Institute of Materials Science

Strongly luminescent CuInS 2 /ZnS core/shell nanocrystals were synthesized from copper iodide, indium acetate, zinc stearate, and dodecanethiol as starting compounds in octadecene solvent. The as-prepared core/shell nanocrystals exhibit a low size distribution (<10%), and present photoluminescence in the range of 550−815 nm with a maximum fluorescence quantum yield (QY) of 60%. Time-resolved fluorescence spectroscopy revealed that the lifetimes of the different spectral components are on the order of hundreds of nanoseconds, indicating that donor−acceptor pair recombinations are at the origin of the observed emission bands. The CuInS 2 /ZnS nanocrystals were subsequently transferred to the aqueous phase via surface ligand exchange with dihydrolipoic acid and used as fluorescent labels for in vivo imaging. After tail vein injection into nude mice, the biodistribution of the quantum dots was monitored during 24 h using fluorescence reflectance imaging.

A novel approach to effectively suppress the “polysulfide shuttle” in Li–S batteries is presented by designing a freestanding, three-dimensional graphene/1T MoS₂ (3DG/TM) heterostructure with highly efficient electrocatalysis properties for lithium polysulfides (LiPSs).

Lithium–sulfur (Li–S) batteries have been regarded as one of the most promising next-generation energy-storage devices, due to their low cost and high theoretical energy density (2600 W h kg⁻¹).

Colloidal graphene: Treatment of graphite powder with a series of certain aromatic solvents under sonication leads to the homologous set of colloidal dispersions containing solubilized graphenes (see image). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Since it was first discovered, thousands of years ago, silkworm silk has been known to be an abundant biopolymer with a vast range of attractive properties. The utilization of silk fibroin (SF), the main protein of silkworm silk, has not been limited to the textile industry but has been further extended to various high-tech application areas, including biomaterials for drug delivery systems and tissue engineering. The outstanding mechanical properties of SF, including its facile processability, superior biocompatibility, controllable biodegradation, and versatile functionalization have allowed its use for innovative applications. In this review, we describe the structure, composition, general properties, and structure-properties relationship of SF. In addition, the methods used for the fabrication and modification of various materials are briefly addressed. Lastly, recent applications of SF-based materials for small molecule drug delivery, biological drug delivery, gene therapy, wound healing, and bone regeneration are reviewed and our perspectives on future development of these favorable materials are also shared.

Stoichoimetric graphene fluoride monolayers are obtained in a single step by the liquid-phase exfoliation of graphite fluoride with sulfolane. Comparative quantum-mechanical calculations reveal that graphene fluoride is the most thermodynamically stable of five studied hypothetical graphene derivatives; graphane, graphene fluoride, bromide, chloride, and iodide. The graphene fluoride is transformed into graphene via graphene iodide, a spontaneously decomposing intermediate. The calculated bandgaps of graphene halides vary from zero for graphene bromide to 3.1 eV for graphene fluoride. It is possible to design the electronic properties of such two-dimensional crystals.

This Special Report presents a description of Geant4-DNA user applications dedicated to the simulation of track structures (TS) in liquid water and associated physical quantities (e.g., range, stopping power, mean free path…). These example applications are included in the Geant4 Monte Carlo toolkit and are available in open access. Each application is described and comparisons to recent international recommendations are shown (e.g., ICRU, MIRD), when available. The influence of physics models available in Geant4-DNA for the simulation of electron interactions in liquid water is discussed. Thanks to these applications, the authors show that the most recent sets of physics models available in Geant4-DNA (the so-called "option4" and "option 6" sets) enable more accurate simulation of stopping powers, dose point kernels, and W-values in liquid water, than the default set of models ("option 2") initially provided in Geant4-DNA. They also serve as reference applications for Geant4-DNA users interested in TS simulations.

We report on the temperature dependence of the quasiparticle density of states in the simple binary compound MgB(2) directly measured using scanning tunneling microscope (STM). To achieve high quality tunneling conditions, a small crystal of MgB(2) is used as a tip in the STM experiment. The "sample" is chosen to be a 2H- NbSe(2) single crystal presenting an atomically flat surface. At low temperature the tunneling conductance spectra show a gap at the Fermi energy followed by two well-pronounced conductance peaks on each side. They appear at voltages V(S) approximately +/-3.8 mV and V(L) approximately +/-7.8 mV. With rising temperature both peaks disappear at the T(C) of the bulk MgB(2), a behavior consistent with the model of two-gap superconductivity. The possibility of a particular proximity effect is also discussed.

Carbon-based sunlight absorbers in solar-driven steam generation have recently attracted much attention due to the possibility of huge applications of low-cost steam for medical sterilization or sanitization, seawater desalination, chemical distillation, and water purification. In this minireview, recent developments in carbon-based sunlight absorbers in solar-driven steam generation systems are reviewed, including graphene, graphite, carbon nanotubes, other carbon materials, and carbon-based composite materials, highlighting important contributions worldwide that promise low-cost, efficient, robust, reusable, chemically stable, and excellent broadband solar absorption. Furthermore, the crucial challenges associated with employing carbon materials in this field are emphasized.

