Protein Structure and Interactions Studied by Electrospray Mass Spectrometry

Since the emergence of electrospray ionization (ESI) mass spectrometry (MS) as a tool for protein structural studies, this area has experienced tremendous growth. ESI-MS is highly sensitive, and it allows the analysis of biological systems ranging in size from a few atoms to large multi-protein complexes. This work aims to solve questions in protein structural biology by using ESI-MS in conjunction with other techniques. We initially apply ESI-MS for studying the monomeric protein cytochrome c (Chapter 2). The physical reasons underlying the irreversible thermal denaturation of this protein remain controversial. By utilizing deconvoluted charge state distributions, oxidative modifications were found to be the major reason underlying the observed behavior. The positions of individual oxidation sites were identified by LC-MS/MS-based tryptic peptide mapping. Chapter 3 and 4 focus on noncovalent protein complexes. ESI allows the transfer of multi-protein complexes into the gas phase, thereby providing a simple approach for monitoring the stoichiometry of these assemblies by MS. It remains somewhat unclear, however, in how far this approach is suitable for measuring binding affinities. We demonstrate that the settings used for rf-only quadrupoles in the ion path are a key factor for ensuring uniform transmission behavior, which is a prerequisite for meaningful Kd measurements. Overall, our data support the viability of the direct ESI-MS approach for determining binding affinities of protein–protein complexes in solution. Having established suitable conditions for the analysis of noncovalent protein complexes, ESI-MS is applied for monitoring the folding and assembly of hemoglobin (Hb). The native structure of this protein comprises four heme-bound subunits. Hb represents an important model system for exploring coupled folding/binding reactions, an area that remains difficult to tackle experimentally. We demonstrate that efficient Hb refolding depends on the heme ligation status. Only under properly optimized conditions is it possible to return denatured Hb to its tetrameric native state with high yield. ESI-MS allows the observation of on-pathway and off-pathway intermediates that become populated during this highly complex self-assembly process. In summary, this work demonstrates that ESI-MS is a highly versatile tool for addressing questions at the interface of chemistry and structural biology

MoS2 Nanoribbon Transistors: Transition from Depletion-mode to Enhancement-mode by Channel Width Trimming

We study the channel width scaling of back-gated MoS2 metal-oxide-semiconductor field-effect transistors (MOSFETs) from 2 {\mu}m down to 60 nm. We reveal that the channel conductance scales linearly with channel width, indicating no evident edge damage for MoS2 nanoribbons with widths down to 60 nm as defined by plasma dry etching. However, these transistors show a strong positive threshold voltage (VT) shift with narrow channel widths of less than 200 nm. Our results also show that transistors with thinner channel thicknesses have larger VT shifts associated with width scaling. Devices fabricated on a 6 nm thick MoS2 crystal underwent the transition from depletion-mode to enhancement-mode.Comment: 3 pages, 3 figures, to appear in IEEE Electron Device Letter

First Experimental Demonstration of Gate-all-around III-V MOSFET by Top-down Approach

The first inversion-mode gate-all-around (GAA) III-V MOSFETs are experimentally demonstrated with a high mobility In0.53Ga0.47As channel and atomic-layer-deposited (ALD) Al2O3/WN gate stacks by a top-down approach. A well-controlled InGaAs nanowire release process and a novel ALD high-k/metal gate process has been developed to enable the fabrication of III-V GAA MOSFETs. Well-behaved on-state and off-state performance has been achieved with channel length (Lch) down to 50nm. A detailed scaling metrics study (S.S., DIBL, VT) with Lch of 50nm - 110nm and fin width (WFin) of 30nm - 50nm are carried out, showing the immunity to short channel effects with the advanced 3D structure. The GAA structure has provided a viable path towards ultimate scaling of III-V MOSFETs.Comment: IEEE IEDM 2011 pp. 769-772; Structures are valuable for low-dimensional physics stud

Magneto-Transport in MoS2: Phase Coherence, Spin Orbit Scattering and the Hall Factor

We have characterized phase coherence length, spin orbit scattering length, and the Hall factor in n-type MoS2 2D crystals via weak localization measurements and Hall-effect measurements. Weak localization measurements reveal a phase coherence length of ~50 nm at T = 400 mK for a few-layer MoS2 film, decreasing as T^-1/2 with increased temperatures. Weak localization measurements also allow us, for the first time without optical techniques, to estimate the spin orbit scattering length to be 430 nm, pointing to the potential of MoS2 for spintronics applications. Via Hall-effect measurements, we observe a low temperature Hall mobility of 311 cm2/Vs at T = 1 K which decreases as a power law with a characteristic exponent {\gamma}=1.5 from 10 K to 60 K. At room temperature, we observe Hall mobility of 24 cm2/Vs. By determining the Hall factor for MoS2 to be 1.35 at T = 1 K and 2.4 at room temperature, we observe drift mobility of 420 cm2/Vs and 56 cm2/Vs at T = 1 K and room temperature, respectively.Comment: ACS Nano nn402377

