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We report the effect of hydrogen on the crystallization process of silicon nanocrystals embedded in a silicon oxide matrix. We show that hydrogen gas during annealing leads to a lower sub-band gap absorption, indicating passivation of defects created during annealing. Samples annealed in pure nitrogen show expected trends according to crystallization theory. Samples annealed in forming gas, however, deviate from this trend. Their crystallinity decreases for increased annealing time. Furthermore, we observe a decrease in the mean nanocrystal size and the size distribution broadens, indicating that hydrogen causes a size reduction of the silicon nanocrystals. [ABSTRACT FROM AUTHOR]

A high resistance nanogap platform was used to trap and electrically characterize 30 nm thiolated double-stranded DNA molecules. High resolution scanning electron microscopy was also used to image the trapped DNA strands. It was found that the surface state of the electrodes and underlying substrate could influence the measurements of trapped molecules when the measured resistances were on the order of TO or greater. Hydrophilic surfaces gave rise to larger leakage currents that could potentially mask the underlying signals from molecules positioned in the nanogap. Finally, the careful handling of the samples and control of the environment is essential to avoid surface charging of the oxide substrate layer as these parasitic charges affect electrical measurements of the nanogap. The presented results thus outline some important considerations when making low-conductance measurements on molecules and should prove useful for the characterization of molecules in molecular electronics or sensors employing nanogap platforms. [ABSTRACT FROM AUTHOR]

Transport measurements have revealed several exotic electronic properties of graphene. The possibility to influence the electronic structure and hence control the conductivity by adsorption or doping with adatoms is crucial in view of electronics applications. Here, we show that in contrast to expectation, the conductivity of graphene increases with increasing concentration of vacancy defects, by more than one order of magnitude. We obtain a pronounced enhancement of the conductivity after insertion of defects by both quantum mechanical transport calculations as well as experimental studies of carbon nano-sheets. Our finding is attributed to the defect induced mid-gap states, which create a region exhibiting metallic behaviour around the vacancy defects. The modification of the conductivity of graphene by the implementation of stable defects is crucial for the creation of electronic junctions in graphene-based electronics devices. [ABSTRACT FROM AUTHOR]

Nanoelectrodes were fabricated combining photolithography, electron beam lithography and focused ion beam milling allowing for large scale integration and nanoengineering of the electrode properties. The structure determination by transmission and scanning electron microscopy showed a highly reproducible gap width. The atomic scale electrode structure was characterized using scanning and transmission electron microscopy. The nanogap resistances were found to be the highest hitherto reported for nanogaps, namely in the 300-1300 TO range. Gold nanoparticles were trapped by ac dielectrophoresis, and the electrodes were shown to be stable enough to endure empty gap voltages as high as 5 V as well as currents high enough to induce fusing of trapped nanoparticles. [ABSTRACT FROM AUTHOR]

The need to acquire multiple angle-resolved electron energy loss spectra (EELS) is one of the several critical challenges associated with electron magnetic circular dichroism (EMCD) experiments. If the experiments are performed by scanning a nanometer to atomic-sized electron probe on a specific region of a sample, the precision of the local magnetic information extracted from such data highly depends on the accuracy of the spatial registration between multiple scans. For an EMCD experiment in a 3-beam orientation, this means that the same specimen area must be scanned four times while keeping all the experimental conditions same. This is a non-trivial task as there is a high chance of morphological and chemical modification as well as non-systematic local orientation variations of the crystal between the different scans due to beam damage, contamination and spatial drift. In this work, we employ a custom-made quadruple aperture to acquire the four EELS spectra needed for the EMCD analysis in a single electron beam scan, thus removing the above-mentioned complexities. We demonstrate a quantitative EMCD result for a beam convergence angle corresponding to sub-nm probe size and compare the EMCD results for different detector geometries., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Polymer-assisted wet transfer of chemical vapor deposited (CVD) graphene has achieved great success towards the true potential for large-scale electronic applications, while the lack of an efficient polymer removal method has been regarded as a crucial factor for realizing high carrier mobility in graphene devices. Hereby, we report an efficient and facile method to clean polymer residues on graphene surface by merely employing solvent mixture of isopropanol (IPA) and water (H 2 O). Raman spectroscopy shows an intact crystal structure of graphene after treatment, and the x-ray photoelectron spectroscopy indicates a significant decrease in the C-O and C=O bond signals, which is mainly attributed to the removal of polymer residues and further confirmed by subsequent atomic force microscopy analysis. More importantly, our gated measurements demonstrate that the proposed approach has resulted in a 3-fold increase of the carrier mobility in CVD graphene with the electron mobility close to 10 000 cm 2 V -1 S -1 , corresponding to an electron mean free path beyond 100 nm. This intrigues the promising application for this novel method in achieving ballistic transport for CVD graphene devices., (Creative Commons Attribution license.)

