Seed-mediated controlled growth of rare earth nanocrystals

University of Technology Sydney. Faculty of Science.With relatively large surface areas and tunable composition and morphology, nanoparticles possess unexpected properties comparing with their bulk counterparts. Controlled synthesis and fine-tuning of their composition, morphology, and surface properties are the fundamental cornerstones in nanoscience and nanotechnology towards optimized overall performance of a variety of nanoparticles discovered today. Lanthanide-doped upconversion nanoparticles (UCNPs) are a new family of luminescent nanomaterials attracting a large amount of research interests, because these materials are capable of converting two or more low-energy photons into one high-energy photon. The controlled synthesis of lanthanide-doped UCNPs with fine-tuning the size, shape and composition becomes the next grand challenge aiming to push their real applications. Also, heterogeneous structured UCNPs have the potential to integrate many different functionalities and positively enhance each property within one nanoscale platform. Direct size/shape/composition-control in the conventional synthesis process, however does remain a challenge via the one-pot wet chemical synthesis route. This thesis thus aims to establish new methods for the fabrication of UCNPs with fine-tuning the size, shape and composition. Then, I use these well-controlled nanocrystals to study the optical property at single nanocrystal level. Further, this knowledge is leveraged to develop a robust engineering protocol for fabrication of monodisperse multifunctional luminescent nanocrystals. The outcomes of this thesis not only include a series of knowledge discovered for controlled growth of lanthanide-doped nanomaterials, but also lead to a range of new applications demonstrated, such as super-resolution nanoscopy imaging, single-particle tracking, and multimodal bioimaging. This thesis begins with a comprehensive review of the size-/shape-dependent properties and the controlled wet-chemical synthesis of nanomaterials, especially for the recently developed UCNPs, forming the introduction Chapter 1. In Chapter 2, I provide the full details of materials and methods employed for seed-mediated growth in this thesis. And the following four chapters summarize the core results from 666 synthesis experiments to produce a range of homogeneous nanocrystals (Chapter 3), heterogeneous core@shell@shell nanocrystals (Chapter 5) and single directional grown barcoded nanorods at arbitrary sizes (Chapter 6), as well as a comprehensive characterization and investigation of crystal growth mechanisms (Chapter 4) that underpins these synthesis techniques. In Chapter 7, I summarize the key achievements presented in this thesis and discusses the potentials of using this developed approach for the fabrication of high-quality on-demand hybrid nanocrystals. Also, I discuss their potential application in new nanotechnologies, such as super-resolution imaging, multimodal bioimaging, optogenetics, nanothermometry, photovoltaics, and laser refrigeration

Spatial and Modal Optimal Transport for Fast Cross-Modal MRI Reconstruction

Multi-modal magnetic resonance imaging (MRI) plays a crucial role in comprehensive disease diagnosis in clinical medicine. However, acquiring certain modalities, such as T2-weighted images (T2WIs), is time-consuming and prone to be with motion artifacts. It negatively impacts subsequent multi-modal image analysis. To address this issue, we propose an end-to-end deep learning framework that utilizes T1-weighted images (T1WIs) as auxiliary modalities to expedite T2WIs' acquisitions. While image pre-processing is capable of mitigating misalignment, improper parameter selection leads to adverse pre-processing effects, requiring iterative experimentation and adjustment. To overcome this shortage, we employ Optimal Transport (OT) to synthesize T2WIs by aligning T1WIs and performing cross-modal synthesis, effectively mitigating spatial misalignment effects. Furthermore, we adopt an alternating iteration framework between the reconstruction task and the cross-modal synthesis task to optimize the final results. Then, we prove that the reconstructed T2WIs and the synthetic T2WIs become closer on the T2 image manifold with iterations increasing, and further illustrate that the improved reconstruction result enhances the synthesis process, whereas the enhanced synthesis result improves the reconstruction process. Finally, experimental results from FastMRI and internal datasets confirm the effectiveness of our method, demonstrating significant improvements in image reconstruction quality even at low sampling rates

Numerical simulation of separation shock characteristics of a piston type explosive bolt

A piston type explosive bolt is modeled by using a hydrocodes AUTODYN. The influence of the charge amount on the separation shock is analyzed. The results show that the separation shock of the piston type explosive bolt mainly includes two aspects: the shock caused by explosive detonation and the impact of the piston at the end of stroke. As the charge amount increases, the collision speed of piston first increases and then decreases, and the separation shock first increases and then stabilizes

Enhancing the specificity and efficiency of polymerase chain reaction using polyethyleneimine-based derivatives and hybrid nanocomposites

