单个铂酞菁分子在正负偏压激发下的电致发光特性研究

本文利用扫描隧道显微镜诱导发光技术,系统地研究了铂酞菁分子在正负偏压激发下的电致发光行为及其相关的电子激发机制. 铂酞菁分子在正负偏压激发下均可以发光,但发光特征有所不同. 在负偏压激发下,观察到了源于中性PtPc分子LUMO→HOMO跃迁的峰位在637 nm处的荧光峰. 荧光强度在三个不同的激发区域呈阶梯状增加. 当激发偏压处于区域(I)时,可以产生较强的荧光,其主导激发机制是载流子注入激发机制;当激发偏压处于区域(II)时,可以产生中等发光强度的荧光,其主导激发机制是非弹性电子散射激发机制;当激发偏压处于区域(III)时,激发电子能量小于荧光光子能量,存在上转换现象,荧光峰非常弱,其激发过程需要自旋三重态作为中继态,并由载流子注入和非弹性电子散射两种机制共同作用产生. 在正偏压激发下,分子的电致发光光谱特征变得更加复杂,具有多个发光峰. 911 nm处的尖锐发光峰起源于PtPc^-阴离子的LUMO+1→LUMO跃迁,其激发主要是由载流子注入激发机制主导.     

Controlled-NOT Gate Based on the Rydberg States of Surface Electrons

Due to the long coherence time and efficient manipulation, the surface electron (SE) provides a perfect 2D platform for quantum computation and quantum simulation. In this work, a theoretical scheme to realize the controlled-NOT gate is proposed, where the two-qubit system is encoded on the four-level Rydberg structure of SE. The state transfer is achieved by a three-level structure with an intermediate level. By simultaneously driving the SE with two external electromagnetic fields, the dark state in the electromagnetically induced transparency effect is exploited to suppress the population of the most dissipative state and increase the robustness against dissipation. The fidelity of the scheme is 0.9989 with experimentally achievable parameters.     

Formation of quaternary all-d-metal Heusler alloy by Co doping fcc type Ni2MnV and mechanical grinding induced B2-fcc transformation

The structure of the all-d-metal alloy Ni$_{50-x}$Co$_{x}$Mn$_{25}$V$_{25}$ ($x = 0$-50) is investigated by using theoretical and experimental methods. The first-principles calculations indicate that the most stable structure of the Ni$_{2}$MnV alloy is face-centered cubic (fcc) type structure with ferrimagnetic state and the equilibrium lattice constant is 3.60 Å, which is in agreement with the experimental result. It is remarkable that replacing partial Ni with Co can turn the alloy from the fcc structure to the B2-type Heusler structure as Co content $x > 37$ by using the melting spinning method, implying that the d-d hybridization between Co/Mn elements and low-valent elements V stabilizes the Heusler structure. The Curie temperature $T_{\rm C}$ of all-d-metal Heuser alloy Ni$_{50-x}$Co$_{x}$Mn$_{25}$V$_{25}$ ($x > 37$) increases almost linearly with the increase of Co due to that the interaction of Co-Mn is stronger than that of Ni-Mn. A magnetic transition from ferromagnetic state to weak magnetic state accompanying with grinding stress induced transformation from B2 to the dual-phase of B2 and fcc has been observed in these all-d-metal Heusler alloys. This phase transformation and magnetic change provide a guide to overcome the brittleness and make the all-d-metal Heusler alloy interesting in stress and magnetic driving structural transition.     