Molecular electronic devices based on few and single-molecules have the advantage that the electronic signature of the device is directly dependent on the electronic structure of the molecules as well as of the electrode-molecule junction. In this work, we use a two-step approach to synthesise functionalized nanomolecular electronic devices (nanoMoED). In first step we apply an organic solvent-based gold nanoparticle (AuNP) synthesis method to form either a 1-dodecanethiol or a mixed 1-dodecanethiol/ ω -tetraphenyl ether substituted 1-dodecanethiol ligand shell. The functionalization of these AuNPs is tuned in a second step by a ligand functionalization process where biphenyldithiol (BPDT) molecules are introduced as bridging ligands into the shell of the AuNPs. From subsequent structural analysis and electrical measurements, we could observe a successful molecular functionalization in nanoMoED devices as well as we could deduce that differences in electrical properties between two different device types are related to the differences in the molecular functionalization process for the two different AuNPs synthesized in first step. The same devices yielded successful NO 2 gas sensing. This opens the pathway for a simplified synthesis/fabrication of molecular electronic devices with application potential., (Creative Commons Attribution license.)

The aging in air inevitably results in the accumulation of airborne hydrocarbon contaminations on a graphene surface, which causes considerable difficulties in the subsequent application of graphene. Herein, we report an electron-beam-activated fluorination/defluorination cycle for achieving a long-term preservation of CVD graphene. After experiencing such cycle, the accumulation of airborne hydrocarbon on the graphene surfaces is strongly reduced, and the initial chemical status of graphene can be restored, which is confirmed by employing atomic force microscopy and X-ray photoelectron microscopy. Our reported approach provides an efficient method for the cleaning and long-term preservation of graphene, and it is particularly useful for graphene microscopy characterizations.

Precipitation is one of the most common processes to synthesize hydroxyapatite, which is the human body's mineral forming bone and teeth, and the golden bioceramic material for bone repair. Generally, the washing step is important in the precipitation method to remove the residuals in solution and to stabilize the phase transformation. However, the influence of residuals in combination with the reaction temperature and time, on calcium phosphate formation, is not well studied. This could help us with a better understanding of the typical synthesis process. We used a fixed starting ion concentration and pH in our study and did not adjust it during the reaction. XRD, FTIR, ICP-OES, and SEM have been used to analyze the samples. The results showed that combining residuals with both reaction temperature and time can significantly influence calcium phosphate formation and transformation. Dicalcium phosphate dihydrate formation and transformation are sensitive to temperature. Increasing temperature (60 °C) can inhibit the formation of acidic calcium phosphate or transform it to other phases, and further the particle size. It was also observed that high reaction temperature (60 °C) results in higher precipitation efficiency than room temperature. A low ion concentration combining reaction temperature and time could still significantly influence the calcium phosphate transformation during the drying.

The lack of a sizeable band gap has so far prevented graphene from building effective electronic and optoelectronic devices despite its numerous exceptional properties. Intensive theoretical research reveals that a band gap larger than 1 eV can only be achieved in sub-3 nm wide graphene nanoribbons (GNRs), but real fabrication of such ultranarrow GNRs still remains a critical challenge. Herein, we demonstrate an approach for the synthesis of ultranarrow and photoluminescent semiconducting GNRs by longitudinally unzipping single-walled carbon nanotubes. Atomic force microscopy reveals the unzipping process, and the resulting 2.2 nm wide GNRs are found to emit strong and sharp photoluminescence at ∼685 nm, demonstrating a very desirable semiconducting nature. This band gap of 1.8 eV is further confirmed by follow-up photoconductivity measurements, where a considerable photocurrent is generated, as the excitation wavelength becomes shorter than 700 nm. More importantly, our fabricated GNR field-effect transistors (FETs), by employing the hexagonal boron nitride-encapsulated heterostructure to achieve edge-bonded contacts, demonstrate a high current on/off ratio beyond 10 5 and carrier mobility of 840 cm 2 /V s, approaching the theoretical scattering limit in semiconducting GNRs at room temperature. Especially, highly aligned GNR bundles with lengths up to a millimeter are also achieved by prepatterning a template, and the fabricated GNR bundle FETs show a high on/off ratio reaching 10 5 , well-defined saturation currents, and strong light-emitting properties. Therefore, GNRs produced by this method open a door for promising applications in graphene-based electronics and optoelectronics.

