From plasmon-enhanced molecular spectroscopy to plasmon-mediated chemical reaction

该论文在田中群教授指导下完成，第一作者为iChEM中心2013级博士生战超。 表面等离激元效应可以在时间和空间上实现光子、电子和热能的重新分配。表面等离激元增强分子光谱由于其具有超高的灵敏度在过去四十年里引起了人们的广泛关注并得到快速发展。近年，表面等离激元效应介导的化学反应得到广泛的关注。该综述系统介绍了表面等离激元效应、表面等离激元增强分子光谱和表面等离激元介导化学反应的背景和基础理论，并与传统热化学、光化学和光催化进行对比。通过将表面等离激元介导化学反应与表面等离激元增强分子光谱以及其它反应类型进行比较，归纳出表面等离激元介导化学反应的独特科学内涵，展示了较完整的表面等离激元介导化学反应的物理化学图像。系统深入地分析了表面等离激元介导化学反应的特色和优势、影响因素及其之间的关联性，进而讨论高效利用表面等离激元来介导化学反应的策略，并对该领域做了展望。【Abstract】The excitation of surface plasmons (SPs), collective oscillation of conduction electrons in nanostructures, can redistribute photon, electron and heat energy in time and space. Making use of this ability, plasmon-enhanced molecular spectroscopies (PEMS) with ultra-high sensitivity and surface selectivity have attracted much attention and developed significantly in the past four decades. Recently, SPs have impacted the discipline of chemistry, through plasmon-mediated chemical reactions (PMCR). PMCR exhibit some obvious differences from, and potential advantages over traditional thermal-chemistry, photo-chemistry and photo-catalysis. Our physicochemical understanding of PMCR is still far from complete. In this review, we analyze the common ground and distinctive features of PEMS and PMCR; comparing as well, PMCR and traditional photo-chemical and thermal-chemical reactions. We then discuss how to advance PMCR by rationally designing and fabricating plasmonic nanostructures, selecting suitable surface/interface mediators and teaming them synergistically.We are deeply grateful to M. Moskovits for his very helpful suggestions and careful academic and English editing throughout the manuscript. This work is financially supported by the National Natural Science Foundation of China (21533006, 21621091, 91427304 and 21403180) and the Ministry of Science and Technology of China (2015CB932300). 研究工作得到国家自然科学基金委(21533006、21621091、91427304）和科技部重大科学研究计划（2015CB932300）的支持

Plasmon-Mediated Chemical Reactions on Nanostructures Unveiled by Surface-Enhanced Raman Spectroscopy.

Surface plasmons (SPs) originating from the collective oscillation of conduction electrons in nanostructured metals (Au, Ag, Cu, etc.) can redistribute not only the electromagnetic fields but also the excited carriers (electrons and holes) and heat energy in time and space. Therefore, SPs can engage in a variety of processes, such as molecular spectroscopy and chemical reaction. Recently, plenty of demonstrations have made plasmon-mediated chemical reactions (PMCRs) a very active research field and make it as a promising approach to facilitate light-driven chemical reactions under mild conditions. Concurrently, making use of the same SPs, surface-enhanced Raman spectroscopy (SERS) with a high surface sensitivity and energy resolution becomes a powerful and commonly used technique for the in situ study of PMCRs. Typically, various effects induced by SPs, including the enhanced electromagnetic field, local heating, excited electrons, and excited holes, can mediate chemical reactions. Herein, we use the para-aminothiophenol (PATP) transformation as an example to elaborate how SERS can be used to study the mechanism of PMCR system combined with theoretical calculations. First, we distinguish the chemical transformation of PATP to 4,4’-dimercaptoazobenzene (DMAB) from the chemical enhancement mechanism of SERS through a series of theoretical and in situ SERS studies. Then, we focus on disentangling the photothermal, hot electrons, and "hot holes" effects in the SPs-induced PATP-to-DMAB conversion. Through varying the key reaction parameters, such as the wavelength and intensity of the incident light, using various core-shell plasmonic nanostructures with different charge transfer properties, we extract the key factors that influence the efficiency and mechanism of this reaction. We confidently prove that the transformation of PATP can occur on account of the oxygen activation induced by the hot electrons or because of the action of hot holes in the absence of oxygen and confirm the critical effect of the interface between the plasmonic nanostructure and reactants. The products of these two process are different. Furthermore, we compare the correlation between PMCRs and SERS, discuss different scenario of PMCRs in situ studied by SERS, and provide some suggestions for the SERS investigation on the PMCRs. Finally, we comment on the mechanism studies on how to distinguish the multieffects of SPs and their influence on the PMCRs, as well as on how to power the chemical reaction and regulate the product selectivity in higher efficiencies

