Vilsmeier formylation of 5,10,15-triphenylcorrole: expected and unusual products

5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry.     

Single‐Crystalline and Near‐Monodispersed NaMF3 (M=Mn,Co, Ni,Mg) and LiMAlF6 (M=Ca,Sr) Nanocrystals from Cothermolysis of Multiple Trifluoroacetates in Solution

We report the synthesis of single‐crystalline and near‐monodispersed NaMF₃ (M=Mn, Co, Ni, Mg), LiMAlF₆ (M=Ca, Sr), and NaMgF₃:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF₃ (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF₃ nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF₃ square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF₃:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF₃ may be a good candidate host material for red upconversion luminescence.     

分子内Diels-Alder反应在有机合成方面的新进展

本文按合成产物的结构类型,综述分子内 Diels-Alder 反应在有机合成方面的新进展。     

Estimation of a quantile in some nonstandard cases

A necessary condition for the asymptotic normality of the sample quantile estimator isf(Q(p))=F(Q(p))>0, whereQ(p) is thep-th quantile of the distribution functionF(x). In this paper, we estimate a quantile by a kernel quantile estimator when this condition is violated. We have shown that the kernel quantile estimator is asymptotically normal in some nonstandard cases. The optimal convergence rate of the mean squared error for the kernel estimator is obtained with respect to the asymptotically optimal bandwidth. A law of the iterated logarithm is also established.This research was partially supported by the new faculty award from the University of Oregon.     

一种基于SPWVD-WVD的高质量时频分析方法及ISAR成像应用

交叉项干扰抑制与高时频聚集度是准确反应信号的时频分布特征的重要因素。传统的魏格纳-维尔分布(Wigner-Ville Distribution,WVD)算法虽能获得较高的时频分辨特征,但分析多成分信号时存在严重的交叉项干扰问题,限制了其实用性;而平滑伪魏格纳-维尔分布(Smoothed Pseudo Wigner-Ville Distribution,SPWVD)算法虽在一定程度上抑制交叉项干扰,但降低了时频聚集度。为了解决上述问题,提出了基于SPWVD-WVD的时频分析方法。该方法利用SPWVD与WVD之间的滤波互消效应,将SPWVD二值化结果与WVD结果进行矩阵运算,最终得到高质量的时频分析结果。实验结果表明,所提出的算法能够有效去除多分量信号的交叉项干扰,提高信号分析结果的时频聚集度,还原多分量信号的真实时频分布。最后将该算法成功应用于逆合成孔径雷达成像中。     

一种基于电荷泵锁相环的快速啁啾发生器

调频连续波(FMCW)雷达常用于测量多个目标的距离和速度,被广泛用于自动驾驶场景中。FMCW雷达产生的线性调频波称为啁啾(Chirp),通常由锁相环(PLL)电路产生。由于带宽有限,传统锯齿啁啾下降时间过长,降低了雷达性能。文章提出了一种基于分段电流电荷泵的快速啁啾发生器设计方案。调频阶段采用最佳电荷泵电流,即最优环路带宽,可保证啁啾的线性度。啁啾下降阶段使用更大的电流,可缩短下降时间。仿真结果表明,啁啾发生器频率输出范围为19.25～20.25 GHz, 1.2 V电压下整体功耗为31.8 mW。PLL带宽为1.5 MHz时,锯齿形啁啾下降的最大调制速率为454 MHz/μs。与恒定电荷泵电流方式相比,下降时间缩短了80%。     

一种43 GHz超高带宽线性驱动电路设计

基于0.13μm SiGe BiCMOS工艺,设计了一种线性驱动电路。该电路具有高速和大摆幅的优势,能线性驱动行波马赫-曾德尔调制器(TW-MZM),可满足光通信系统100 Gbit/s单通道的应用需求。驱动电路包括连续时间线性均衡(CTLE)电路、可变增益放大(VGA)电路和基于Cascode结构改进优化的输出级电路,实现了增益可调,且避免发生由较大输出摆幅导致的晶体管击穿。仿真结果表明,电路的-3 dB带宽为43 GHz,其增益在15～25 dB内可调。在56 Gbaud NRZ/PAM4的输入信号下,测得的眼图形状良好,差分输出摆幅峰-峰值达4 V,电路整体功耗为1.02 W,面积为0.33 mm²。     

基于自注意力机制和CycleGAN的高分三号ScanSAR图像的扇贝效应抑制

高分三号卫星是我国首颗分辨率达到1 m的C波段 多极化合成孔径雷达(synthetic aperture radar,SAR) 卫星,其中扫描 式合成孔径雷达(scan synthetic aperture radar,ScanSAR)模式是高分三号卫星重要的工 作模式之一,由于该模式的工作机制导致生成的图像可能发生扇贝效应,一般呈现为明暗相 间的条纹。本文针对高分三号卫星ScanSAR模式下存在的扇贝效应,提出自注意力机制与循 环一致对抗网络(cycle-consistent adversarial networks,CycleGAN)结合的模型对Scan S AR图像进行处理,从而抑制扇贝效应产生的条纹现象。本文所示方法与传统扇贝效应抑制方 法和深度学习相关算法进行比较,并通过亮度均值、平均梯度等指标进行分析。实验结果表 明,本文方法可以对高分三号ScanSAR图像存在的扇贝效应进行较好的处理,有效抑制图像 的条纹现象,使得图像质量得到提升,具有较大的实用意义。     

一种波形可移植性量化评估的模糊综合评判法

要实现高效低成本的波形跨平台移植,需要通过量化评估优选出可移植性强的波形来进行移植。针对波形可移植性量化评估重要性,分析了影响波形可移植性量化评估的重要因素,提出了一种有效的波形可移植性量化评估模糊综合评判法,以软件无线电硬件平台因素为例论述了该方法的实现原理及流程。通过验证表明,该方法合理可行,具有很好的应用价值。     

面向典型战场应用的目标智能融合技术

针对战场多源信息融合的典型应用需求,提出了基于人工智能的目标信息融合技术思路,并对其中的两项关键技术,即新型融合知识库构建技术和基于本体核的目标知识融合技术进行了分析,最后对多源信息融合系统在应用过程中存在的技术问题及其解决思路进行了探讨。