Zethrene and Dibenzozethrene: Masked Biradical Molecules?

The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature ¹H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σ_max=4323 GM at 530 nm].     

Self-calibration method for cerium-doped lanthanum bromide scintillator detector in the 0.1–2.0 MeV energy range

In recent years, the cerium-doped lanthanum bromide, LaBr₃ (Ce = 5 %) detector is increasingly playing an important role in radiation measurements because of its higher energy resolution (~3 % at 662 keV), faster luminescence decay time (~35 ns) and higher detection efficiency compared to 7.65 cm × 7.65 cm NaI(Tl) detector. Intrinsic spectra between 1,800 and 3,000 keV derived from internal radioactivity within LaBr₃(Ce) scintillators have been investigated in some literatures, and these results are confirmed by the experiments in this work. In this paper, a new method for LaBr₃(Ce) detector energy calibration from 100 to 2,000 keV is proposed using the intrinsic spectra (self-calibration) instead of the standard gamma sources. Proof-of-concept experiment results show that self-calibration can guarantee energy accuracy of better than 0.815 % and can be applied outside the laboratory. The stability and applicability of this method are also investigated systematically.     

Phase‐preserved macroscopic visible‐light carpet cloaking beyond two dimensions

Transformation optics, a recent geometrical design strategy of light manipulation with both ray trajectories and optical phase controlled simultaneously, promises an invisibility cloaking device that can render a macroscopic object invisible even to a scientific instrument measuring optical phase. Recent “carpet” cloaks have extended their cloaking capability to broadband frequency ranges and macroscopic scales, but they only demonstrated the recovery of ray trajectories after passing through the cloaks, while whether the optical phase would reveal their existence still remains unverified. In this paper, a phase‐preserved macroscopic visible‐light carpet cloak is demonstrated in a geometrical construction beyond two dimensions. As an extension of previous two‐dimensional (2D) macroscopic carpet cloaks, this almost‐three‐dimensional carpet cloak exhibits three‐dimensional (3D) invisibility for illumination near its center (i.e. with a limited field of view), and its ideal wide‐angle invisibility performance is preserved in multiple 2D planes intersecting in the 3D space. Optical path length is measured with a broadband pulsed‐laser interferometer, which provides unique experimental evidence on the geometrical nature of transformation optics.

     

基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

Synthesis and bioevaluation of radioiodated nitroimidazole-based hypoxia imaging agents containing different charged substituents

Journal of Radioanalytical and Nuclear Chemistry - In this work, a series of radiolabeled 2-nitroimidazole-based iodotriazoles containing positively charged, negatively charged, or neutral...     

Spatiotemporally-regulated multienzymatic polymerization endows hydrogel continuous gradient and spontaneous actuation

There are several natural materials which have evolved functional gradients,ingeniously attaining maximal efficacy from limited components.Herein,we utilized the spatiotemporal distribution of initiator acetylacetone to regulate the multienzyme polymerization and fabricate a chitosan-polymer hydrogel.The temporal priority order of acetylacetone was higher than phenolmodified chitosan by density functional theory calculation.The acetylacetone within the gelatin could gradually diffuse spatially into the chitosan hydrogel to fabricate the composite hydrogel with gradient network structure.The gradient hydrogel possessed a transferring topography from the two-dimensional pattern.A continuously decreased modulus along with acetylacetone diffusion was confirmed by atomic force microscope-based force mapping experiment.The water-retaining ability of various regions was confirmed by low-field nuclear magnetic resonance(NMR)and thermogravimetric analysis(TG)analysis,which led to the spontaneous actuation of gradient hydrogel with maximum 1821°/h curling speed and 227°curling angle.Consequently,the promising gradient hydrogels could be applied as intelligent actuators and flexible robots.     

Suppression of charge imbalance via Li+-Mn4+ co-incorporated Sr2YSbO6 red phosphors for warm w-LEDs

Mn⁴⁺-activated double perovskite phosphors with composition diversity have presented excellent luminescent performances. However, the charge imbalance between Mn⁴⁺ and matrix cations would increase non-radiative recombination and reduce the structural stability. Here, novel high-efficiency stable Li⁺/Mn⁴⁺ co-incorporated Sr₂YSbO₆ red phosphors are successfully synthesized via a solid-state reaction method for warm w-LEDs, where the Li⁺ ions have the effect of charge balance for Sr₂YSbO₆:Mn⁴⁺ and reduce the non-radiative energy transfer among Mn⁴⁺ ions. It is demonstrated that the substitution of Li⁺–Mn⁴⁺ pairs for Sb⁵⁺ can enhance the bonding with low-shifted diffraction peaks and high emission intensity, and prolong the decay lifetime, compared with those of Mn⁴⁺ single-doped ones. Impressively, the thermal stability is enhanced to 89.72% from 84.61% at the original value of 303 K. Finally, a w-LED device based on the optimal phosphor Sr₂YSbO₆:0.01Mn⁴⁺/0.01Li⁺ red component exhibits a correlated color temperature of 4487 K and color rendering index of 80.2. Therefore, the incorporated Li⁺ ions serve as both charge compensator and co-activator in Mn⁴⁺-activated double perovskite phosphors with the aim of high luminescent performance and thermal stability.     

Rician noise reduction in magnetic resonance images using adaptive non-local mean and guided image filtering

This paper proposes a Rician noise reduction method for magnetic resonance (MR) images. The proposed method is based on adaptive non-local mean and guided image filtering techniques. In the first phase, a guidance image is obtained from the noisy image through an adaptive non-local mean filter. Sobel operators are applied to compute the strength of edges which is further used to control the spread of the kernel in non-local mean filtering. In the second phase, the noisy and the guidance images are provided to the guided image filter as input to restore the noise-free image. The improved performance of the proposed method is investigated using the simulated and real data sets of MR images. Its performance is also compared with the previously proposed state-of-the art methods. Comparative analysis demonstrates the superiority of the proposed scheme over the existing approaches.     

Enhanced weak-signal sensitivity in two-photon microscopy by adaptive illumination

We describe a technique to enhance both the weak-signal relative sensitivity and the dynamic range of a laser scanning optical microscope. The technique is based on maintaining a fixed detection power by fast feedback control of the illumination power, thereby transferring high measurement resolution to weak signals while virtually eliminating the possibility of image saturation. We analyze and demonstrate the benefits of adaptive illumination in two-photon fluorescence microscopy.