Search

Colloidal quantum dot (CQD) infrared (IR) photodetectors can be fabricated and operated with larger spectral tunability, fewer limitations in terms of cooling requirements and substrate lattice matching, and at a potentially lower cost than detectors based on traditional bulk materials. Silver selenide (Ag2Se) has emerged as a promising sustainable alternative to current state-of-the-art toxic semiconductors based on lead, cadmium, and mercury operating in the IR. However, an impeding gap in available absorption bandwidth for Ag2Se CQDs exists in the short-wave infrared (SWIR) region due to degenerate doping by the environment, switching the CQDs from intrinsic interband semiconductors in the near-infrared (NIR) to intraband absorbing CQDs in the mid-wave infrared (MWIR). Herein, we show that the small molecular p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) can be used to extract electrons from the 1Sestate of MWIR active Ag2Se CQDs to activate their intrinsic energy gap in the SWIR window. We demonstrate quenching of the MWIR Ag2Se absorbance peak, shifting of nitrile vibrational peaks characteristic of charge-neutral F4-TCNQ, as well as enhanced CQD absorption around ∼2500 nm after doping both in ambient and under air-free conditions. We elucidate the doping mechanism to be one that involves an integer charge transfer akin to doping in semiconducting polymers. These indications of charge transfer are promising milestones on the path to achieving sustainable SWIR Ag2Se CQD photodetectors.

Tailoring nanoscale catalysts to targeted applications is a vital component in reducing the carbon footprint of industrial processes; however, understanding and controlling the nanostructure influence on catalysts is challenging. Molybdenum disulfide (MoS2), a transition metal dichalcogenide (TMD) material, is a popular example of a nonplatinum-group-metal catalyst with tunable nanoscale properties. Doping with transition metal atoms, such as cobalt, is one method of enhancing its catalytic properties. However, the location and influence of dopant atoms on catalyst behavior are poorly understood. To investigate this knowledge gap, we studied the influence of Co dopants in MoS2nanosheets on catalytic hydrodesulfurization (HDS) through a well-controlled, ligand-directed, tunable colloidal doping approach. X-ray absorption spectroscopy and density functional theory calculations revealed the nonmonotonous relationship between dopant concentration, location, and activity in HDS. Catalyst activity peaked at 21% Co:Mo as Co saturates the edge sites and begins basal plane doping. While Co prefers to dope the edges over basal sites, basal Co atoms are demonstrably more catalytically active than edge Co. These findings provide insight into the hydrogenolysis behavior of doped TMDs and can be extended to other TMD materials.

The DNA damage response (DDR) is intertwined with signaling pathways downstream of oncogenic receptor tyrosine kinases (RTKs). To drive research into the application of targeted therapies as radiosensitizers, a better understanding of this molecular crosstalk is necessary. We present here the characterization of a previously unreported MET RTK phosphosite, Serine 1016 (S1016) that represents a potential DDR-MET interface. MET S1016 phosphorylation increases in response to irradiation and is mainly targeted by DNA-dependent protein kinase (DNA-PK). Phosphoproteomics unveils an impact of the S1016A substitution on the overall long-term cell cycle regulation following DNA damage. Accordingly, the abrogation of this phosphosite strongly perturbs the phosphorylation of proteins involved in the cell cycle and formation of the mitotic spindle, enabling cells to bypass a G2 arrest upon irradiation and leading to the entry into mitosis despite compromised genome integrity. This results in the formation of abnormal mitotic spindles and a lower proliferation rate. Altogether, the current data uncover a novel signaling mechanism through which the DDR uses a growth factor receptor system for regulating and maintaining genome stability.

Increasing the number of environmental stressors could decrease ecosystem functioning in soils. Yet this relationship has not been globally assessed outside laboratory experiments. Here, using two independent global standardized field surveys, and a range of natural and human factors, we test the relationship between the number of environmental stressors exceeding different critical thresholds and the maintenance of multiple ecosystem services across biomes. Our analysis shows that having multiple stressors, from medium levels (>50%), negatively and significantly correlates with impacts on ecosystem services and that having multiple stressors crossing a high-level critical threshold (over 75% of maximum observed levels) reduces soil biodiversity and functioning globally. The number of environmental stressors exceeding the >75% threshold was consistently seen as an important predictor of multiple ecosystem services, therefore improving prediction of ecosystem functioning. Our findings highlight the need to reduce the dimensionality of the human footprint on ecosystems to conserve biodiversity and function.