Hybrid lead halide perovskites have reached comparable efficiencies to state-of-the-art silicon solar cell technologies. However, a remaining key challenge toward commercialization is the resolution of the perovskite device instability. In this work, we identify for the first time the mobile nature of bis(trifluoromethanesulfonyl)imide (TFSI - ), a typical anion extensively employed in p-type dopants for 2,2'7,7'-tetrakis( N , N -di- p -methoxyphenylamine)-9,9'spirofluorene (spiro-OMeTAD). We demonstrate that TFSI - can migrate through the perovskite layer via the grain boundaries and accumulate at the perovskite/electron-transporting layer (ETL) interface. Our findings reveal that the migration of TFSI - enhances the device performance and stability, resulting in highly stable p-i-n cells that retain 90% of their initial performance after 1600 h of continuous testing. Our systematic study, which targeted the effect of the nature of the dopant and its concentration, also shows that TFSI - acts as a dynamic defect-healing agent, which self-passivates the perovskite crystal defects during the migration process and thereby decreases nonradiative recombination pathways.

Graphene has stimulated great enthusiasm in a variety of fields, while its chemically inert surface still remains challenging for functionalization towards various applications. Herein, we report an approach to fabricate non-covalently functionalized graphene by employing π-π stacking interactions, which has potentialities for enhanced ammonia detection. 5,5'-Di(4-biphenylyl)-2,2'-bithiophene (BP2T) molecules are used in our work for the non-covalent functionalization through strong π-π interactions of aromatic structures with graphene, and systematic investigations by employing various spectroscopic and microscopic characterization methods confirm the successful non-covalent attachment of the BP2T on the top of graphene. From our gas sensing experiments, the BP2T functionalized graphene is promising for ammonia sensing with a 3-fold higher sensitivity comparing to that of the pristine graphene, which is mainly attributed to the enhanced binding energy between the ammonia and BP2T molecules derived by employing the Langmuir isotherm model. This work provides essential evidence of the π-π stacking interactions between graphene and aromatic molecules, and the reported approach also has the potential to be widely employed in a variety of graphene functionalizations for chemical detection., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We investigate the magnetic properties of amorphous Sm 10 Co 90 /Co 60 (Al 70 Zr 30 ) 40 /Co 85 (Al 70 Zr 30 ) 15 exchange-spring magnet trilayers. The magnetically soft Co 85 (Al 70 Zr 30 ) 15 layer is coupled to the magnetically hard Sm 10 Co 90 layer through the weakly magnetic low- T c Co 60 (Al 70 Zr 30 ) 40 spacer layer. The strength of the coupling can be controlled with temperature and the coupling persists above the intrinsic T c of the spacer layer due to a long-range magnetic proximity effect. Polarized neutron reflectivity is used to examine the magnetic profile of the trilayers during magnetization reversal. A two-step switching occurs, with the switching angle of the soft layer strongly dependent on the strength of the coupling. In the strong coupling regime a magnetic state can be achieved where the soft layer magnetization is perpendicular to the hard layer whereas in the weak coupling regime the soft layer reverses fully., (© 2021 IOP Publishing Ltd.)

Graphdiyne oxide (GDYO) is a carbon-based nanomaterial possessing sp 2 and sp-hybridized carbon atoms with many promising applications. However, its biocompatibility and potential biodegradability remain poorly understood. Using human primary monocyte-derived macrophages as a model we show here that GDYO elicited little or no cytotoxicity toward classically activated (M1) and alternatively activated (M2) macrophages. Moreover, GDYO reprogrammed M2 macrophages towards M1 macrophages, as evidenced by the elevation of specific cell surface markers and cytokines and the induction of NOS2 expression. We could also show inducible nitric oxide synthase (iNOS)-dependent biodegradation of GDYO in M1 macrophages, and this was corroborated in an acellular system using the peroxynitrite donor, SIN-1. Furthermore, GDYO elicited the production of pro-inflammatory cytokines in a biodegradation-dependent manner. Our findings shed new light on the reciprocal interactions between GDYO and human macrophages. This is relevant for biomedical applications of GDYO such as the re-education of tumor-associated macrophages or TAMs.

