Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS3) whiskers are made out of weakly interacting TiS3 layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS3 both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS3 have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the AgS-S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS3 with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.
We present two-dimensional Mg(OH)2 sheets and their vertical heterojunctions with CVD-MoS2 for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)2 sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)2 have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)2 is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)2 sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)2 sheets together with CVD-MoS2 in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS2 sheets to Mg(OH)2, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)2, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.
Binary transition metal dichalcogenide monolayers share common properties such as a direct optical bandgap, spin-orbit splittings of hundreds of meV, light–matter interaction dominated by robust excitons and coupled spin-valley states. Here we demonstrate spin-orbit-engineering in Mo[(1-x)]WxSe2 alloy monolayers for optoelectronics and applications based on spin- and valley-control. We probe the impact of the tuning of the conduction band spin-orbit spin-splitting on the bright versus dark exciton population. For MoSe2 monolayers, the photoluminescence intensity decreases as a function of temperature by an order of magnitude (4–300 K), whereas for WSe2 we measure surprisingly an order of magnitude increase. The ternary material shows a trend between these two extreme behaviors. We also show a non-linear increase of the valley polarization as a function of tungsten concentration, where 40% tungsten incorporation is sufficient to achieve valley polarization as high as in binary WSe2.
Alloying selenium into ReS2 in the creation of ReS2xSe2-x, tunes the band gap and changes its vibrational spectrum. Depositing this alloy using bottom up approach has resulted in the loss of crystallinity. This loss of crystallinity was evidenced by grain boundaries and point defect shown by TEM images.
Also, in the creation of TiS3xSe3-x, by alloying Se into TiS3, a fixed ratio of 8% selenium deposit into TiS3 host matrix is observed. This is despite the vastly differing precursor amounts and growth temperatures, as evinced by detailed TEM, EDAX, TEM diffraction, and Raman spectroscopy measurements. This unusual behavior contrasts with other well-known layered material systems such as MoSSe, WMoS2 where continuous alloying can be attained. Cluster expansion theory calculations suggest that only limited composition (x) can be achieved. Considering the fact that TiSe3 vdW crystals have not been synthesized in the past, these alloying rejections can be attributed to energetic instability in the ternary phase diagrams estimated by calculations performed. Overall findings highlight potential means and challenges in achieving stable alloying in promising direct gap and high carrier mobility TiS3 materials.
We described the rapid production of the domain III (DIII) of the envelope (E) protein in plants as a vaccine candidate for West Nile Virus (WNV). Using various combinations of vector modules of a deconstructed viral vector expression system, DIII was produced in three subcellular compartments in leaves of Nicotiana benthamiana by transient expression. DIII expressed at much higher levels when targeted to the endoplasmic reticulum (ER) than that targeted to the chloroplast or the cytosol, with accumulation level up to 73 μg DIII per gram of leaf fresh weight within 4 days after infiltration. Plant ER-derived DIII was soluble and readily purified to > 95% homogeneity without the time-consuming process of denaturing and refolding. Further analysis revealed that plant-produced DIII was processed properly and demonstrated specific binding to an anti-DIII monoclonal antibody that recognizes a conformational epitope. Furthermore, subcutaneous immunization of mice with 5 and 25 μg of purified DIII elicited a potent systemic response. This study provided the proof of principle for rapidly producing immunogenic vaccine candidates against WNV in plants with low cost and scalability.
The increasing world demand for human biologics cannot be met by current production platforms based primarily on mammalian cell culture due to prohibitive cost and limited scalability [1]. Recent progress in plant expression vector development, downstream processing, and glycoengineering has established plants as a superior alternative to biologic production [2–4]. Plants not only offer the traditional advantages of proper eukaryotic protein modification, potential low cost, high scalability, and increased safety but also allow the production of biologics at unprecedented speed to control potential pandemics or with specific glycoforms for better efficacy or safety (biobetters) [5, 6]. The approval of the first plant-made biologic (PMB) by the United States Food and Drug Administration (FDA) for treating Gaucher’s disease heralds a new era for PMBs and sparks new innovations in this field [7, 8].
Background:
Environmental heat exposure is a public health concern. The impacts of environmental heat on mortality and morbidity at the population scale are well documented, but little is known about specific exposures that individuals experience.
Objectives:
The first objective of this work was to catalyze discussion of the role of personal heat exposure information in research and risk assessment. The second objective was to provide guidance regarding the operationalization of personal heat exposure research methods.
Discussion:
We define personal heat exposure as realized contact between a person and an indoor or outdoor environment that poses a risk of increases in body core temperature and/or perceived discomfort. Personal heat exposure can be measured directly with wearable monitors or estimated indirectly through the combination of time–activity and meteorological data sets. Complementary information to understand individual-scale drivers of behavior, susceptibility, and health and comfort outcomes can be collected from additional monitors, surveys, interviews, ethnographic approaches, and additional social and health data sets. Personal exposure research can help reveal the extent of exposure misclassification that occurs when individual exposure to heat is estimated using ambient temperature measured at fixed sites and can provide insights for epidemiological risk assessment concerning extreme heat.
Conclusions:
Personal heat exposure research provides more valid and precise insights into how often people encounter heat conditions and when, where, to whom, and why these encounters occur. Published literature on personal heat exposure is limited to date, but existing studies point to opportunities to inform public health practice regarding extreme heat, particularly where fine-scale precision is needed to reduce health consequences of heat exposure.