AbstractAmong EvergreenHealth Home Care Service professionals, no coronavirus disease 2019 (COVID-19) cases were reported when they were instructed to use standard, contact, and droplet precautions with eye protection while providing home health care to patients diagnosed with laboratory-confirmed severe acute respiratory coronavirus virus 2 (SARS-CoV-2). These precautions might provide some level of protection against coronavirus disease 2019 (COVID-19) among home healthcare personnel.

The intensive use of pesticides and their subsequent distribution to the environment and non-target organisms is of increasing concern. So far, little is known about the occurrence of pesticides in soils of untreated areas─such as ecological refuges─as well as the processes contributing to this unwanted pesticide contamination. In this study, we analyzed the presence and abundance of 46 different pesticides in soils from extensively managed grassland sites, as well as organically and conventionally managed vegetable fields (60 fields in total). Pesticides were found in all soils, including the extensive grassland sites, demonstrating a widespread background contamination of soils with pesticides. The results suggest that after conversion from conventional to organic farming, the organic fields reach pesticide levels as low as those of grassland sites not until 20 years later. Furthermore, the different pesticide composition patterns in grassland sites and organically managed fields facilitated differentiation between long-term persistence of residues and diffuse contamination processes, that is, short-scale redistribution (spray drift) and long-scale dispersion (atmospheric deposition), to offsite contamination.

To analyze gastroschisis annual incidence, mortality rates, and trends in the Brazilian state of Rio Grande do Sul from the year 2000 to the year 2017.

Understanding the interfacial properties between an atomic layer and its substrate is of key interest at both the fundamental and technological levels. From Fermi level pinning to strain engineering and superlubricity, the interaction between a single atomic layer and its substrate governs electronic, mechanical and chemical properties. Here, we measure the hardly accessible interfacial transverse shear modulus of an atomic layer on a substrate. By performing measurements on bulk graphite, and on epitaxial graphene films on SiC with different stacking orders and twisting, as well as in the presence of intercalated hydrogen, we find that the interfacial transverse shear modulus is critically controlled by the stacking order and the atomic layer–substrate interaction. Importantly, we demonstrate that this modulus is a pivotal measurable property to control and predict sliding friction in supported two-dimensional materials. The experiments demonstrate a reciprocal relationship between friction force per unit contact area and interfacial shear modulus. The same relationship emerges from simulations with simple friction models, where the atomic layer–substrate interaction controls the shear stiffness and therefore the resulting friction dissipation.

Pesticides are applied in large quantities to agroecosystems worldwide. To date, few studies assessed the occurrence of pesticides in organically managed agricultural soils, and it is unresolved whether these pesticide residues affect soil life. We screened 100 fields under organic and conventional management with an analytical method containing 46 pesticides (16 herbicides, 8 herbicide transformation products, 17 fungicides, seven insecticides). Pesticides were found in all sites, including 40 organic fields. The number of pesticide residues was two times and the concentration nine times higher in conventional compared to organic fields. Pesticide number and concentrations significantly decreased with the duration of organic management. Even after 20 years of organic agriculture, up to 16 different pesticide residues were present. Microbial biomass and specifically the abundance of arbuscular mycorrhizal fungi, a widespread group of beneficial plant symbionts, were significantly negatively linked to the amount of pesticide residues in soil. This indicates that pesticide residues, in addition to abiotic factors such as pH, are a key factor determining microbial soil life in agroecosystems. This comprehensive study demonstrates that pesticides are a hidden reality in agricultural soils, and our results suggest that they have harmful effects on beneficial soil life.

CRISPR-Cas9 deletion (CRISPR-del) is the leading approach for eliminating DNA from mammalian cells and underpins a variety of genome-editing applications. Target DNA, defined by a pair of double-strand breaks (DSBs), is removed during nonhomologous end-joining (NHEJ). However, the low efficiency of CRISPR-del results in laborious experiments and false-negative results. By using an endogenous reporter system, we show that repression of the DNA-dependent protein kinase catalytic subunit (DNA-PKcs)—an early step in NHEJ—yields substantial increases in DNA deletion. This is observed across diverse cell lines, gene delivery methods, commercial inhibitors, and guide RNAs, including those that otherwise display negligible activity. We further show that DNA-PKcs inhibition can be used to boost the sensitivity of pooled functional screens and detect true-positive hits that would otherwise be overlooked. Thus, delaying the kinetics of NHEJ relative to DSB formation is a simple and effective means of enhancing CRISPR-deletion.

