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Because of the lack of contact and spacer doping techniques for two-dimensional (2D) transistors, most high-performance 2D devices have been produced with nontypical structures that contain electrical gating in the contact regions. In the present study, we used chloroauric acid (HAuCl4) as a strong p-dopant for WSe2 monolayers used in transistors. The HAuCl4-doped devices exhibited a record-low contact resistance of 0.7 kΩ·µm under a doping concentration of 1.76 × 1013 cm-2. In addition, an extrinsic carrier diffusion phenomenon was discovered in the HAuCl4-WSe2 system. With a suitably designed spacer length for doping, a normally off, high-performance underlap top-gate device can be produced without the application of additional gating in the contact and spacer regions.
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Because of the intrinsic low carrier density of monolayer two-dimensional (2D) materials, doping is crucial for the performance of underlap top-gated 2D devices. However, wet etching of a high-k (dielectric constant) dielectric layer is difficult to implement without causing performance deterioration on the devices; therefore, finding a suitable spacer doping technique for 2D devices is indispensable. In this study, we developed a remote doping (RD) method in which defective SiOx can remotely dope the underlying high-k capped 2D regions without directly contacting these materials. This method achieved a doping density as high as 1.4 × 1013 cm-2 without reducing the mobility of the doped materials; after 1 month, the doping concentration remained as high as 1.2 × 1013 cm-2. Defective SiOx can be used to dope most popular 2D transition-metal dichalcogenides. The low-k properties of SiOx render it ideal for spacer doping, which is very attractive from the perspective of circuit operation. In our experiments, MoS2 and WS2 underlap top-gate devices exhibited 10× and 200× increases in their on-currents, respectively, after being doped with SiOx. These results indicate that SiOx doping can be conducted to manufacture high-performance 2D devices.
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Understanding the water state in Nafion is not only crucial for operating a proton-exchange membrane (PEM)-based fuel cell, but also intimately related to the elucidation of the proton transport mechanism in a PEM. Although many studies have been published on this subject, some controversies and ambiguities remain unresolved. In this work, we design three different types of Nafion samples by substituting protons with lithium or sodium cations. We also pay special attention to the preparation of samples for carrying out broad-range variable temperature solid state NMR experiments so that no membrane dehydration occurs during the long experimental time at low temperatures. With these precautions and improvements, clear and largely straightforward information could be obtained to ensure minimal ambiguity and complexity in the interpretation of the experimental data. Our results show that about 40-60% of water remains unfrozen at -70 °C, depending on the type of the substituting cation. Both the 1H and 2H spectral and relaxation results indicate that water freezing starts from the center of the nanopores inside Nafion and increases gradually as the temperature decreases. The protons remain dissociated with sulfonate groups even at the lowest temperature we reached (-70 °C), whereas both lithium and sodium are associated with sulfonate groups at most temperatures below 0 °C. The experimental data also suggest that besides frozen and unfrozen water, there is broad distribution of water state and dynamics in Nafion as the temperature is lowered from above zero down to -70 °C. The effect of the size of the substituting cation significantly affects the properties of supercooled water by modifying the cation-water interaction and impeding the rotation of sulfonate groups. These novel results not only help us in establishing a better understanding of the water state in Nafion and its performance as a proton exchange mebrane, but also provide insights into water freezing, antifreeze and supercooling in other nanoscopic environments.
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Molecular imaging based on magnetic resonance imaging (MRI) requires a contrast agent with high relaxivity and specificity. Much effort has been devoted to this goal over the past decades. In this work, we continue this endeavor by synthesizing an MRI contrast agent that can penetrate the cellular membrane and bind with specific proteins. It was characterized with one- and two-dimensional NMR spectroscopy, NMR micro-imaging, and mass spectroscopy. The target specificity has been further confirmed by both molecular dynamics simulation and micro-imaging on a living biological system. It is one of the largest of peptide-based bioactivated MRI contrast agents, and its relaxivity enhancement factor is among the highest of MRI contrast agents hitherto published. We envision interesting applications and extension of this smart MRI contrast agent with bio-specificity and high contrast for molecular imaging.