The rear interface of kesterite absorbers with Mo back contact represents one of the possible sources of nonradiative voltage losses (Δ V oc,nrad ) because of the reported decomposition reactions, an uncontrolled growth of MoSe 2 , or a nonoptimal electrical contact with high recombination. Several intermediate layers (IL), such as MoO 3 , TiN, and ZnO, have been tested to mitigate these issues, and efficiency improvements have been reported. However, the introduction of IL also triggers other effects such as changes in alkali diffusion, altered morphology, and modifications in the absorber composition, all factors that can also influence Δ V oc,nrad . In this study, the different effects are decoupled by designing a special sample that directly compares four rear structures (SLG, SLG/Mo, SLG/Al 2 O 3 , and SLG/Mo/Al 2 O 3 ) with a Na-doped kesterite absorber optimized for a device efficiency >10%. The IL of choice is Al 2 O 3 because of its reported beneficial effect to reduce the surface recombination velocity at the rear interface of solar cell absorbers. Identical annealing conditions and alkali distribution in the kesterite absorber are preserved, as measured by time-of-flight secondary ion mass spectrometry and energy-dispersive X-ray spectroscopy. The lowest Δ V oc,nrad of 290 mV is measured for kesterite grown on Mo, whereas the kesterite absorber on Al 2 O 3 exhibits higher nonradiative losses up to 350 mV. The anticipated field-effect passivation from Al 2 O 3 at the rear interface could not be observed for the kesterite absorbers prepared by the two-step process, further confirmed by an additional experiment with air annealing. Our results suggest that Mo with an in situ formed MoSe 2 remains a suitable back contact for high-efficiency kesterite devices.

When magnetic properties are analysed in a transmission electron microscope using the technique of electron magnetic circular dichroism (EMCD), one of the critical parameters is the sample orientation. Since small orientation changes can have a strong impact on the measurement of the EMCD signal and such measurements need two separate measurements of conjugate EELS spectra, it is experimentally non-trivial to measure the EMCD signal as a function of sample orientation. Here, we have developed a methodology to simultaneously map the quantitative EMCD signals and the local orientation of the crystal. We analyse, both experimentally and by simulations, how the measured magnetic signals evolve with a change in the crystal tilt. Based on this analysis, we establish an accurate relationship between the crystal orientations and the EMCD signals. Our results demonstrate that a small variation in crystal tilt can significantly alter the strength of the EMCD signal. From an optimisation of the crystal orientation, we obtain quantitative EMCD measurements.

The strength of the interlayer exchange coupling in [Fe/MgO][Formula: see text](001) superlattices with 2 ≤ N ≤ 10 depends on the number of bilayer repeats (N). The exchange coupling is antiferromagnetic for all the investigated thicknesses while being nine times larger in a sample with N = 4 as compared to N = 2. The sequence of the magnetic switching in two of the samples (N = 4, N = 8) is determined using polarized neutron reflectometry. The outermost layers are shown to respond at the lowest fields, consistent with having the weakest interlayer exchange coupling. The results are consistent with the existence of quantum well states defined by the thickness of the Fe and the MgO layers as well as the number of repeats (N) in [Fe/MgO][Formula: see text](001)superlattices.

Understanding the biological fate of graphene-based materials such as graphene oxide (GO) is crucial to assess adverse effects following intentional or inadvertent exposure. Here we provide first evidence of biodegradation of GO in the gastrointestinal tract using zebrafish as a model. Raman mapping was deployed to assess biodegradation. The degradation was blocked upon knockdown of nos2a encoding the inducible nitric oxide synthase (iNOS) or by pharmacological inhibition of NOS using l-NAME, demonstrating that the process was nitric oxide (NO)-dependent. NO-dependent degradation of GO was further confirmed in vitro by combining a superoxide-generating system, xanthine/xanthine oxidase (X/XO), with an NO donor (PAPA NONOate), or by simultaneously producing superoxide and NO by decomposition of SIN-1. Finally, by using the transgenic strain Tg(mpx:eGFP) to visualize the movement of neutrophils, we could show that inhibition of the degradation of GO resulted in increased neutrophil infiltration into the gastrointestinal tract, indicative of inflammation.

The implementation of electronics applications based on molecular electronics devices is hampered by the difficulty of placing a single or a few molecules with application-specific electronic properties in between metallic nanocontacts. Here, we present a novel method to fabricate 20 nm sized nanomolecular electronic devices (nanoMoED) using a molecular place-exchange process of nonconductive short alkyl thiolates with various short chain conductive oligomers. After the successful place-exchange with short-chain conjugated oligomers in the nanoMoED devices, a change in device resistance of up to four orders of magnitude for 4,4'-biphenyldithiol (BPDT), and up to three orders of magnitude for oligo phenylene-ethynylene (OPE), were observed. The place-exchange process in nanoMoEDs are verified by measuring changes in device resistance during repetitive place-exchange processes between conductive and nonconductive molecules and surface-enhanced Raman spectroscopy. This opens vast possibilities for the fabrication and application of nanoMoED devices with a large variety of molecules.