Two-dimensional transition metal carbides and nitrides (MXenes) have accumulated tremendous interest recently due to their high conductivity and excellent figures of merit in electromagnetic interference shielding and other applications. Large-area freestanding films of MXenes are important for versatility in application; however, alternative processing methods are needed for large-scale production. In this work, we demonstrate fabrication of Ti3C2TxMXene freestanding films through drop-casting onto hydrophobic plastic substrates. Freestanding MXene films prepared using the drop-casting method can be fabricated in large areas (>125 cm2) and thicknesses (23.2 μm), and have smooth surfaces (14 nm RMS roughness) while maintaining high electrical conductivity (~7,000 S cm−1). Moreover, these MXene films can be micropatterned in three dimensions by processing on commercially available microstructured plastics, resulting in a 38% increase in normalized electromagnetic interference shielding efficiency compared with flat films. The results presented here suggest a scalable path toward creating MXene freestanding films for prototypes and industrialization.

With the rapidly expanding pandemic of SARS‐CoV‐2, there is concern that solid organ transplant recipients will be particularly vulnerable to infection and may experience a more severe clinical course. We report four cases of COVID‐19 in solid organ transplant recipients including recipients of kidney, liver, lung, and heart transplants. We describe each patient's medical history including transplantation history, their clinical presentation and workup, and their course from diagnosis to either hospital discharge or to improvement in symptoms. These reports demonstrate a range of symptoms, clinical severity, and disease course in solid organ transplant recipients with COVID‐19, including two hospitalized patients and two patients managed entirely in the outpatient setting. The authors report four cases of SARS‐CoV‐2 infection in kidney, liver, lung, and heart transplant recipients in Seattle, Washington, with a range of disease severity and favorable outcomes.

BackgroundProgrammes for collective smoking cessation, based on the British model Stoptober, are proposed by public health units in many countries. There is a need for data estimating the rate at which participants in these programmes are successful in quitting smoking. We report a prospective study carried out as part of a large-scale collective cessation programme conducted in Switzerland in 2017.Methods1112 participants among the 7008 smokers enrolled in the collective cessation programme were recruited before the start of the attempt. Continuous abstinence was measured 10 days, 3 months and 6 months after the start of the attempt. Participants who dropped out at follow-up were considered to have failed the attempt (worst-case scenario).ResultsThe continuous abstinence rate was at least 37.9% at 10-day follow-up, 18.8% at 3-month follow-up and 13.1% at 6-month follow-up. Similar levels of continuous abstinence as the worst-case scenario were found in sensitivity analyses including those whose quit attempt started before the beginning of the programme and where multiple imputation was used to replace dropouts. Sensitivity analyses using complete cases or an indicator of abstinence which allows occasional lapses found around double the abstinence rates.ConclusionsOur results support the potential usefulness of large-scale collective cessation campaigns and suggest that such programmes based on social networks are promising areas for future smoking cessation programme activity.

The application of a novel UV fs Laser Ablation Ionization Mass Spectrometry approach for chemical depth profiling of low-melting point, high surface roughness SnAg solder bump features is presented. The obtained submicrometer resolved three-dimensional compositional data reveal unprecedented information on the distribution of individual elements inside the solder bump matrix. Moreover, the determination of matrix-matched relative sensitivity coefficients allows the first report on quantitative assessment of the SnAg alloy composition. These results significantly contribute to an in-depth understanding of the SnAg plating process. This experimental procedure may find application in future additive performance screening.

The ability to precisely control the localization of enzymes on a surface is critical for several applications including biosensing, bionanoreactors, and single molecule studies. Despite recent advances, fabrication of enzyme patterns with resolution at the single enzyme level is limited by the lack of lithography methods that combine high resolution, compatibility with soft, polymeric structures, ease of fabrication, and high throughput. Here, a method to generate enzyme nanopatterns (using thermolysin as a model system) on a polymer surface is demonstrated using thermochemical scanning probe lithography (tc-SPL). Electrostatic immobilization of negatively charged sulfonated enzymes occurs selectively at positively charged amine nanopatterns produced by thermal deprotection of amines along the side-chain of a methacrylate-based copolymer film via tc-SPL. This process occurs simultaneously with local thermal quasi-3D topographical patterning of the same polymer, offering lateral sub-10 nm resolution, and vertical 1 nm resolution, as well as high throughput (5.2 × 104μm2/h). The obtained single-enzyme resolution patterns are characterized by atomic force microscopy (AFM) and fluorescence microscopy. The enzyme density, the surface passivation, and the quasi-3D arbitrary geometry of these patterned pockets are directly controlled during the tc-SPL process in a single step without the need of markers or masks. Other unique features of this patterning approach include the combined single-enzyme resolution over mm2areas and the possibility of fabricating enzymes nanogradients.