Dc magnetization, ac susceptibility, and zero-field-cooled relaxation measurements are carried out for a cluster glass compound of ${\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5}{\mathrm{CoO}}_{3}.$ The temperature dependence of the magnetic properties could be distinguished into two regimes: a high-temperature regime with the time-independent parameters originating probably from the intracluster ferromagnetism, and a lower-temperature regime where the freezing of clusters takes place with a considerabe frequency dependence of a shoulder in ${\ensuremath{\chi}}^{\ensuremath{'}}(T)$ and a hump in ${\ensuremath{\chi}}^{\ensuremath{''}}(T).$ The cusp in ${M}_{\mathrm{ZFC}}(T)$ at ${T}_{a},$ as well as the high-temperature maximum in ${\ensuremath{\chi}}^{\ensuremath{'}}(T)$ are discussed in terms of an existence of the local anisotropy inside the clusters. The high-temperature maximum in ${\ensuremath{\chi}}^{\ensuremath{''}}(T)$ is interpreted in connection to the reversibility temperature, ${T}_{r}.$ Empirically, we found ${T}_{r}\ensuremath{\propto}\ensuremath{-}H$ while ${T}_{a}\ensuremath{\propto}\ensuremath{-}{H}^{0.58}.$ We report also the long-time relaxation and the ageing phenomenon in this compound. The ageing effect is much more pronounced in the ferromagnetic state than in the cluster glass state and the system does not reach equilibrium for time scales up to ${10}^{4} \mathrm{s}.$ The relaxation and ageing effects are attributed to the cluster growth slowed down by the presence of the frustration.

The advent of a Li⁺ or Na⁺ glass electrolyte with a cation conductivity <italic>σ</italic>_i &gt; 10⁻² S cm⁻¹ at 25 °C and a motional enthalpy Δ<italic>H</italic>_m = 0.06 eV that is wet by a metallic lithium or sodium anode is used to develop a new strategy for an all-solid-state, rechargeable, metal-plating battery.

The alterations in the microvascular system of diabetes mellitus patients are responsible for the most devastating complications of this widespread disease. In the kidney, the microangiopathy leads to thickening of the glomerular capillary basement membrane but also to the expansion of the mesangial matrix and thickening of the tubular basement membrane. Several mechanisms are implicated in the pathogenesis of diabetic renal microangiopathy. These include increased synthesis of type IV collagen following hyperglycaemia-induced alteration of the pattern of podocyte-integrin expression, decreased expression of matrix metalloproteinases (MMP-2 and 3), and increased expression of tissue inhibitor of metalloproteinase (TIMP). An altered morphology of podocytes accompanies these basement membrane alterations. Other factors which may contribute to renal matrix accumulation include vascular endothelial growth factor (VEGF), since treatment with anti-VEGF antibodies attenuates glomerular basement membrane thickening, platelet-derived growth factor (PDGF) (B chain) and its receptor, which appear to be highly expressed in mesangial and visceral epithelial cells and might play a role in the development of diabetic nephropathy. Also oxygen radicals/oxidative stress may play a role in matrix accumulation in diabetic nephropathy as aminoguanidine, an inhibitor of the formation of advanced glycation end-products but with antioxidant properties, attenuates diabetic nephropathy. Retinal diabetic microangiopathy follows much the same principles, be it that microvascular proliferation is a distinctive element in the retina. Nephropathy and retinopathy occur frequently but not always together, indicating that in their multifactorial pathogenesis much remains to be clarified.

Metal–organic framework precursors were employed to fabricate single-atom catalysts, where Fe implanted nitrogen-doped carbon (Fe₁-N-C) exhibits excellent performance for electrocatalytic nitrogen reduction in acidic media.