Charge transfer dynamics are of importance in functional materials used in devices ranging from transistors to photovoltaics. The understanding of charge transfer in particular of how fast electrons tunnel away from an excited state and where they end up, is necessary to tailor materials used in devices. We have investigated charge transfer dynamics in different forms of the layered two-dimensional material molybdenum disulphide (MoS2, in single crystal, nanocrystalline particles and crystallites in a reduced graphene oxide network) using core-hole clock spectroscopy. By recording the electrons in the sulphur KLL Auger electron kinetic energy range we have measured the prevalence of localised and delocalised decays from a state created by core excitation using X-rays. We show that breaking the crystal symmetry of the single crystal into either particles or sheets causes the charge transfer from the excited state to occur faster, even more so when incorporating it in a graphene oxide network. The interface between the MoS2 and the reduced graphene oxide forms a Schottky barrier which changes the ratio between local and delocalised decays creating two distinct regions in the charge transfer dependent on the energy of the excited electron. Thereby we show that ultra-fast charge transfer in MoS2 can be tailored, a result which can be used in the design of emergent devices.

The paper [Prasongkit et al. , RSC Adv. , 2016, 64 , 59299] by Prasongkit and Rocha calculates the binding energy of gas molecules attached to 1-8-biphenyl-dithiol (BPDT) molecules. We find from our calculations, that the binding energies calculated for the NO 2 molecules are too low, most likely due to lacking optimization of the site at which the gas molecule binds to the BPDT. Though not shown explicitly here, the same statement might apply to the other gas molecules used in this paper., Competing Interests: The group of K. Leifer working in Electron Microscopy and Nano-Engineering at Uppsala University, Sweden, has carried out gas sensor measurements since 2009 starting with measurements on graphene.5 On the background of the gas sensing work on graphene, Leifer proposed in 2011 to build a nanoMoED (nanomolecular electronics) device functionalized with BPDT and try to carry out gas sensing experiments with environmental gases. This idea was nourished by the interdisciplinary centre at Uppsala University, U3MEC (Uppsala University Unimolecular Electronics Centre). After successful initial results, in 2013, we gathered again with the colleagues from theory to discuss possible DFT calculations of the gas sensing effects in uni-molecular devices. At this time, J. Prasongkit was a guest researcher at Uppsala University and our theory colleagues invited her to the meetings., (This journal is © The Royal Society of Chemistry.)

Molecules have high potential for novel applications as building blocks for electronic devices such as sensors due to the versatility of their electronic properties. Their use in devices offers a great potential for further miniaturization of electronic devices. We describe a method where nanoparticles functionalized with short-chain organic molecules are used to build a molecular electronics device (nanoMoED) sensor for studying electrical properties of organic molecules. We also report the application of such a nanoMoED for detecting environmental gases. Here we provide a detailed description of the nanoMoED fabrication process, nanoparticle synthesis and functionalization, the basics of the electrical measurements, and nanoMoED applications. The platform described here is capable of detecting electrical current flowing through just a few molecules. The versatility of such nanoMoEDs makes this platform suitable for a wide range of molecular electronics and molecular sensing applications.

Ceramic coatings may be applied onto metallic components of joint replacements for improved wear and corrosion resistance as well as enhanced biocompatibility, especially for metal-sensitive patients. Silicon nitride (SiN x ) coatings have recently been developed for this purpose. To achieve a high coating density, necessary to secure a long-term performance, is however challenging, especially for sputter deposited SiN x coatings, since these coatings are insulating. This study investigates the time-dependent performance of sputter-deposited SiN x based coatings for joint applications. SiN x coatings with a thickness in the range of 4.3-6.0 µm were deposited by reactive high power impulse magnetron sputtering onto flat discs as well as hip heads made of CoCrMo. SiN x compositional analysis by X-ray photoelectron spectroscopy showed N/Si ratios between 0.8 and 1.0. Immersion of the flat disks in fetal bovine serum solution over time as well as short-term wear tests against ultra-high molecular weight polyethylene (UHMWPE) discs showed that a high coating density is required to inhibit tribocorrosion. Coatings that performed best in terms of chemical stability were deposited using a higher target power and process heating.