Research has started to investigate personality traits of social entrepreneurs because such traits in commercial entrepreneurs have been found to affect new venture creation/success. In this exploratory study, we apply the person‐environment fit theory and analyze specific social entrepreneurial personality dimensions (i.e., altruism, empathic concern, personal distress, compassion), and classical entrepreneurial personality dimensions (i.e., need for achievement (nAch), entrepreneurial self‐efficacy (ESE), general self‐efficacy, risk‐taking propensity) to identify differences between prospective social and commercial entrepreneurs. Using a sample of 85 prospective entrepreneurs, results show that prospective social entrepreneurs differ from prospective commercial entrepreneurs in the personality dimensions of personal distress, nAch, ESE, and risk‐taking propensity.

State-of-the-art laser ablation (LA) depth-profiling techniques (e.g. LA-ICP-MS, LIBS, and LIMS) allow for chemical composition analysis of solid materials with high spatial resolution at micro- and nanometer levels. Accurate determination of LA-volume is essential to correlate the recorded chemical information to the specific location inside the sample. In this contribution, we demonstrate two novel approaches towards a better quantitative analysis of LA craters with dimensions at micrometer level formed by femtosecond-LA processes on single-crystalline Si(100) and polycrystalline Cu model substrates. For our parametric crater evolution studies, both the number of applied laser shots and the pulse energy were systematically varied, thus yielding 2D matrices of LA craters which vary in depth, diameter, and crater volume. To access the 3D structure of LA craters formed on Si(100), we applied a combination of standard lithographic and deep reactive-ion etching (DRIE) techniques followed by a HR-SEM inspection of the previously formed crater cross sections. As DRIE is not applicable for other material classes such as metals, an alternative and more versatile preparation technique was developed and applied to the LA craters formed on the Cu substrate. After the initial LA treatment, the Cu surface was subjected to a polydimethylsiloxane (PDMS) casting process yielding a mold being a full 3D replica of the LA craters, which was then analyzed by HR-SEM. Both approaches revealed cone-like shaped craters with depths ranging between 1 and 70 μm and showed a larger ablation depth of Cu that exceed the one of Si by a factor of about 3.

In this contribution highly sensitive and quantitative analytical methodologies based on femtosecond Laser Ablation Ionization Mass Spectrometry (fs-LIMS) for the analysis of model systems and state-of-the-art Cu interconnects are reviewed and discussed. The method development introduces in a first stage a 1D chemical depth profiling approach on electrodeposited Cu films containing periodically confined organic layers. Optimization of measurement conditions on these test platforms enabled depth profiling investigations with vertical resolution at the nm level. In a second stage, a matrix-free laser desorption methodology was developed that allowed for preliminary molecular identification of the embedded organic contaminants beyond elementary composition. These studies provided specific fragmentation markers in the lower mass range, which support a previously proposed reaction mechanism responsible for successful leveling employing a new class of plating additives for Damascene processes. Further combined LIMS and Scanning Auger Microscopy (SAM) studies on through-silicon-vias (TSV) interconnects confirmed the embedment upon plating of the organic additives at the upper side-walls of the TSV channel in the boundary between the Cu seed layer and the electrodeposited Cu.

ABSTRACTThe first step in preservative measures for artworks in airtight showcases is the exclusion of outgassing from construction materials or, at least, limitation of the emissions to a minimum acceptable level if the volatile organic compounds (VOCs) generated may be qualified as harmless. Once it is ascertained that the objects in the showcases are responsible for VOC emissions, a step forward becomes necessary, implying showcase ventilation with air flowing through active sorbent materials. Solid phase micro-extraction (SPME) followed by GC separation and MS identification has been applied for checking the outgassing characteristics of different types of materials used for the construction of airtight showcases, and the method was found particularly attractive in terms of speed and sensitivity, suitable for measurements in presence of low-emitting materials. Sampling could also be done in the case interiors, thus making possible detection and recognition of emissions from art objects within a case. A comprehensive preventive conservation scheme has been further devised by means of active air circulation within the showcase and functional sorbent materials along the flow, for complete suppression of gaseous compounds. Control of the compounds in the air flow and of their filtration efficacy was achieved by direct sampling, also using SPME fibers. Continuous monitoring of the air quality in the showcases has been developed with insertion of a photoionization detector capable of detecting the VOCs in the air by inducing molecular ionization, and measuring the generated photocurrent. The system is not selective, but gives the total concentration, reaching ppb sensitivity with high-quality data. In addition it includes temperature and humidity sensors, making the whole a useful instrument for environment control.

