科研成果

Abstract We present a novel and effective photocatalytic method for the methylation of ?-diketones with controllable degrees of deuterium incorporation via development of new methyl sources. By utilizing a methylamine-water system as the methyl precursor and a cascade assembly strategy for deuteration degree control, we synthesized methylated compounds with varying degrees of deuterium incorporation, showcasing the versatility of this approach. We examined a range of ?-diketone substrates and synthesized key intermediates for drug and bioactive compounds with varying degrees of deuterium incorporation, ranging from 0 to 3. We also investigated and discussed the postulated reaction pathway. This work demonstrates the utility of readily available reagents, methylamines and water, as a new methyl source, and provides a simple and efficient strategy for the synthesis of degree-controllable deuterium-labelled compounds.

Hydroxyl radical (•OH) and sulfate radical (SO4•−) produced in advanced oxidation processes (AOPs) have been widely studied for organic contaminants degradation, however, the different radical characteristics and reaction mechanisms on organics degradation are still needed. In this study, a homogeneous Co(II)/peroxymonosulfate activation system was established for caffeine (CAF) degradation, and pH was controlled to regulate the radicals production. The different attack routes driven by SO4•− and •OH were deeply explored by transformation products (TPs) identification and theoretical calculations. Specifically, a method on dynamic electronic structure analysis of reactants (R), transition state (TS) and intermediates (IMs) during reaction was proposed, which was applied to elucidate the underlying mechanism of CAF oxidation by •OH and SO4•− at the molecular orbital level. In total, SO4•− is kinetically more likely to attack CAF than •OH due to its higher oxidation potential and electrophilicity index. Single electron transfer reaction (SET) is only favorable for SO4•−due to its higher electron affinity than •OH, while only •OH can react with CAF via hydrogen atom abstraction (HAA) route. Radical adduct formation (RAF) is the most favorable route for both •OH and SO4•− attack according to both kinetics and thermodynamics results. These findings can significantly promote the understanding on the degradation mechanism of organic pollutants driven by •OH and SO4•− in AOPs.

This paper reviews current progress and future challenges of digital technology applications for energy system transition in the context of net-zero. A list of case studies for such digitization enabled optimal design and operation of energy systems at various temporal and spatial scales are reviewed in the paper, including model predictive control, enterprise-wide optimization, eco-industrial park data management, and smart city. The key technological innovations across these applications, such as virtual representation of physical entities, ontological knowledge base, data-driven high dimensional surrogate model based parameterization are also inspected in the paper. Future challenges in terms of data privacy and security are also discussed as potential barriers for digitalization enabled net-zero energy system transition.

Steam-assisted gravity drainage (SAGD) is a mature heavy oil thermal recovery technology but inherently limited to low recovery efficiency at mid-late stage due to the increasing heat loss in the steam chamber. Here, the dimethyl ether (DME)-assisted SAGD technology and its relevant transport and interfacial properties are specifically investigated through physical 2D heavy oil simulation. A total of four-set physical experiments, with different DME injection ratios, were conducted and compared with the traditional SAGD. The experimental results indicate DME is capable of reducing the heavy oil’s viscosity and interfacial tension at high temperatures. Three stages, rising, lateral expansion, and descending stages, are determined in the SAGD steam chamber’s development; the mid-late SAGD stage is defined when the steam chamber extends to the caprock boundary. With DME additions at the mid-late SAGD stage, higher oil recovery factor and sweep efficiency could be reached and the dew point temperature of steam chamber’s lead decreases by 0.7–1.8 °C. The optimum gas–water ratio is determined to be 3:1, with the fastest oil recovery growth and the highest final cumulative oil-vapor ratio of 0.163. This study provides reliable experimental bases and valuable analyses for the DME-SAGD technology and its application in heavy oil reservoirs.