Expression of the Alzheimer's disease associated polypeptide Aβ42 and the human polypeptide hormon islet amyloid polypeptide (hIAPP) and the prohormone precursor (hproIAPP) in neurons of Drosophila melanogaster leads to the formation of protein aggregates in the fat body tissue surrounding the brain. We determined the structure of these membrane-encircled protein aggregates using transmission electron microscopy (TEM) and observed the dissolution of protein aggregates after starvation. Electron tomography (ET) as an extension of transmission electron microscopy revealed that these aggregates were comprised of granular subunits having a diameter of 20 nm aligned into highly ordered structures in all three dimensions. The three dimensional (3D) lattice of hIAPP granules were constructed of two unit cells, a body centered tetragonal (BCT) and a triclinic unit cell. A 5-fold twinned structure was observed consisting of the cyclic twinning of the BCT and triclinic unit cells. The interaction between the two nearest hIAPP granules in both unit cells is not only governed by the van der Waals forces and the dipole-dipole interaction but potentially also by filament-like structures that can connect the nearest neighbors. Hence, our 3D structural analysis provides novel insight into the aggregation process of hIAPP in the fat body tissue of Drosophila melanogaster., Competing Interests: The authors have declared that no competing interests exist.

To increase the energy storage density of lithium-ion batteries, silicon anodes have been explored due to their high capacity. One of the main challenges for silicon anodes are large volume variations during the lithiation processes. Recently, several high-performance schemes have been demonstrated with increased life cycles utilizing nanomaterials such as nanoparticles, nanowires, and thin films. However, a method that allows the large-scale production of silicon anodes remains to be demonstrated. Herein, we address this question by suggesting new scalable nanomaterial-based anodes. Si nanoparticles were grown on nanographite flakes by aerogel fabrication route from Si powder and nanographite mixture using polyvinyl alcohol (PVA). This silicon-nanographite aerogel electrode has stable specific capacity even at high current rates and exhibit good cyclic stability. The specific capacity is 455 mAh g -1 for 200 th cycles with a coulombic efficiency of 97% at a current density 100 mA g -1 .

Hydrogen peroxide (H 2 O 2 ) quantification in biomedicine is valuable as inflammation biomarker but also in assays employing enzymes that generate or consume H 2 O 2 linked to a specific biomarker. Optical H 2 O 2 detection is typically performed through peroxidase-coupled reactions utilizing organic dyes that suffer, however, from poor stability/reproducibility and also cannot be employed in situ in dynamic complex cell cultures to monitor H 2 O 2 levels in real-time. Here, we utilize enzyme-mimetic CeO 2 nanocrystals that are sensitive to H 2 O 2 and study the effect of H 2 O 2 presence on their electronic and luminescent properties. We produce and dope with Eu 3+ these particles in a single-step by flame synthesis and directly deposit them on Si and glass substrates to fabricate nanoparticle layers to monitor in real-time and in situ the H 2 O 2 concentrations generated by Streptococcus pneumoniae clinical isolates. Furthermore, the small CeO 2 :Eu 3+ nanocrystals are combined in a single-step with larger, non-responsive Y 2 O 3 :Tb 3+ nanoparticles during their double-nozzle flame synthesis to engineer hybrid luminescent nanoaggregates as ratiometric robust biosensors. We demonstrate the functionality of these biosensors by monitoring their response in the presence of a broad range of H 2 O 2 concentrations in vitro from S. pneumoniae, highlighting their potential for facile real-time H 2 O 2 detection in vitro in cell cultures., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The interaction of a gas molecule with a sensing material causes the highest change in the electronic structure of the latter, when this material consists of only a few atoms. If the sensing material consists of a short, conductive molecule, the sensing action can be furthermore probed by connecting such molecules to nanoelectrodes. Here, we report that NO2 molecules that adhere to 4,4'-biphenyldithiol (BPDT) bound to Au surfaces lead to a change of the electrical transmission of the BPDT. The related device shows reproducible, stable measurements and is so far the smallest (<20 nm) gas sensor. It demonstrates modulation of charge transport through molecules upon exposure to nitrogen dioxide down to concentrations of 55 ppb. We have evaluated several devices and exposure conditions and obtained a close to linear dependence of the sensor response on the gas concentration.