Assessment of the economic impacts of heat waves: A case study of Nanjing, China

The southeast region of China is frequently affected by summer heat waves. Nanjing, a metropolitan city in Jiangsu Province, China, experienced an extreme 14-day heat wave in 2013. Extreme heat can not only induce health outcomes in terms of excess mortality and morbidity (hospital admissions) but can also cause productivity losses for self-paced indoor workers and capacity losses for outdoor workers due to occupational safety requirements. All of these effects can be translated into productive working time losses, thus creating a need to investigate the macroeconomic implications of heat waves on production supply chains. Indeed, industrial interdependencies are important for capturing the cascading effects of initial changes in factor inputs in a single sector on the remaining sectors and the economy. To consider these effects, this paper develops an interdisciplinary approach by combining meteorological, epidemiological and economic analyses to investigate the macroeconomic impacts of heat waves on the economy of Nanjing in 2013. By adopting a supply-driven input-output (IO) model, labour is perceived to be a key factor input, and any heat effect on human beings can be viewed as a degradation of productive time and human capital. Using this interdisciplinary tool, our study shows a total economic loss of 27.49 billion Yuan for Nanjing in 2013 due to the heat wave, which is equivalent to 3.43% of the city's gross value of production in 2013. The manufacturing sector sustained 63.1% of the total economic loss at 17.34 billion Yuan. Indeed, based on the ability of the IO model to capture indirect economic loss, our results further suggest that although the productive time losses in the manufacturing and service sectors have lower magnitudes than those in the agricultural and mining sectors, they can entail substantial indirect losses because of industrial interdependencies. This important conclusion highlights the importance of incorporating industrial interdependencies and indirect economic assessments in disaster risk studies

Loss of work productivity in a warming world: differences between developed and developing countries

Comparable estimates of the heat-related work productivity loss (WPL) in different countries over the world are difficult partly due to the lack of exact measures and comparable data for different counties. In this study, we analysed 4363 responses to a global online survey on the WPL during heat waves in 2016. The participants were from both developed and developing countries, facilitating estimates of the heat-related WPL across the world for the year. The heat-related WPL for each country involved was then deduced for increases of 1.5, 2, 3 and 4 °C in the global mean surface temperature under the representative concentration pathway scenarios in climate models. The average heat-related WPL in 2016 was 6.6 days for developing countries and 3.5 days for developed countries. The estimated heat-related WPL was negatively correlated with the gross domestic product per capita. When global surface temperatures increased by 1.5, 2, 3 and 4 °C, the corresponding WPL was 9 (19), 12 (31), 22 (61) and 33 (94) days for developed (developing) countries, quantifying how developing countries are more vulnerable to climate change from a particular point of view. Moreover, the heat-related WPL was unevenly distributed among developing countries. In a 2°C-warmer world, the heat-related WPL would be more than two months in Southeast Asia, the most influenced region. The results are considerable for developing strategy of adaptation especially for developing countries

Investigations of supported Au-Pd nanoparticles on synthesized CeO2 with different morphologies and application in solvent-free benzyl alcohol oxidation

Au-Pd bimetallic nanoparticles immobilized on series of CeO2 supports with different morphologies, e.g., rod, cube, and polyhedrons were prepared through the deposition-precipitation method with a consequent investigation on their catalytic performances for benzyl alcohol oxidation in the absence of solvent. The experimental results exhibited that the morphology of CeO2 has a markedly impact on the catalytic performance of Au-Pd/CeO2. In which Au-Pd supported on CeO2 rod could achieve higher benzyl alcohol conversion than that supported on CeO2 polyhedrons and CeO2 cube, however, CeO2 cube supported Au-Pd showed the highest selectivity towards the production of benzaldehyde. ICP-AES, XRD, Raman, N2-BET, TEM, HAADF-STEM, and XPS were conducted to characterize the catalysts. The results revealed that the excellent behavior of Au-Pd/CeO2-rod in benzyl alcohol oxidation was closely related with the smaller size of CeO2 particle, the higher concentration of oxygen defects in support and the higher number of Ce3+ and Pd2+ species on the catalyst surface. The present study on the morphologies of CeO2 support in solvent-free benzyl alcohol oxidation would offer a notable approach for the future catalyst design

Polyethyleneimine-coated MXene quantum dots improve cotton tolerance to Verticillium dahliae by maintaining ROS homeostasis

Verticillium dahliae is a soil-borne hemibiotrophic fungal pathogen that threatens cotton production worldwide. In this study, we assemble the genomes of two V. dahliae isolates: the more virulence and defoliating isolate V991 and nondefoliating isolate 1cd3-2. Transcriptome and comparative genomics analyses show that genes associated with pathogen virulence are mostly induced at the late stage of infection (Stage II), accompanied by a burst of reactive oxygen species (ROS), with upregulation of more genes involved in defense response in cotton. We identify the V991-specific virulence gene SP3 that is highly expressed during the infection Stage II. V. dahliae SP3 knock-out strain shows attenuated virulence and triggers less ROS production in cotton plants. To control the disease, we employ polyethyleneimine-coated MXene quantum dots (PEI-MQDs) that possess the ability to remove ROS. Cotton seedlings treated with PEI-MQDs are capable of maintaining ROS homeostasis with enhanced peroxidase, catalase, and glutathione peroxidase activities and exhibit improved tolerance to V. dahliae. These results suggest that V. dahliae trigger ROS production to promote infection and scavenging ROS is an effective way to manage this disease. This study reveals a virulence mechanism of V. dahliae and provides a means for V. dahliae resistance that benefits cotton production