Providing forecasts for ultra-long time series plays a vital role in various activities, such as investment decisions, industrial production arrangements, and farm management. This paper develops a novel distributed forecasting framework to tackle the challenges of forecasting ultra-long time series using the industry-standard MapReduce framework. The proposed model combination approach retains the local time dependency. It utilizes a straightforward splitting across samples to facilitate distributed forecasting by combining the local estimators of time series models delivered from worker nodes and minimizing a global loss function. Instead of unrealistically assuming the data generating process (DGP) of an ultra-long time series stays invariant, we only make assumptions on the DGP of subseries spanning shorter time periods. We investigate the performance of the proposed approach with AutoRegressive Integrated Moving Average (ARIMA) models using the real data application as well as numerical simulations. Our approach improves forecasting accuracy and computational efficiency in point forecasts and prediction intervals, especially for longer forecast horizons, compared to directly fitting the whole data with ARIMA models. Moreover, we explore some potential factors that may affect the forecasting performance of our approach.

Over the past 40 years, global tertiary expansion has been driven in part by the rise of the non-university sector. The growth of this sector, which includes vocational colleges, also contributes to increasingly diverse national higher education systems. Prior research has focused on inter-state variation in national systems, while very few studies have explored intra-state variation in the expansion of non-university sector. Building on the policy innovation and diffusion model, this study uses event history analysis to investigate key drivers behind Chinese prefecture cities' adoption of vocational colleges during the latest tertiary education expansion. The study employs a rich panel dataset from 273 Chinese cities between 2000 and 2014. Findings suggest that the socioeconomic and the politico-institutional contexts matter the most for cities' policy adoption, and the influence of policy diffusion is negative but not significant. Moreover, there is substantial heterogeneity across time and region. The characteristics of early adopters significantly differ from those of late adopters, and the diffusion paths vary within and across regions. This study illustrates that the emergence of sub-national government affiliated non-university institutions is driven by a complex combination of socioeconomic, politico-institutional, and policy forces. Results highlight the regional contextual factors that may override coercive pressure from national strategies to promote the non-university sector expansion and the structural diversity in the context of less developed economies.

Previous studies on the determinants of household tourism expenditure have assumed that households independently determine their tourism expenditure. However, the possible influence of neighbours on tourism expenditure has been overlooked. This study is the first to apply spatial lag analysis to investigate the neighbour effect in the determination of rural household tourism expenditure. The results indicate that there is a significant neighbour effect on the tourism expenditure of rural households. This neighbour effect varies by region and by household head attributes. This paper suggests that the neighbour effect does help to explain household tourism consumption in rural areas.

Electron paramagnetic resonance (EPR) spectroscopy using sterically hindered amine is extensively applied to detect singlet oxygen (1O2) possibly generated in advanced oxidation processes. However, EPR-detectable 1O2 signals were observed in not only the 1O2-dominated hydrogen peroxide (H2O2)/hypochlorite (NaClO) reaction but surprisingly also the 1O2-absent Fe(II)/H2O2, UV/H2O2, and ferrate [Fe(VI)] process with even stronger intensities. By taking advantage of the characteristic reaction between 1O2 and 9,10-diphenyl-anthracene and near-infrared phosphorescent emission of 1O2, 1O2 was excluded in the Fe(II)/H2O2, UV/H2O2, and Fe(VI) process. The false detection of 1O2 was ascribed to the direct oxidation of hindered amine to piperidyl radical by reactive species [e.g., •OH and Fe(VI)/Fe(V)/Fe(IV)] via hydrogen transfer, followed by molecular oxygen addition (forming a piperidylperoxyl radical) and back reaction with piperidyl radical to generate a nitroxide radical, as evidenced by the successful identification of a piperidyl radical intermediate at 100 K and theoretical calculations. Moreover, compared to the highly oxidative species (e.g., •OH and high-valence Fe), the much lower reactivity of 1O2 and the profound nonradiative relaxation of 1O2 in H2O resulted it too selective and inefficient in organic contaminant destruction. This study demonstrated that EPR-based 1O2 detection could be remarkably misled by common oxidative species and thereby jeopardize the understandings on 1O2.

This research develops a spatial analytical framework to investigate the spatial distribution and dynamic evolution of academic patent commercialization. The results showed that the gravity center of academic patents commercialization in China shifted from southwest to northeast from 2010 to 2019, showing the characteristics of alternating spatial convergence and spatial divergence. Moreover, economic development will promote the centralization of the commercialization of academic patents, while local fiscal science and technology expenditure, development of local public libraries, regional urbanization and traffic decentralization will promote the decentralization of the commercialization of academic patents. Those findings affirm that spatial convergence or divergence of academic patent commercialization is the dynamic result of the contrast between the two forces of centralization and decentralization. This study provides an analytical framework for scholars to explore the dynamic spatial pattern evolution of academic patent commercialization.