DNA technology based bio-responsive nanomaterials have been widely studied as promising tools for biomedical applications. Gold nanoparticles (AuNPs) and graphene oxide (GO) sheets are representative zero- and two-dimensional nanomaterials that have long been combined with DNA technology for point-of-care diagnostics. Herein, a cascade amplification system based on duplex-specific nuclease (DSN)-assisted target recycling and electrocatalytic water-splitting is demonstrated for the detection of microRNA. Target microRNAs can form DNA: RNA heteroduplexes with DNA probes on the surface of AuNPs, which can be hydrolyzed by DSN. MicroRNAs are preserved during the reaction and released into the suspension for the digestion of multiple DNA probes. After the DSN-based reaction, AuNPs are collected and mixed with GO to form AuNP/GO nanocomposite on an electrode for the following electrocatalytic amplification. The utilization of AuNP/GO nanocomposite offers large surface area, exceptional affinity to water molecules, and facilitated mass diffusion for the water-splitting reaction. For let-7b detection, the proposed biosensor achieved a limit detection of 1.5 fM in 80 min with a linear detection range of approximately four orders of magnitude. Moreover, it has the capability of discriminating non-target microRNAs containing even single-nucleotide mismatches, thus holding considerable potential for clinical diagnostics., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The weak signal strength in electron magnetic circular dichroism (EMCD) measurements remains one of the main challenges in the quantification of EMCD related EELS spectra. As a consequence, small variations in peak intensity caused by changes of background intervals, choice of method for extraction of signal intensity and equally differences in sample quality can cause strong changes in the EMCD signal. When aiming for high resolution quantitative EMCD, an additional difficulty consists in the fact that the two angular resolved EELS spectra needed to obtain the EMCD signal are taken at two different instances and it cannot be guaranteed that the acquisition conditions for these two spectra are identical. Here, we present an experimental setup where we use a double hole aperture in the transmission electron microscope to obtain the EMCD signal in a single acquisition. This geometry allows for the parallel acquisition of the two electron energy loss spectra (EELS) under exactly the same conditions. We also compare the double aperture acquisition mode with the qE acquisition mode which has been previously used for parallel acquisition of EMCD. We show that the double aperture mode not only offers better signal to noise ratio as compared to qE mode but also allows for much higher acquisition times to significantly improve the signal quality which is crucial for quantitative analysis of the magnetic moments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Transparent/translucent glass ceramics (GCs) have broad applications in biomedicine, armor, energy, and constructions. However, GCs with improved optical properties typically suffer from impaired mechanical properties, compared to traditional sintered full-ceramics. We present a method of obtaining high-strength, translucent GCs by preparing ZrO 2 -SiO 2 nanocrystalline glass ceramics (NCGCs) with a microstructure of monocrystalline ZrO 2 nanoparticles (NPs), embedded in an amorphous SiO 2 matrix. The ZrO 2 -SiO 2 NCGC with a composition of 65%ZrO/35%SiO 2 (molar ratio, 65Zr) achieved an average flexural strength of 1 GPa. This is one of the highest flexural strength values ever reported for GCs. ZrO 2 NPs bond strongly with SiO 2 matrix due to the formation of a thin (2-3 nm) amorphous Zr/Si interfacial layer between the ZrO 2 NPs and SiO 2 matrix. The diffusion of Si atoms into the ZrO 2 NPs forms a Zr-O-Si superlattice. Electron tomography results show that some of the ZrO 2 NPs are connected in one direction, forming in situ ZrO 2 nanofibers (with length of ∼500 nm), and that the ZrO 2 nanofibers are stacked in an ordered way in all three dimensions. The nanoarchitecture of the ZrO 2 nanofibers mimics the architecture of mineralized collagen fibril in cortical bone. Strong interface bonding enables efficient load transfer from the SiO 2 matrix to the 3D nanoarchitecture built by ZrO 2 nanofibers and NPs, and the 3D nanoarchitecture carries the majority of the external load. These two factors synergistically contribute to the high strength of the 65Zr NCGC. This study deepens our fundamental understanding of the microstructure-mechanical strength relationship, which could guide the design and manufacture of other high-strength, translucent GCs.

