail, but, in principle, one could make a wide variety of multicomponent systems by controlling the composition of the polymer ink, polymer feature size, and metal precursor concentrations. Indeed, it is possible to use this approach to synthesize alloy nanoparticles comprised of combinations of Au, Ag, Pd, Ni, Co, and Pt. Here, such structures have been made with diameters deliberately tailored in the 10–20 nm range and characterized by STEM and EDS for structural and elemental composition. The catalytic activity of one class of AuPd alloy nanoparticles made via this method was evaluated with respect to the reduction of 4-nitrophenol with NaBH4. In addition to being the first catalytic studies of particles made by SPBCL, these proof-of-concept experiments demonstrate the potential for SPBCL as a new method for studying the fundamental science and potential applications of alloy nanoparticles in areas such as heterogeneous catalysis.
Supramolecular chemistry has emerged as an important technique for the formation of biomaterials, including nano- and microparticles and hydrogels. One specific class of supramolecular chemistry is ...the direct association of guest–host pairs, which involves host macrocycles such as cyclodextrins and cucurbitnurils and a wide range of guest molecules, where association is typically driven by molecule size and hydrophobicity. These systems are of particular interest in the biomedical field due to their dynamic nature, chemical diversity, relative ease of synthesis, and ability to interact with biological or synthetic molecules. In this review, we discuss aspects of polymeric material assembly mediated by guest–host interactions, including the fundamentals of assembly into functional biomedical materials. Additionally, applications of biomaterials that utilize guest–host interactions are discussed with a focus on injectable material formulations, the sequestration and delivery of encapsulated cargo (i.e., drugs, biomolecules), and the investigation of cell–material interactions (i.e., adhesion, differentiation, and delivery). While methodologies for guest–host mediated assembly and biological interaction have rapidly evolved in recent years, they remain far from realizing their full potential in the biomaterials field.
Nanocellulose in food packaging: A review Ahankari, Sandeep S.; Subhedar, Aditya R.; Bhadauria, Swarnim S. ...
Carbohydrate polymers,
03/2021, Letnik:
255
Journal Article
Recenzirano
•NC is emerging as a biodegradable and sustainable alternative to the current synthetic packaging barrier films.•WVTR of NC based composite films has decreased to ∼ 15 g/m2/day; a performance closer ...to its petro-based counterparts.•NC assists in the controlled release of antimicrobial agents in active packaging.•Biodegradable films that utilize methods like plant extract reduction, UV reduction are employ completely green routes.
The research in eco-friendly and sustainable materials for packaging applications with enhanced barrier, thermo-mechanical, rheological and anti-bacterial properties has accelerated in the last decade. Last decade has witnessed immense interest in employing nanocellulose (NC) as a sustainable and biodegradable alternative to the current synthetic packaging barrier films. This review article gathers the research information on NC as a choice for food packaging material. It reviews on the employment of NC and its various forms including its chemico-physical treatments into bio/polymers and its impact on the performance of nanocomposites for food packaging application. The review reveals the fact that the research trends towards NC based materials are quite promising for Active Packaging (AP) applications, including the Controlled Release Packaging (CRP) and Responsive Packaging (RP). Finally, it summarizes with the challenges of sustainable packaging, gray areas that need an improvement/focus in order to commercially exploit this wonderful material for packaging application.
Conspectus Metal–organic and covalent–organic frameworks (MOFs/COFs) have been extensively studied for fundamental interests and their promising applications, taking advantage of their unique ...structural properties, i.e., high porosity and large surface-to-volume ratio. However, their electronic and magnetic properties have been somewhat overlooked because of their relatively poor performance as conductive and/or magnetic materials. Recent experimental breakthroughs in synthesizing two-dimensional (2D) π-conjugated MOFs/COFs with high conductivity and robust magnetism through doping have generated renewed and increasing interest in their electronic properties. Meanwhile, comprehensive theoretical studies of the underlying physical principles have led to discovery of many exotic quantum states, such as topological insulating states, which were only observed in inorganic systems. Especially, the diversity and high tunability of MOFs/COFs have provided a playground to explore novel quantum physics and quantum chemistry as well as promising applications. The band theory has empowered us to understand the most fundamental electronic properties of inorganic crystalline materials, which can also be used to better understand MOFs/COFs. The first obvious difference between the two is that instead of atomic orbitals residing at lattice sites of inorganic crystals, molecular orbitals of organic ligands are predominant in MOFs/COFs. The second key difference is that usually all atomic orbitals in an inorganic crystal are subject to one common group of lattice symmetry, while atomic orbitals of metal ion and molecular orbitals of different organic ligands in MOFs/COFs belong to different subgroups of lattice symmetries. Both these differences will impact the band structure of MOFs/COFs, in particular making it more complex. Consequently, which subset of bands are of most importance depends strongly on the location of Fermi level, i.e., electron counting and charge doping. Furthermore, there are usually two types of characteristic electrons coupled in MOFs, i.e., strongly correlated localized d and f electrons and diffusive s and p electrons, which interplay with lattice, orbital, and spin degrees of freedom, leading to more exotic topological and magnetic band structures. In this Account, we present an up-to-date review of recent theoretical developments to better understand the exotic band structures of MOFs/COFs. Starting from three fundamental 2D lattice models, i.e., honeycomb, Kagome, and Lieb lattices, exotic Dirac and flat bands as well as the intriguing topological quantum states they host, e.g., quantum spin Hall and quantum anomalous Hall states, are outlined. In addition to the single-lattice models, we further elaborate on combined lattice model Hamiltonians, which give rise to overlapping bands hosting novel quantum states, such as nodal-line Dirac semimetal and unconventional superconducting states. Also, first-principles predictions of candidate MOFs/COFs that host these exotic bands and hence quantum phases are reviewed, which greatly extends the pool of materials beyond inorganic crystals for hosting exotic band structures.