Significance of ST-segment deviation in patients with acute pulmonary embolism and negative T waves

Background: Common electrocardiogram (ECG) manifestations in acute pulmonary em­bolism (APE) include ST-segment deviation (STDV) along with negative T-waves (NTW). STDV could occur in 3 typical ischemic patterns: (i) the left ventricular (LV) subendocardial ischemic pattern; (ii) the right ventricular (RV) transmural ischemic pattern; and (iii) the LV subendocardial plus RV transmural ischemic pattern. The purpose of this study was to evalu­ate the relationship of STDV and adverse clinical outcomes and to identify the relationship of relatively normal ECG and favorable clinical outcomes. Methods: Retrospective analysis of electronic charts in APE patients was performed in a tertiary hospital. ECGs on admission were obtained and classified as with or without STDV. Adverse clinical outcomes were defined as need to intensify therapy and 30-day mortality. Relatively normal ECG was defined as without any STDV, abnormal QRS morphology in lead V1 and S1Q3T3. Results: From a total of 210 patients with NTW, 131 had STDV ≥ 0.1 mV, while 79 did not. Patients with STDV had worse evolution: higher incidence of dyspnea, hypotension, cardiogen­ic shock, intensification of therapy, and death compared to patients without STDV (p = 0.001 for each variable). The majority (89%) of the patients with STDV presented with 1 of the 3 typical ischemic ECG patterns. LV subendocardial ischemic pattern (OR = 4.963, p = 0.004), RV transmural ischemic pattern (OR = 3.128, p = 0.021) and LV subendocardial plus RV transmural ischemic pattern (OR = 3.036, p = 0.017) independently predicted the need to intensify therapy. RV transmural ischemic pattern (OR = 4.227, p = 0.031) and LV subendocardial plus RV transmural ischemic pattern (OR = 4.022, p = 0.032) independently predicted 30-day mortality. Compared to the patients with abnormal ECG, the patients with relatively normal ECG had a significant lower incidence of death (0% vs. 16%; p = 0.001) and need to intensify therapy during hospitalization (6% vs. 30%; p = 0.002). Conclusions: Ischemic ECG patterns are common ECG manifestations of APE and predict worse evolution and 30-day mortality. Additionally, relatively normal ECGs may associate with favorable clinical outcomes

A novel planarization method based on photoinduced confined chemical etching

National Science Foundation of China [91023043, 21021002, 91023006]A photoinduced confined chemical etching system based on TiO2 nanotube arrays is developed for the planarization of the copper surface, which is proved to be a prospective stress-free chemical planarization method for metals and semiconductors

Electrochemical mechanical micromachining based on confined etchant layer technique

National Science Foundation of China [91023006, 91023047, 91023043, 21061120456, 21021002]; Natural Science Foundation of Fujian Province of China [2012J06004]; Fundamental Research Funds for the Central Universities [2010121022]; Scientific Research Foundation for the Returned Overseas Chinese Scholars (State Education Ministry)The confined etchant layer technique (CELT) has been proved an effective electrochemical microfabrication method since its first publication at Faraday Discussions in 1992. Recently, we have developed CELT as an electrochemical mechanical micromachining (ECMM) method by replacing the cutting tool used in conventional mechanical machining with an electrode, which can perform lathing, planing and polishing. Through the coupling between the electrochemically induced chemical etching processes and mechanical motion, ECMM can also obtain a regular surface in one step. Taking advantage of CELT, machining tolerance and surface roughness can reach micro-or nano-meter scale

Single-Molecule Plasmonic Optical Trapping

人们对于在常温常压条件下尤其是溶液环境中俘获或者操控微观粒子的追求从未停止，以期不断减少可操控的微观粒子的尺寸，最终实现单分子操控的目标。化学化工学院田中群教授和洪文晶教授团队合作，利用等离激元光学纳米间隙实现单分子的直接捕获与释放。该工作由化学化工学院田中群教授、洪文晶教授以及萨本栋微米纳米科学技术研究院杨扬副教授共同指导，由化学化工学院已毕业博士生战超提出思路并设计实验、与萨本栋微米纳米研究院已毕业硕士生王干共同完成主要实验工作，已毕业博士生易骏完成理论模拟工作。魏珺颖硕士、博士生李之豪、陈招斌高工和师佳副教授参与了部分研究和课题讨论。【Abstract】The volume of the object that can be manipulated in solution is continuously decreasing toward an ultimate goal of a single molecule. However, Brownian motions suppress the molecular trapping. To date, free-molecule trapping in solution has not been accomplished. Here, we develop a strategy to directly trap, investigate, and release single molecules (∼2 nm) in solution by using an adjustable plasmonic optical nanogap, which has been further applied for selective single-molecule trapping. Comprehensive experiments and theoretical simulations demonstrated that the trapping force originated from plasmonic nanomaterials. This technique opens an avenue to manipulate single molecules and other objects in the size range of primary interest for physics, chemistry, and life and material sciences without the limitations of strong bonding group, ultra-high vacuum, and ultra-low temperature, and makes possible controllable single-molecule manipulation and investigation as well as bottom-up construction of nanodevices and molecular machines.This work is financially supported by the National Natural Science Foundation of China (21533006, 21621091, 21673195, 21973079, and 21722305), and the National Key R&D Program (2017YFA0204902, 2015CB932300). 该工作得到国家自然科学基金、国家重点研发计划课题的资助，以及固体表面物理化学国家重点实验室、能源材料化学协同创新中心的支持

