An optimal perturbation bound

Cai and Zhang establish separate perturbation bounds for distances with spectral and Frobenius norms (Cai T, Zhang A. Rate‐optimal perturbation bounds for singular subspaces with applications to high‐dimensional statistics. The Annals of Statistics. 2018; Vol. 46, No. 1: 60?89). We extend their theorem to each unitarily invariant norm. It turns out that our estimation is optimal as well.     

13.56 MHz/2 MHz柱状感性耦合等离子体参数的对比研究

通过Langmuir双探针和发射光谱诊断方法,对比研究了驱动频率为13.56 MHz和2 MHz柱状感性耦合等离子体中电子密度和电子温度的径向分布规律.结果表明:在高频和低频放电中,输入功率的增加对等离子体参数产生了不同的影响,高频放电中主要提升了电子密度,低频放电中则主要提升了电子温度.固定气压为10 Pa,分别由高频和低频驱动时,电子密度的径向分布均为"凸型".而电子温度的分布差异比较明显,高频驱动时,电子温度在腔室中心较为平坦,在边缘略有上升;低频驱动时,电子温度随径向距离的增加而逐渐下降.为了进一步分析造成这种差异的原因,在相同放电条件下采集了氩等离子体的发射光谱图,利用分支比法计算了亚稳态粒子的数密度,发现电子温度的径向分布始终与亚稳态粒子的径向分布相反.继续升高气压到100 Pa,发现不论高频还是低频放电,电子密度的径向分布均从"凸型"转变为"马鞍形",较低气压时电子密度的均匀性有了一定的提升,但低频的均匀性更好.     

Synergism of Interface and Electronic Effects: Bifunctional N-Doped Ni3S2/N-Doped MoS2 Hetero-Nanowires for Efficient Electrocatalytic Overall Water Splitting

The realization of water electrolysis on the basis of highly active, cost-effective electrocatalysts is significant yet challenging for achieving sustainable hydrogen production from water. Herein, N-doped Ni₃S₂/N-doped MoS₂ 1D hetero-nanowires supported by Ni foam (N-Ni₃S₂/N-MoS₂/NF) are readily synthesized through a chemical transformation strategy by using NiMoO₄ nanowire array growth on Ni foam (NiMoO₄/NF) as the starting material. With the in situ generation of Ni₃S₂/MoS₂ heterointerfaces within nanowires and the incorporation of N⁻ anions, an extraordinary hydrophilic nature with abundant, well-exposed active sites and optimal reaction dynamics for both oxidation and reduction of water are obtained. Attributed to these properties, as-converted N-Ni₃S₂/N-MoS₂/NF exhibits highly efficient electrocatalytic activities for both hydrogen and oxygen evolution reactions under alkaline conditions. The superior bifunctional properties of N-Ni₃S₂/N-MoS₂/NF enable it to effectively catalyze the overall water-splitting reaction.     

A Near-Infrared-Controllable Artificial Metalloprotease Used for Degrading Amyloid-β Monomers and Aggregates

Proteolysis of amyloid-β (Aβ) is a promising approach against Alzheimer's disease. However, it is not feasible to employ natural hydrolases directly because of their cumbersome preparation and purification, poor stability, and hazardous immunogenicity. Therefore, artificial enzymes have been developed as potential alternatives to natural hydrolases. Since specific cleavage sites of Aβ are usually embedded inside the β-sheet structures that restrict access by artificial enzymes, this strongly hinders their efficiency for practical applications. Herein, we construct a NIR (near-IR) controllable artificial metalloprotease (MoS₂-Co) using a molybdenum disulfide nanosheet (MoS₂) and a cobalt complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (Codota). Evidenced by detailed experimental and theoretical studies, the NIR-enhanced MoS₂-Co can circumvent the restriction by simultaneously inhibition of β-sheet formation and destroying β-sheet structures of the preformed Aβ aggregates in living cell. Furthermore, our designed MoS₂-Co is an easy to graft Aβ-target agent that prevents misdirected or undesirable hydrolysis reactions, and has been demonstrated to cross the blood brain barrier. This method can be adapted for hydrolysis of other kinds of amyloids.     

The Linear Optical Unambiguous Discrimination of Hyperentangled Bell States Assisted by Time Bin

A linear optical unambiguous discrimination of hyperentangled Bell states is proposed for two‐photon systems entangled in both the polarization and momentum degrees of freedom (DOFs) assisted by time bin. This unambiguous discrimination scheme can completely identify 16 orthogonal hyperentangled Bell states using only linear optical elements, where the function of the auxiliary entangled Bell state is replaced by time bin. Moreover, the possibility of extending this scheme for distinguishing hyperentangled Bell states in n DOFs is discussed, and it shows that $2^{n+k+1}$ hyperentangled Bell states in n ( $n\ge 2$) DOFs can be distinguished with k ( $k<n$) auxiliary entangled states of additional DOFs by introducing a time delay, which decreases the auxiliary entanglement resource required for unambiguous discrimination of hyperentangled Bell state. Therefore, this scheme provides a new way for distinguishing hyperentangled states with current technology, which will extend the application of discrimination of hyperentangled states via linear optics to other quantum information protocols besides hyperdense coding schemes in the future.     

