Rational design of iridium–porphyrin conjugates for novel synergistic photodynamic and photothermal therapy anticancer agents

Near-infrared (NIR) emitters are important probes for biomedical applications. Nanoparticles (NPs) incorporating mono- and tetranuclear iridium(iii) complexes attached to a porphyrin core have been synthesized. They possess deep-red absorbance, long-wavelength excitation (635 nm) and NIR emission (720 nm). TD-DFT calculations demonstrate that the iridium–porphyrin conjugates herein combine the respective advantages of small organic molecules and transition metal complexes as photosensitizers (PSs): (i) the conjugates retain the long-wavelength excitation and NIR emission of porphyrin itself; (ii) the conjugates possess highly effective intersystem crossing (ISC) to obtain a considerably more long-lived triplet photoexcited state. These photoexcited states do not have the usual radiative behavior of phosphorescent Ir(iii) complexes, and they play a very important role in promoting the singlet oxygen (¹O₂) and heat generation required for photodynamic therapy (PDT) and photothermal therapy (PTT). The tetranuclear 4-Ir NPs exhibit high ¹O₂ generation ability, outstanding photothermal conversion efficiency (49.5%), good biocompatibility, low half-maximal inhibitory concentration (IC₅₀) (0.057 μM), excellent photothermal imaging and synergistic PDT and PTT under 635 nm laser irradiation. To our knowledge this is the first example of iridium–porphyrin conjugates as PSs for photothermal imaging-guided synergistic PDT and PTT treatment in vivo.

Iridium–porphyrin conjugates assembled in nanoparticles are photosensitizers that exhibit excellent photothermal imaging and synergistic PDT and PTT in vivo.     

On the Relative Twist Formula of l-adic Sheaves

We propose a conjecture on the relative twist formula of l-adic sheaves, which can be viewed as a generalization of Kato—Saito's conjecture. We verify this conjecture under some transversal assumptions. We also define a relative cohomological characteristic class and prove that its formation is compatible with proper push-forward. A conjectural relation is also given between the relative twist formula and the relative cohomological characteristic class.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.     

碳纳米管的可控长度拾取及导电性分析

拾取指定长度的半导体性碳纳米管对大规模制造碳纳米管场效应管具有重要意义.本文提出了一种利用原子力显微镜探针和钨针对碳纳米管进行可控长度拾取的方法并进行了碳纳米管导电性分析.在扫描电子显微镜下搭建微纳操作系统,针对切割操作过程中原子力显微镜探针、钨针和碳纳米管的接触情况进行了力学建模和拾取长度误差分析.建立了单根金属性碳纳米管、单根半导体性碳纳米管及碳纳米管束与钨针接触的电路模型,推导了接入不同性质碳纳米管后电路的电流电压特性方程.使用原子力显微镜探针对碳纳米管的空间位姿进行调整,控制钨针对碳纳米管上目标位置进行通电切割,同时获取切割电路中的电流电压数据.实验结果表明,本文提出的方法能够有效控制所拾取碳纳米管的长度,增加碳纳米管与原子力显微镜探针的水平接触长度能够减小碳纳米管形变导致的拾取长度误差,建立的电流电压特性方程能够用于分析碳纳米管的导电性.     

EicC对撞光学设计

EicC是中国科学院近代物理研究所计划建造的中国电子-离子对撞机装置,该对撞机质心能位于20 GeV附近,是研究海夸克的最佳能量窗口,同时还可研究胶子和价夸克。EicC对撞粒子为高极化率质子和电子束团,质子环pRing采用八字环设计方案,可以更好地保持极化质子束团极化率,电子环eRing采用跑道形环设计方案,可以更好地利用隧道空间。该装置电子束流能量中心值为3.5 GeV,电子束RMS发射度为水平方向60 nm·rad,垂直方向60 nm·rad,对撞点b函数为水平方向0.4 m,垂直方向0.12 m;质子束流能量中心值20 GeV,质子束RMS发射度为水平方向300 nm·rad,垂直方向180 nm·rad,对撞点b函数为水平方向0.08 m,垂直方向0.04 m,设计亮度2×1033 cm–2s–1。EicC采用双对撞区非对称光学设计,通过对EicC不同色品补偿方案的研究,最终确定了弧区加短直线节共同补偿的色品补偿方案;通过研究对撞点处b函数以及对撞点间相移对动力学孔径的影响,最终得到pRing动力学孔径大于8 s(s为束团RMS尺寸)、eRing动力学孔径大于20 s,满足大于束团尺寸6 s的要求。     

An improved evaluation of the neutron background in the PandaX-Ⅱ experiment

In dark matter direct detection experiments,neutron is a serious source of background,which can mimic the dark matter-nucleus scattering signals.In this paper,we present an improved evaluation of the neutron background in the PandaX-II dark matter experiment by a novel approach.Instead of fully relying on the Monte Carlo simulation,the overall neutron background is determined from the neutron-induced high energy signals in the data.In addition,the probability of producing a dark-matter-like background per neutron is evaluated with a complete Monte Carlo generator,where the correlated emission of neutron(s)andγ(s)in the(α,n)reactions and spontaneous fissions is taken into consideration.With this method,the neutron backgrounds in the Run 9(26-ton-day)and Run 10(28-ton-day)data sets of PandaX-II are estimated to be(0.66±0.24)and(0.47±0.25)events,respectively.     

Anisotropic phononic crystal structure with low-frequency bandgap and heat flux manipulation

This study presents a two-dimensional phononic crystal with heat flux manipulation and wide bandgaps of out-of-plane modes within the low-frequency range. The anisotropic matrix made of spiral-multilayered materials with different thermal conductivities, and the coating layer inserted with metal are designed for heat flux manipulation. Rubber-coated metal cylinders are periodically embedded in the anisotropic matrix to obtain the low-frequency bandgaps of out-of-plane modes. Numerical simulation is carried out to validate the heat and elastic characteristics of the spiral-multilayered anisotropic structure and reveal the effects of the laying angle and temperature on the bandgaps. Subsequently, a spiral-multilayered plate with periodic structures is studied, which shows an obvious vibration attenuation in the frequency ranges of the bandgaps and a deflected heat flux from the initial propagation direction. In the experimental investigation, the multi-phase spiral-multilayered anisotropic plate is simplified to a single-phase anisotropic plate made of aluminum. The characteristics of this type of anisotropic phononic crystal structure may pave the way for the design of a new kind of thermo-acoustic metamaterial serving in combined thermal and acoustic environments.     

新冠疫情对我国信贷风险冲击的定量测算

文章建立了宏观经济传导模型和信贷风险传导模型,根据对GDP的估计,对新型冠状病毒感染肺炎疫情下的2020年全国和若干疫情严重省市的不良贷款率进行了定量测算.假设一季度内疫情得以控制,全年GDP增速下降至5.7％的情景下,预计全国年末不良贷款率约3％,不良贷款余额比2019年增加逾80％,接近2019年国内商业银行贷款损...     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.     

开展化学实验技能竞赛促进实验教学

通过开展实验技能竞赛等措施 ,增强学生的动手能力 ,提高实验教学水平 ,促进实验教学 ,建立有工程特色的化学实验体系