Single-molecule detection is the ultimate sensitivity in analytical chemistry and has been largely unavailable in electrochemical analysis. Here, we demonstrate the feasibility of detecting ...electrochemically inactive single biomacromolecules, such as enzymes, antibodies, and DNA, by blocking a solution redox reaction when molecules adsorb and block electrode sites. By oxidizing a large concentration of potassium ferrocyanide on an ultramicroelectrode (UME, radius ≤150 nm), time-resolved, discrete adsorption events of antibodies, enzymes, DNA, and polystyrene nanospheres can be differentiated from the background by their “footprint”. Further, by assuming that the mass transport of proteins to the electrode surface is controlled mainly by diffusion, a size estimate using the Stokes–Einstein relationship shows good agreement of electrochemical data with known protein sizes.
Self-powered artificial nanomotors are currently attracting increased interest as mimics of biological motors but also as potential components of nanomachinery, robotics, and sensing devices. We have ...recently described the controlled shape transformation of polymersomes into bowl-shaped stomatocytes and the assembly of platinum-driven nanomotors. However, the platinum encapsulation inside the structures was low; only 50% of the structures contained the catalyst and required both high fuel concentrations for the propelling of the nanomotors and harsh conditions for the shape transformation. Application of the nanomotors in a biological setting requires the nanomotors to be efficiently propelled by a naturally available energy source and at biological relevant concentrations. Here we report a strategy for enzyme entrapment and nanomotor assembly via controlled and reversible folding of polymersomes into stomatocytes under mild conditions, allowing the encapsulation of the proteins inside the stomach with almost 100% efficiency and retention of activity. The resulting enzyme-driven nanomotors are capable of propelling these structures at low fuel concentrations (hydrogen peroxide or glucose) via a one-enzyme or two-enzyme system. The confinement of the enzymes inside the stomach does not hinder their activity and in fact facilitates the transfer of the substrates, while protecting them from the deactivating influences of the media. This is particularly important for future applications of nanomotors in biological settings especially for systems where fast autonomous movement occurs at physiological concentrations of fuel.
In this study, the antioxidant and antiradical properties of some phyto lignans (nordihydroguaiaretic acid, secoisolariciresinol, secoisolariciresinol diglycoside, and α-(-)-conidendrin) and ...mammalian lignans (enterodiol and enterolactone) were examined by different antioxidant assays. For this purpose, radical scavenging activities of phyto and mammalian lignans were realized by 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) radical (ABTS
) scavenging assay and 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) scavenging assay. Additionally, the reducing ability of phyto and mammalian lignans were evaluated by cupric ions (Cu
) reducing (CUPRAC) ability, and ferric ions (Fe
) and Fe
-(TPTZ)2
complex reducing (FRAP) abilities. Also, half maximal inhibitory concentration (IC
) values were determined and reported for DPPH
and ABTS
scavenging influences of all of the lignan molecules. The absorbances of the lignans were found in the range of 0.150-2.320 for Fe
reducing, in the range of 0.040-2.090 for Cu
reducing, and in the range of 0.360-1.810 for the FRAP assay. On the other hand, the IC
values of phyto and mammalian lignans were determined in the ranges of 6.601-932.167 µg/mL for DPPH
scavenging and 13.007-27.829 µg/mL for ABTS
scavenging. In all of the used bioanalytical methods, phyto lignans, as secondary metabolites in plants, demonstrated considerably higher antioxidant activity compared to that of mammalian lignans. In addition, it was observed that enterodiol and enterolactone exhibited relatively weaker antioxidant activities when compared to phyto lignans or standard antioxidants, including butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), Trolox, and α-tocopherol.
Selective oxidation to synthesize nitriles is critical for feedstock manufacturing in the chemical industry. Current strategies typically involve substitutions of alkyl halides with toxic cyanides or ...the use of strong oxidation reagents (oxygen or peroxide) under ammoxidation/oxidation conditions, setting considerable challenges in energy efficiency, sustainability, and production safety. Herein, we demonstrate a facile, green, and safe electrocatalytic route for selective oxidation of amines to nitriles under ambient conditions, assisted by the anodic water oxidation on metal-doped α-Ni(OH)2 (a typical oxygen evolution reaction catalyst). By controlling the balance between co-adsorption of the amine molecule and hydroxyls on the catalyst surface, we demonstrate that Mn doping significantly promotes the subsequent chemical oxidation of amines, resulting in Faradaic efficiencies of 96% for nitriles under ≥99% conversion. This anodic oxidation is further coupled with cathodic hydrogen evolution for overall atomic economy and additional green energy production.
Most general anaesthetics and classical benzodiazepine drugs act through positive modulation of γ-aminobutyric acid type A (GABA
) receptors to dampen neuronal activity in the brain
. However, direct ...structural information on the mechanisms of general anaesthetics at their physiological receptor sites is lacking. Here we present cryo-electron microscopy structures of GABA
receptors bound to intravenous anaesthetics, benzodiazepines and inhibitory modulators. These structures were solved in a lipidic environment and are complemented by electrophysiology and molecular dynamics simulations. Structures of GABA
receptors in complex with the anaesthetics phenobarbital, etomidate and propofol reveal both distinct and common transmembrane binding sites, which are shared in part by the benzodiazepine drug diazepam. Structures in which GABA
receptors are bound by benzodiazepine-site ligands identify an additional membrane binding site for diazepam and suggest an allosteric mechanism for anaesthetic reversal by flumazenil. This study provides a foundation for understanding how pharmacologically diverse and clinically essential drugs act through overlapping and distinct mechanisms to potentiate inhibitory signalling in the brain.
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