Primordial black holes and third order scalar induced gravitational waves

The process of primordial black hole (PBH) formation is inevitably accompanied by scalar induced gravitational waves (SIGWs). The strong correlation between PBH and SIGW signals may offer a promising approach to detecting PBHs in upcoming gravitational wave experiments, such as the Laser Interferometer Space Antenna (LISA). We investigate third order SIGWs during a radiation-dominated era in the case of the monochromatic primordial power spectrum \begin{document}$ \mathcal{P}_{\zeta}=A_{\zeta}k_*\delta\left(k-k_*\right) $\end{document}. For LISA observations, the relationships between the signal-to-noise ratio (SNR) and monochromatic primordial power spectrum are studied systematically, revealing that the effects of third order SIGWs extend the cutoff frequency from \begin{document}$ 2f_* $\end{document} to \begin{document}$ 3f_* $\end{document} and lead to an approximately 200% increase in the SNR for the frequency band from \begin{document}$ 10^{-5} $\end{document}Hz to \begin{document}$ 1.6\times 10^{-3} $\end{document}Hz, corresponding to PBHs with masses in the range \begin{document}$4\times 10^{-12}M_{\odot} \sim 10^{-7}M_{\odot}$\end{document}. We find that there is a critical value, \begin{document}$ A_*=1.76\times 10^{-2} $\end{document}, for the amplitude of the monochromatic primordial power spectra, such that when \begin{document}$ A_{\zeta}>A_* $\end{document}, the energy density of third order SIGWs is larger than that of second order SIGWs.     

Near threshold nucleation and growth of cavitation bubbles generated with a picosecond laser

The nucleation and growth of cavitation bubbles few micrometers in size in water generated by a 60 ps 515 nm fiber laser is observed and visualized near nucleation threshold. The study is performed by monitoring the plasma size, the cavitation bubble size and the emitted shock waves. The latter two aspects are supported by the Gilmore model using a Noble-Abel-stiffened-gas (NASG) equations of state. For the first time, two types of cavitation events are identified and visualized that exhibit a difference of more than two orders of magnitude in the excitation energy converted to mechanical effects with minimal change in excitation laser pulse energy. The result is localized cavitation and reduced mechanical stress on water-based media with potentially positive implications for laser treatments of biological tissue.     

A New,Highly Potent 1,8‐Naphthalimide‐based Fluorescence “Turn off” Chemosensor Capable of Cu2+ Detection in China's Yellow River Water Samples

A new 1,8‐naphthalimide‐based fluorescence “turn off” chemosensor, N‐phenyl‐4‐(3,3′‐((2‐aminoethyl)azanediyl)dipropanoic acid)‐1,8‐naphthalimide ( MAST ), for the detection of Cu²⁺ was synthesized. Upon treatment with Cu²⁺, in coexistence with various competitive metal ions in HEPES‐buffered dimethylsulfoxide (DMSO) solution (v/v, 1:1; pH 7.4), MAST displayed a high selectivity toward Cu²⁺ with a fluorescence quenching of 83.67%. Additionally, a good linear response of MAST for the detection of Cu²⁺ was obtained in the concentration range of 10 × 10⁻⁶ to 50 × 10⁻⁶ M. A 1:1 stoichiometric interaction of MAST with Cu²⁺ was observed, and the association constant and detection limit were calculated to be 1.37 × 10⁶ and 0.69 × 10⁻⁸ M, respectively. The sensing mechanism of the chemosensor toward Cu²⁺ was proposed due to the effect of the paramagnetic nature of Cu²⁺ and reverse‐photo‐induced electron transfer (PET) process. Ultimately, the proposed chemosensor was applied to quantify Cu²⁺ in real‐world water samples, with excellent recovery rates of 98.00–109.80% observed.     

激光诱导击穿光谱结合CARS变量选择方法定量检测倍硫磷含量

利用双脉冲激光诱导击穿光谱(LIBS)技术对溶液中的倍硫磷含量进行定量检测。采用二通道高精度光谱仪采集不同浓度倍硫磷样品在206.28~481.77 nm波段的LIBS光谱,并对光谱进行多元散射校正(MSC)、标准正态变量变换(SNV)及3点平滑预处理,根据偏最小二乘(PLS)建模确定最优的预处理方法。在此基础上,利用竞争性自适应重加权算法(CARS)筛选与倍硫磷相关的重要变量,然后应用PLS回归建立溶液中倍硫磷含量的定量分析模型,并与单变量定量分析模型及未变量选择的PLS定量分析模型进行比较。结果表明,相比单变量定量分析模型及原始光谱PLS定量分析模型,CARS-PLS定量分析模型的性能更优,其模型的校正集和预测集的决定系数及平均相对误差分别为0.969 4、15.537%和0.995 9、5.016%。此外,与原始光谱PLS模型相比,CARS-PLS模型仅使用其中1.9%的波长变量,但预测集平均误差却由9.829%下降为5.016%。由此可见,LIBS技术检测溶液中的倍硫磷含量具有一定的可行性,且CARS方法能简化定量分析模型,提高模型的预测精度。     