Persistent, mobile, and toxic (PMT) substances are affecting the safety of drinking water and are threatening the environment and human health. Many PMT substances are used in industrial processing or consumer products, but their sources and emissions mostly remain unclear. This study presents a long-term source distribution and emission estimation of melamine, a high-production-volume PMT substance of emerging global concern. The results indicate that in China, approximately 1858.7 kilotonnes (kt) of melamine were released into the water (∼58.9%), air (∼27.0%), and soil systems (∼14.1%) between 1995 and 2020, mainly from its production and use in the decorative panels, textiles, and paper industries. The textile and paper industries have the highest emission-to-consumption ratios, with more than 90% emissions per unit consumption. Sewage treatment plants are the largest source of melamine in the environment for the time being, but in-use products and their wastes will serve as significant melamine sources in the future. The study prompts priority action to control the risk of PMT substances internationally.

The association between pandemic experience and immediate mental health risks, such as depression, is well-documented, yet the long-term effects remain unclear. This study examines the impact of early childhood exposure to the 2003 SARS pandemic on adulthood mental health after 17 years in China, using data from the 2020 China Family Panel Studies (CFPS). The analysis included 6289 participants, aged 3 to 30 years during the SARS outbreak, with an average age of 35.3 years at the time of survey. Adulthood mental health was assessed using Center for Epidemiologic Studies Depression Scale (CESD) and an indicator of clinical depression. The severity of local SARS outbreaks was assessed by cumulative cases per 10,000 population. Results show that each additional case per 10,000 population was linked to a 1.617-fold (95% confidence interval (CI): 1.425–1.836) increase in odds of depression after 17 years for younger children (aged 3–12 years in 2003) relative to older cohorts (aged 13-30). This risk was higher in children from rural areas (adjusted odds ratio (aOR) 3.64; 95% CI 2.92–4.55), with poor physical health (1.98; 1.59–2.48), and from low-income families (2.87; 2.03–4.05). The childhood pandemic experience elevated the probability of developing depression-prone personality traits, which contributes to the enduring impact of childhood pandemic experiences on adulthood mental health. These findings highlight the long-lasting psychological impact of early-childhood pandemic exposure, underscoring the need for targeted interventions to mitigate its effects on the younger generation and emphasizing the importance of monitoring long-term mental health and personality development in children post-pandemics, particularly in light of COVID-19.

Earth's mantle has a two-layered structure, with the upper and lower mantle domains separated by a seismic discontinuity at about 660 km (refs. 1,2 ). The extent of mass transfer between these mantle domains throughout Earth's history is, however, poorly understood. Continental crust extraction results in Ti-stable isotopic fractionation, producing isotopically light melting residues 3–7 . Mantle recycling of these components can impart Ti isotope variability that is trackable in deep time. We report ultrahigh-precision 49 Ti/ 47 Ti ratios for chondrites, ancient terrestrial mantle-derived lavas ranging from 3.8 to 2.0 billion years ago (Ga) and modern ocean island basalts (OIBs). Our new Ti bulk silicate Earth (BSE) estimate based on chondrites is 0.052 ± 0.006‰ heavier than the modern upper mantle sampled by normal mid-ocean ridge basalts (N-MORBs). The 49 Ti/ 47 Ti ratio of Earth's upper mantle was chondritic before 3.5 Ga and evolved to a N-MORB-like composition between approximately 3.5 and 2.7 Ga, establishing that more continental crust was extracted during this epoch. The +0.052 ± 0.006‰ offset between BSE and N-MORBs requires that <30% of Earth's mantle equilibrated with recycled crustal material, implying limited mass exchange between the upper and lower mantle and, therefore, preservation of a primordial lower-mantle reservoir for most of Earth's geologic history. Modern OIBs record variable 49 Ti/ 47 Ti ratios ranging from chondritic to N-MORBs compositions, indicating continuing disruption of Earth's primordial mantle. Thus, modern-style plate tectonics with high mass transfer between the upper and lower mantle only represents a recent feature of Earth's history.