Tissue microarray analysis reveals a tight correlation between protein expression pattern and progression of esophageal squamous cell carcinoma

BACKGROUND: The development of esophageal squamous cell carcinoma (ESCC) progresses a multistage process, collectively known as precursor lesions, also called dysplasia (DYS) and carcinoma in situ (CIS), subsequent invasive lesions and final metastasis. In this study, we are interested in investigating the expression of a variety of functional classes of proteins in ESCC and its precursor lesions and characterizing the correlation of these proteins with ESCC malignant progression. METHODS: Fas, FADD, caspase 8, CDC25B, fascin, CK14, CK4, annexin I, laminin-5γ2 and SPARC were analyzed using immunohistochemistry on tissue microarray containing 205 ESCC and 173 adjacent precursor lesions as well as corresponding normal mucosa. To confirm the immunohistochemical results, three proteins, fascin, CK14 and laminin-5γ2, which were overexpressed in ESCC on tissue microarray, were detected in 12 ESCC cell lines by Western blot assay. RESULTS: In ESCC and its precursor lesions, FADD, CDC25B, fascin, CK14, laminin-5γ2 and SPARC were overexpressed, while Fas, caspase 8, CK4 and annexin I were underexpressed. The abnormalities of these proteins could be classified into different groups in relation to the stages of ESCC development. They were "early" corresponding to mild and moderate DYS with overexpression of fascin, FADD and CDC25B and underexpression of Fas, caspase 8, CK4 and annexin I, "intermediate" to severe DYS and CIS with overexpression of FADD and CK14, and "late" to invasive lesions (ESCC) and to advanced pTNM stage ESCC lesions with overexpression of CK14, laminin-5γ2 and SPARC. CONCLUSION: Analyzing the protein expression patterns of Fas, FADD, caspase 8, CDC25B, fascin, CK14, CK4, annexin I, laminin-5γ2 and SPARC would be valuable to develop rational strategies for early detection of lesions at risk in advance as well as for prevention and treatment of ESCC

Neutrino Physics with JUNO

The Jiangmen Underground Neutrino Observatory (JUNO), a 20 kton multi-purposeunderground liquid scintillator detector, was proposed with the determinationof the neutrino mass hierarchy as a primary physics goal. It is also capable ofobserving neutrinos from terrestrial and extra-terrestrial sources, includingsupernova burst neutrinos, diffuse supernova neutrino background, geoneutrinos,atmospheric neutrinos, solar neutrinos, as well as exotic searches such asnucleon decays, dark matter, sterile neutrinos, etc. We present the physicsmotivations and the anticipated performance of the JUNO detector for variousproposed measurements. By detecting reactor antineutrinos from two power plantsat 53-km distance, JUNO will determine the neutrino mass hierarchy at a 3-4sigma significance with six years of running. The measurement of antineutrinospectrum will also lead to the precise determination of three out of the sixoscillation parameters to an accuracy of better than 1\%. Neutrino burst from atypical core-collapse supernova at 10 kpc would lead to ~5000inverse-beta-decay events and ~2000 all-flavor neutrino-proton elasticscattering events in JUNO. Detection of DSNB would provide valuable informationon the cosmic star-formation rate and the average core-collapsed neutrinoenergy spectrum. Geo-neutrinos can be detected in JUNO with a rate of ~400events per year, significantly improving the statistics of existing geoneutrinosamples. The JUNO detector is sensitive to several exotic searches, e.g. protondecay via the $p\to K^++\bar\nu$ decay channel. The JUNO detector will providea unique facility to address many outstanding crucial questions in particle andastrophysics. It holds the great potential for further advancing our quest tounderstanding the fundamental properties of neutrinos, one of the buildingblocks of our Universe