Due to substantial phonon scattering induced by various structural defects, the in-plane thermal conductivity (K) of graphene films (GFs) is still inferior to the commercial pyrolytic graphite sheet (PGS). Here, the problem is solved by engineering the structures of GFs in the aspects of grain size, film alignment, and thickness, and interlayer binding energy. The maximum K of GFs reaches to 3200 W m -1 K -1 and outperforms PGS by 60%. The superior K of GFs is strongly related to its large and intact grains, which are over four times larger than the best PGS. The large smooth features about 11 µm and good layer alignment of GFs also benefit on reducing phonon scattering induced by wrinkles/defects. In addition, the presence of substantial turbostratic-stacking graphene is found up to 37% in thin GFs. The lacking of order in turbostratic-stacking graphene leads to very weak interlayer binding energy, which can significantly decrease the phonon interfacial scattering. The GFs also demonstrate excellent flexibility and high tensile strength, which is about three times higher than PGS. Therefore, GFs with optimized structures and properties show great potentials in thermal management of form-factor-driven electronics and other high-power-driven systems., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Quantitative analysis of noisy electron spectrum images requires a robust estimation of the underlying background signal. We demonstrate how modern data compression methods can be used as a tool for achieving an analysis result less affected by statistical errors or to speed up the background estimation. In particular, we demonstrate how a multilinear singular value decomposition (MLSVD) can be used to enhance elemental maps obtained from a complex sample measured with energy electron loss spectroscopy. Furthermore, the usage of vertex component analysis (VCA) for a basis vector centered estimation of the background is demonstrated. Arising computational benefits in terms of model accuracy and computational costs are studied., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Modified supersaturated phosphate buffer solutions were used to synthesize phosphate-based spheres, including calcium phosphate (CaP), strontium phosphate (SrP) and barium phosphate (BaP). A series of ions concentrations in the modified phosphate buffer solutions were investigated in order to study their effects in precipitates morphologies. During synthesis, it was found that magnesium was the key factor in sphere formation. The morphologies of calcium phosphate, strontium phosphate and barium phosphate precipitates varied as the concentration of magnesium ions varied. When sufficient magnesium was provided, the precipitates appeared spherical, and the diameter was in range of 0.5-2 μm. The morphologies, compositions and structure of spheres were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N 2 adsorption analysis. Moreover, the application of magnesium substituted calcium phosphate spheres in dentin tubules occlusion was investigated.

The optical and electrical properties of Si rich SiC (SRSC) solar cell absorber layers will strongly depend on interfacial layers between the Si and the SiC matrix and in this work, we analyze hitherto undiscovered interfacial layers. The SRSC thin films were deposited using a plasma-enhanced chemical vapor deposition (PECVD) technique and annealed in a nitrogen environment at 1100 °C. The thermal treatment leads to metastable SRSC films spinodally decomposed into a Si-SiC nanocomposite. After the thermal treatment, the coexistence of crystalline Si and SiC nanostructures was analysed by high resolution transmission electron microscopy (HRTEM) and electron diffraction. From the quantitative extraction of the different plasmon signals from electron energy-loss spectra, an additional structure, amorphous SiC (a-SiC) was found. Quantitative spectroscopic electron tomography was developed to obtain three dimensional (3D) plasmonic maps. In these 3D spectroscopic maps, the Si regions appear as network structures inside the SiC matrix where the a-SiC appears as an interfacial layer separating the matrix and Si network. The presence of the a-SiC interface can be explained in the framework of the nucleation and growth model.

We propose an experimental setup based on a streak camera approach inside an energy filter to measure time resolved properties of materials in the transmission electron microscope (TEM). In order to put in place the streak camera, a beam sweeper was built inside an energy filter. After exciting the TEM sample, the beam is swept across the CCD camera of the filter. We describe different parts of the setup at the example of a magnetic measurement. This setup is capable to acquire time resolved diffraction patterns, electron energy loss spectra (EELS) and images with total streaking times in the range between 100ns and 10μs., (Copyright © 2016 Elsevier B.V. All rights reserved.)

While the performance of magnetic tunnel junctions based on metal/oxide interfaces is determined by hybridization, charge transfer, and magnetic properties at the interface, there are currently only limited experimental techniques with sufficient spatial resolution to directly observe these effects simultaneously in real-space. In this letter, we demonstrate an experimental method based on Electron Magnetic Circular Dichroism (EMCD) that will allow researchers to simultaneously map magnetic transitions and valency in real-space over interfacial cross-sections with sub-nanometer spatial resolution. We apply this method to an Fe/MgO bilayer system, observing a significant enhancement in the orbital to spin moment ratio that is strongly localized to the interfacial region. Through the use of first-principles calculations, multivariate statistical analysis, and Electron Energy-Loss Spectroscopy (EELS), we explore the extent to which this enhancement can be attributed to emergent magnetism due to structural confinement at the interface. We conclude that this method has the potential to directly visualize spin and orbital moments at buried interfaces in magnetic systems with unprecedented spatial resolution.

The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S 0 ), becomes exergonic in the first triplet state (T 1 ). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T 1 state and also in its first singlet excited state (S 1 ), opposite to S 0 , where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T 1 -state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T 1 and S 1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO 2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

We report the effect of hydrogen on the crystallization process of silicon nanocrystals embedded in a silicon oxide matrix. We show that hydrogen gas during annealing leads to a lower sub-band gap absorption, indicating passivation of defects created during annealing. Samples annealed in pure nitrogen show expected trends according to crystallization theory. Samples annealed in forming gas, however, deviate from this trend. Their crystallinity decreases for increased annealing time. Furthermore, we observe a decrease in the mean nanocrystal size and the size distribution broadens, indicating that hydrogen causes a size reduction of the silicon nanocrystals.