毛细管电泳-激光诱导荧光检测法测定卡托普利和N-乙酰-L-半胱氨酸

建立了一种高效、快速的毛细管电泳分离-激光诱导荧光(CE-LIF)检测卡托普利(CAP)和N-乙酰-L-半胱氨酸(NAC)的分析方法。采用1,3,5,7-四甲基-8-溴甲基-二氟二硼-二吡咯甲川(TMMB-Br)为柱前衍生试剂,在50 mmol/L磷酸盐缓冲溶液(pH=8.5)中,40℃下进行衍生反应10min。以荧光素为内标,25mmol/L硼酸盐缓冲溶液(pH=9.5)为电泳背景电解质,14min内达到基线分离。CAP和NAC的检出限分别为0.65nmol/L、0.76nmol/L。将该方法应用于人体尿液和血清中这两种物质的测定,回收率在97.0%~105.7%之间。     

Stimulus‐Responsive Nanoparticles and Associated (Reversible) Polymorphism via Polymerization Induced Self‐assembly (PISA)

Polymerization‐induced self‐assembly (PISA) is an extremely versatile method for the in situ preparation of soft‐matter nanoparticles of defined size and morphologies at high concentrations, suitable for large‐scale production. Recently, certain PISA‐prepared nanoparticles have been shown to exhibit reversible polymorphism (“shape‐shifting”), typically between micellar, worm‐like, and vesicular phases (order–order transitions), in response to external stimuli including temperature, pH, electrolytes, and chemical modification. This review summarises the literature to date and describes molecular requirements for the design of stimulus‐responsive nano‐objects. Reversible pH‐responsive behavior is rationalised in terms of increased solvation of reversibly ionized groups. Temperature‐triggered order–order transitions, conversely, do not rely on inherently thermo‐responsive polymers, but are explained based on interfacial LCST or UCST behavior that affects the volume fractions of the core and stabilizer blocks. Irreversible morphology transitions, on the other hand, can result from chemical post‐modification of reactive PISA‐made particles. Emerging applications and future research directions of this “smart” nanoparticle behavior are reviewed.

     

Facile Fabrication of AIE‐Active Fluorescent Polymeric Nanoparticles with Ultra‐Low Critical Micelle Concentration Based on Ce(IV) Redox Polymerization for Biological Imaging Applications

Fluorescent polymeric nanoparticles (FPNs) with aggregation‐induced emission (AIE) property have received increasing attention and possess promising biomedical application potential in the recent years. Many efforts have been devoted to the fabrication methodologies of FPNs and significant advance has been achieved. In this contribution, a novel strategy for the fabrication of AIE‐active amphiphilic copolymers is reported for the first time based on the Ce(IV) redox polymerization. As an example, ene group containing AIE‐active dye (named as Phe‐alc) is directly grafted onto a water soluble polymer polyethylene glycol (PEG) in H₂O/THF system under low temperature. Thus‐obtained amphiphilic fluorescent polymers will self‐assemble into FPNs with ultra‐low critical micelle concentration, ultra‐brightness, and great water dispersibility. Biological evaluation results suggest that the PEG‐poly(Phe‐alc) possess excellent biocompatibility and can be used for tracing their behavior in cells using confocal laser scanning microscope. These features make PEG‐poly(Phe‐alc) FPNs promising candidates for many biomedical applications, such as cell imaging, drug delivery vehicles, and targeted tracing. More importantly, many other functional groups can also be incorporated into these AIE‐active FPNs through the redox polymerization. Therefore, the redox polymerization should be a facile and effective strategy for fabrication of AIE‐active FPNs.