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

The precise synthesis of poly(thioester)s with diverse structures is still a significant challenge in the polymeric materials field. Herein, we report a novel approach to the synthesis of well‐defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts. Both the cation and anion have strong effects on the copolymerization. [PPN]OAc ([PPN]=bis(triphenylphosphine)iminium) with a bulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with a completely alternating structure, controlled molecular weight, and narrow polydispersity. The poly(thioester) obtained from succinic thioanhydride and propylene sulfide is a typical semicrystalline material, possessing a high refractive index of up to 1.78. Because it uses readily available monomers, this method is expected to open up a new route to poly(thioester)s with diverse structures and properties.     

湍流大气传输中跟踪抖动对远场影响的仿真研究

分析了跟踪抖动对湍流大气传输远场光斑的影响。基于麦克斯韦电磁场理论,采用大气相干长度对大气湍流进行描述,推导了发射光束因跟踪抖动导致光轴偏离的远场表达式。在此基础上,利用相位屏法模拟抖动引起的倾斜相位和大气折射率起伏引起的相位调制,并采用低频补偿的功率谱反演法对传输过程进行了数值仿真。分析了不同跟踪抖动、湍流强度条件下远场光斑质心脱靶量的变化,以及不同尺寸模拟目标的回波概率。分析结果表明,在传输距离为10 km时,强湍流造成的远场光斑脱靶量可达几十μrad;当跟踪抖动较大时,湍流强弱对脱靶量影响差别很小。最后,对一定尺寸的模拟目标,从探测回波概率的角度给出了发射系统跟踪抖动量的控制范围。     

A [001]-Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide-Spectrum-Responsive Photocatalytic Hydrogen Evolution from Pure Water

Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h⁻¹ from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.     

Catalytic cross-coupling of aniline by pyrite and dissolved oxygen under alkaline conditions

Pyrite catalyzes oxidation of various organic contaminants by dissolved oxygen (DO) under acidic conditions; however, the catalytic mechanism under alkaline conditions is still not clear. In this study, we observe increased oxidation rates of aniline with increasing pHs (7.0–11.0). Electron paramagnetic resonance (EPR) analysis and quenching experiments rule out contributions of •OH, O₂^•−, ¹O₂ and Fe (IV) to aniline oxidation and suggest that the Fe (III)–OOH peroxo and/or H₂O₂ are the primary oxidative species in the oxidation of aniline at pH 11.0. In addition, 200 mg L⁻¹ H₂O₂ does not apparently increase the oxidation rate of aniline, which also rules out the predominant contribution of the produced H₂O₂ to aniline oxidation. We therefore suggest that the Fe (III)–OOH peroxo is indeed the primary oxidative species in the pyrite–DO system under alkaline conditions. Analyses of solid total organic carbon (TOC), gas chromatography–mass spectrometry and Fourier-transform infrared spectroscopy further reveal that more than 83.3% aniline has been polymerized to polyaniline, instead of being mineralized into CO₂ and H₂O, indicating that H-abstraction from aniline by the Fe (III)–OOH peroxo is an important step in the oxidation of aniline under alkaline conditions. This study provides new insight into the oxidative species in the pyrite–DO system, and opens a new door for organic degradations under alkaline conditions.     

Efficient structural modification of electron-withdrawing substituents on Pt(II) complexes for red emitters: A theoretical study

In this study, the electronic structures and optical properties of a cyclometalated Pt(II) complex (M1) and a series of derivatives (M1–F, M1–CF₃, and M1–CN) with electron-withdrawing substituents (–F, –CF₃, and –CN) at the carbazole moiety were theoretically investigated by density functional theory and time-dependent density functional theory. The calculation results reveal that these Pt complexes display deep red phosphorescence emission above Λ = 640 nm. When the ³MLCT/π → π* to triplet metal-centered ³MC/d–d state decay mechanism is taken into consideration, the nonradiative decay rate constant (k_nr) decreased in the order M1 > M1–CF₃ > M1–F > M1–CN. The <T₁|H_SOC|S_m> and kr values of M1-F are similar with those of M1, however the Knr rate ofM1-F is larger than that of M1. M1–F is expected to have improved quantum yields. Moreover, through the analyses of the HOMO/LUMO level and triplet energy, it is found that the introduction of –F and –CN substituents in M1 results in efficient energy transfer from the host material 4,4′-N,N′-dicarbazole-biphenyl to these complexes. In view of the electroluminescent applications in organic light-emitting diodes, M1–F can serve as efficient deep-red guest materials with improved electron injection and transport ability.