This tutorial review explains the emerging understanding of the surface and bulk chemistry - electrochemical performance relations in anode supports (aka secondary current collectors, substrates, templates, hosts) for lithium, sodium and potassium metal batteries (LMBs, SMBs or NMBs, and KMBs or PMBs). In relation to each section, the possible future research directions that may yield both new insight and improved cycling behavior are explored. Representative case studies from Li, Na and K metal anode literature are discussed. The tutorial starts with an overview of the solid electrolyte interphase (SEI), covering both the "classic" understanding of the SEI structure and the "modern" insights obtained by site-specific cryogenic stage TEM analysis. Next, the multiple roles of supports in promoting cycling stability are detailed. Without an optimized support architecture, the metal-electrolyte interface becomes geometrically unstable at a lower current density and cycle number. Taking into consideration the available literature on LMBs, SMBs and KMBs, it is concluded that effective architectures are geometrically complex and electrochemically lithiophilic, sodiophilic or potassiophilic, so as to promote conformal electrochemical wetting of the metal during plating/stripping. One way that philicity is achieved is through support oxygen surface chemistry, which yields a reversibly reactive metal-support interface. Examples of this include the well-known oxygen-carbon moieties in reduced graphene oxide (rGO), as well as classic ion battery reversible conversion reaction oxides such as SnO2. Unreactive surfaces lead to dewetted island growth of the metal, which is a precursor to dendrites, and possibly to non-uniform dissolution. Surveying the literature on various Li, Na and K metal supports, it is concluded that the key bulk thermodynamic property that will predict electrochemical wetting behavior is the enthalpy of infinite solution (ΔsolH∞) of the metal (solute) into the support (solvent). Large and negative ΔsolH∞ promotes uniform metal wetting on the support surface, corresponding to relatively low plating overpotential. Positive ΔsolH∞ promotes dewetted islands and a relatively high overpotential. This simple rule explains a broad range of studies on Li, Na and K metal - support interactions, including the previously reported correlation between mutual solubility and wetting.

Abstract The molecular weight and molecular weight distribution of a polymer can markedly affect its mechanical properties. While this has been recognized for a long time, quantitative studies have been relatively difficult to perform for a number of reasons. A major problem has been the characterization of the complete molecular weight distribution curve by fractionation methods because fraction collection and the determination of the various molecular weight averages of polymers is time consuming. Additionally, measurement of the number-average molecular weight, [Mbar]n, by classical osmometry procedure is often unreliable.

Common toxicity patterns emerge across toxicity tests with species from different trophic levels.

In this work, we construct an ultrathin graphene/GaS heterostructure and investigate its electronic properties as well as the effect of vertical strain using density functional theory. The calculated results of the equilibrium interlayer spacing (3.356 Å) and the binding energy show that the intrinsic properties of isolated graphene and GaS monolayers can be preserved and the weak van der Waals interactions are dominated in the heterostructures. The van der Waals heterostructure (vdWH) forms an n-type Schottky contact with a small Schottky barrier height of 0.51 eV. This small Schottky barrier height can also be tuned by applying vertical strain. Furthermore, we find that the n-type Schottky contact of the vdWH can be changed to p-type when the interlayer spacing is decreased and exceeded to 2.60 Å. These findings show the great potential application of the graphene/GaS vdWH for designing next generation devices.

An ultrafast technique for chemical insertion of Zn ions is demonstrated with an open-tunnel oxide host, and the Zn-inserted oxide serves as an excellent insertion anode for both aqueous and non-aqueous Zn-based batteries.

Titanium dioxide (TiO2) has attracted increasing attention as a candidate for the photocatalytic reduction of carbon dioxide (CO2) to convert anthropogenic CO2 gas into fuels combined with storage of intermittent and renewable solar energy in forms of chemical bonds for closing the carbon cycle. However, pristine TiO2 possesses a large band gap (3.2 eV), fast recombination of electrons and holes, and low selectivity for the photoreduction of CO2. Recently, considerable progress has been made in the improvement of the performance of TiO2 photocatalysts for CO2 reduction. In this review, we first discuss the fundamentals of and challenges in CO2 photoreduction on TiO2-based catalysts. Next, the recently emerging progress and advances in TiO2 nanostructured and hybrid materials for overcoming the mentioned obstacles to achieve high light-harvesting capability, improved adsorption and activation of CO2, excellent photocatalytic activity, the ability to impede the recombination of electrons-holes pairs, and efficient suppression of hydrogen evolution are discussed. In addition, approaches and strategies for improvements in TiO2-based photocatalysts and their working mechanisms are thoroughly summarized and analyzed. Lastly, the current challenges and prospects of CO2 photocatalytic reactions on TiO2-based catalysts are also presented.

Abstract Recently, we have developed a novel family of functionalized nanostructures that exhibit liquid‐like behavior in the absence of solvents and preserve their nanostructure in the liquid state. The gallery of nanostructures developed so far includes functionalized silica and magnetic iron oxide nanoparticles, layer‐like organosilicate nanoparticles, polyoxometalate clusters, and organic–inorganic hybrid networks. In an effort to demonstrate the wider applicability of this concept and to provide a deeper insight into this class of materials, the present work cites additional paradigms of functionalized nanostructures with similar behavior as above. In one case, surface functionalization of anatase nanoparticles (TiO 2 , an inorganic nanostructure) with a quaternary ammonium organosilane leads to ionically modified nanoparticles that, when electrostatically combined with a poly(ethylene glycol) (PEG)‐tailed sulfonate anion, exhibit liquid‐like behavior in the absence of solvents. In a different but quite interesting case of a bionanostructure, ion‐exchange functionalization of a DNA oligonucleotide with a PEG‐tailed quaternary ammonium cation leads to an easily separable liquid derivative with attractive features. These examples show the versatility of this concept over a range of nanostructures.