Asunto(s)
Medios de Contraste/química , Imagen por Resonancia Magnética/métodos , Imagen Molecular/métodos , Péptidos/metabolismo , HumanosRESUMEN
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Contrast enhancement agents are often employed in magnetic resonance imaging (MRI) for clinical diagnosis and biomedical research. However, the current theory on MRI contrast generation does not consider the ubiquitous presence of macromolecular crowders in biological systems, which poses the risk of inaccurate data interpretation and misdiagnosis. To address this issue, herein the macromolecular crowding effects on MRI contrast agent are investigated with the 1H relaxation rate of water in aqueous solutions of Dotarem with different concentrations of macromolecules. Two representative macromolecular crowder systems are used: polyethylene glycol (with no specific secondary structure) and bovine serum albumin (with compact secondary and tertiary structures). The water 1H relaxation rates in various solutions are measured in a fixed magnetic field and in variable magnetic fields. The results show significant crowding effects for both crowders. The relaxation rate is proportional to the concentration of the MRI contrast agent but shows conspicuous superlinearity with respect to the concentration of the crowder. The size of polyethylene glycol does not affect the relaxivity of water in Dotarem solutions. The above effects are verified with T1- and T2-weighted NMR microimages. These results highlight the importance of the effect of macromolecular crowding on the MRI contrast agent and are valuable for understanding the mechanism of MRI contrast agents and designing new-generation MRI contrast agents.
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Phosphorus metabolism and circulation are essential bio-physicochemical processes during development of a plant and have been extensively studied and known to be affected by temperature, humidity, lighting, hormones etc. However, a quantitative description of how various phosphorous species evolve over time has not been reported. In this work, a combined 31P liquid and solid state NMR spectroscopic methodology is employed, supported by a new extraction scheme and data analysis method, to carry out a quantitative investigation of phosphorous circulation in germinating sesame seeds in dark and under illumination with and without adding a growth hormone. The spectra show that only slight changes occur for phosphorous metabolism at the initial stage but a rapid change takes place between 48-96 hours after germination is started. The metabolism is found to be temperature dependent and affected by illumination and hormone. However, neither illumination nor hormone affects the final residual concentration of phytin. Moreover, phytin does not flow out of cotyledon and the phosphorous flowing to other parts of the plant is always in the inorganic form. The overall evolution profile of phytate consumption is found to be a Gaussian decaying function. These findings can be explained with a dynamic model on phytin conversion.
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(1)H, (17)O, and (19)F solid state NMR spectroscopies have been used to investigate water penetration in Nafion-117 under mechanical spinning. It is found that both (1)H and (17)O spectra depend on the orientation of the membrane with respect to the magnetic field. The intensities of the side chain (19)F spectra depend slightly on the orientation of membrane with respect to the magnetic field, but the backbone (19)F spectra do not exhibit orientation dependence. By analyzing the orientation dependent (1)H and (17)O spectra and time-resolved (1)H spectra, we show that the water loaded in Nafion-117, under high spinning speed, may penetrate into regions that are normally inaccessible by water. Water penetration is enhanced as the spinning speed is increased or the spinning time is increased. In the meantime, mechanical spinning accelerates water exchange. It is also found that water penetration by mechanical spinning is persistent; i.e., after spinning, water remains in those newly found regions. While water penetration changes the pores and channels in Nafion, (19)F spectra indicate that the chemical environments of the polymer backbone do not show change. These results provide new insights about the structure and dynamics of Nafion-117 and related materials. They are relevant to proton exchange membrane aging and offer enlightening points of view on antiaging and modification of this material for better proton conductivity. It is also interesting to view this phenomenon in the perspective of forced nanofiltration.