Abstract

Atomically thin graphene exhibits fascinating mechanical properties, although its hardness and transverse stiffness are inferior to those of diamond. So far, there has been no practical demonstration of the transformation of multilayer graphene into diamond-like ultrahard structures. Here we show that at room temperature and after nano-indentation, two-layer graphene on SiC(0001) exhibits a transverse stiffness and hardness comparable to diamond, is resistant to perforation with a diamond indenter and shows a reversible drop in electrical conductivity upon indentation. Density functional theory calculations suggest that, upon compression, the two-layer graphene film transforms into a diamond-like film, producing both elastic deformations and sp2to sp3chemical changes. Experiments and calculations show that this reversible phase change is not observed for a single buffer layer on SiC or graphene films thicker than three to five layers. Indeed, calculations show that whereas in two-layer graphene layer-stacking configuration controls the conformation of the diamond-like film, in a multilayer film it hinders the phase transformation. Indentation in bilayer epitaxial graphene induces its reversible transformation into a diamond-like structure with stiffness and hardness comparable to diamond.

Reproducing in vitro the complex multiscale physical features of human tissues creates novel biomedical opportunities and fundamental understanding of cell−environment interfaces and interactions. While stiffness has been recognized as a key driver of cell behavior, systematic studies on the role of stiffness have been limited to values in the KPa−MPa range, significantly below the stiffness of bone. Here, a platform enabling the tuning of the stiffness of a biocompatible polymeric interface up to values characteristic of human bone is reported, which are in the GPa range, by using extremely thin polymer films on glass and cross‐linking the films using ultraviolet (UV) light irradiation. It is shown that a higher stiffness is related to better adhesion, proliferation, and osteogenic differentiation, and that it is possible to switch on/off cell attachment and growth by solely tuning the stiffness of the interface, without any surface chemistry or topography modification. Since the stiffness is tuned directly by UV irradiation, this platform is ideal for rapid and simple fabrication of stiffness patterns and gradients, thus representing an innovative tool for combinatorial studies of the synergistic effect of tissue environmental cues on cell behavior, and creates new opportunities for next‐generation biosensors, single‐cell patterning, and lab‐on‐a‐chip devices. A novel platform to tune the stiffness of a biocompatible polymeric interface up to values characteristic of the bone tissue (GPa range)  using ultraviolet (UV) cross‐linking is reported. Since cell growth and differentiation are here controlled solely by the UV‐tunable stiffness of the polymer, this platform is ideal for the simple and rapid fabrication of stiffness patterns and gradients for various biomedical applications.

ABSTRACTBackground: L-DOPA is an amino acid precursor to the neurotransmitter dopamine that is extensively used as a prodrug for the treatment of Parkinson’s disease. However, L-DOPA is an unstable compound: when exposed to light or added to aqueous solutions, it may degrade, compromising its therapeutic properties.Methods: In this work, a new type of drug-loaded cyclodextrin-based nanosponge, obtained using molecular imprinting, is described for the prolonged and controlled release of L-DOPA. The molecularly imprinted nanosponges (MIP-NSs) were synthesized by cross-linking β-cyclodextrin with 1,1ʹ-carbonyldiimidazole in DMF in the presence of L-DOPA as a template molecule. TGA, DSC and FTIR analyses were performed to characterize the interactions between L-DOPA and the two nanosponge structures. Quantitative NMR spectroscopy was used to determine the amount and the affinity of L-DOPA entrapped in the nanosponges. The in vitroL-DOPA release kinetics from the NSs were quantitatively determined by HPLC analysis.Results: The MIP-NSs show a slower and more prolonged release profile than the non-imprinted nanosponges. No degradation of the L-DOPA hosted in the MIP-NSs was observed after long-term storage at room temperature.Conclusions: The MIP-NSs are a promising alternative for the storage and controlled delivery of L-DOPA.

The search for novel tools to control magnetism at the nanoscale is crucial for the development of new paradigms in optics, electronics and spintronics. So far, the fabrication of magnetic nanostructures has been achieved mainly through irreversible structural or chemical modifications. Here, we propose a new concept for creating reconfigurable magnetic nanopatterns by crafting, at the nanoscale, the magnetic anisotropy landscape of a ferromagnetic layer exchange-coupled to an antiferromagnetic layer. By performing localized field cooling with the hot tip of a scanning probe microscope, magnetic structures, with arbitrarily oriented magnetization and tunable unidirectional anisotropy, are reversibly patterned without modifying the film chemistry and topography. This opens unforeseen possibilities for the development of novel metamaterials with finely tuned magnetic properties, such as reconfigurable magneto-plasmonic and magnonic crystals. In this context, we experimentally demonstrate spatially controlled spin wave excitation and propagation in magnetic structures patterned with the proposed method.