There is a general necessity to improve the specificity and efficiency of the polymerase chain reaction (PCR), and exploring the PCR-enhancing mechanism still remains a great challenge. In this paper we report the use of branched polyethyleneimine (PEI)-based derivatives and hybrid nanocomposites as a novel class of enhancers to improve the specificity and efficiency of a nonspecific PCR system. We show that the surface-charge polarity of PEI and PEI derivatives plays a major role in their effectiveness to enhance the PCR. Positively charged amine-terminated pristine PEI, partially (50%) acetylated PEI (PEI-Ac50), and completely acetylated PEI (PEI-Ac) are able to improve PCR efficiency and specificity with an optimum concentration order of PEI < PEI-Ac50 < PEI-Ac, whereas negatively charged carboxyl-terminated PEI (PEI-SAH; SAH denotes succinamic acid groups) and neutralized PEI modified with both polyethylene glycol (PEG) and acetyl (Ac) groups (PEI-PEG-Ac) are unable to improve PCR specificity and efficiency even at concentrations three orders of magnitude higher than that of PEI. Our data clearly suggests that the PCR-enhancing effect is primarily based on the interaction between the PCR components and the PEI derivatives, where electrostatic interaction plays a major role in concentrating the PCR components locally on the backbones of the branched PEI. In addition, multiwalled carbon nanotubes modified with PEI and PEI-stabilized gold nanoparticles are also able to improve the PCR specificity and efficiency with an optimum PEI concentration less than that of the PEI alone, indicating that the inorganic component of the nanocomposites may help improve the interaction between PEI and the PCR components. The developed PEI-based derivatives or nanocomposites may be used as efficient additives to enhance other PCR systems for different biomedical applications

Three-dimensional controlled growth of monodisperse sub-50 nm heterogeneous nanocrystals

The ultimate frontier in nanomaterials engineering is to realize their composition control with atomic scale precision to enable fabrication of nanoparticles with desirable size, shape and surface properties. Such control becomes even more useful when growing hybrid nanocrystals designed to integrate multiple functionalities. Here we report achieving such degree of control in a family of rare-earth-doped nanomaterials. We experimentally verify the co-existence and different roles of oleate anions (OA-) and molecules (OAH) in the crystal formation. We identify that the control over the ratio of OA- to OAH can be used to directionally inhibit, promote or etch the crystallographic facets of the nanoparticles. This control enables selective grafting of shells with complex morphologies grown over nanocrystal cores, thus allowing the fabrication of a diverse library of monodisperse sub-50 nm nanoparticles. With such programmable additive and subtractive engineering a variety of three-dimensional shapes can be implemented using a bottom-up scalable approach

Seizing the window of opportunity to mitigate the impact of climate change on the health of Chinese residents

The health threats posed by climate change in China are increasing rapidly. Each province faces different health risks. Without a timely and adequate response, climate change will impact lives and livelihoods at an accelerated rate and even prevent the achievement of the Healthy and Beautiful China initiatives. The 2021 China Report of the Lancet Countdown on Health and Climate Change is the first annual update of China’s Report of the Lancet Countdown. It comprehensively assesses the impact of climate change on the health of Chinese households and the measures China has taken. Invited by the Lancet committee, Tsinghua University led the writing of the report and cooperated with 25 relevant institutions in and outside of China. The report includes 25 indicators within five major areas (climate change impacts, exposures, and vulnerability; adaptation, planning, and resilience for health; mitigation actions and health co-benefits; economics and finance; and public and political engagement) and a policy brief. This 2021 China policy brief contains the most urgent and relevant indicators focusing on provincial data: The increasing health risks of climate change in China; mixed progress in responding to climate change. In 2020, the heatwave exposures per person in China increased by 4.51 d compared with the 1986–2005 average, resulting in an estimated 92% increase in heatwave-related deaths. The resulting economic cost of the estimated 14500 heatwave-related deaths in 2020 is US$176 million. Increased temperatures also caused a potential 31.5 billion h in lost work time in 2020, which is equivalent to 1.3% of the work hours of the total national workforce, with resulting economic losses estimated at 1.4% of China’s annual gross domestic product. For adaptation efforts, there has been steady progress in local adaptation planning and assessment in 2020, urban green space growth in 2020, and health emergency management in 2019. 12 of 30 provinces reported that they have completed, or were developing, provincial health adaptation plans. Urban green space, which is an important heat adaptation measure, has increased in 18 of 31 provinces in the past decade, and the capacity of China’s health emergency management increased in almost all provinces from 2018 to 2019. As a result of China’s persistent efforts to clean its energy structure and control air pollution, the premature deaths due to exposure to ambient particulate matter of 2.5 μm or less (PM2.5) and the resulting costs continue to decline. However, 98% of China’s cities still have annual average PM2.5 concentrations that are more than the WHO guideline standard of 10 μg/m3. It provides policymakers and the public with up-to-date information on China’s response to climate change and improvements in health outcomes and makes the following policy recommendations. (1) Promote systematic thinking in the related departments and strengthen multi-departmental cooperation. Sectors related to climate and development in China should incorporate health perspectives into their policymaking and actions, demonstrating WHO’s and President Xi Jinping’s so-called health-in-all-policies principle. (2) Include clear goals and timelines for climate-related health impact assessments and health adaptation plans at both the national and the regional levels in the National Climate Change Adaptation Strategy for 2035. (3) Strengthen China’s climate mitigation actions and ensure that health is included in China’s pathway to carbon neutrality. By promoting investments in zero-carbon technologies and reducing fossil fuel subsidies, the current rebounding trend in carbon emissions will be reversed and lead to a healthy, low-carbon future. (4) Increase awareness of the linkages between climate change and health at all levels. Health professionals, the academic community, and traditional and new media should raise the awareness of the public and policymakers on the important linkages between climate change and health.</p