Optical Trapping with Focused Surface Waves

Near-field optical trapping can be realized with focused evanescent waves that are excited at the water–glass interface due to the total internal reflection, or with focused plasmonic waves excited on the water–gold interface. Herein, the performance of these two kinds of near-field optical trapping techniques is compared using the same optical microscope configuration. Experimental results show that only a single-micron polystyrene bead can be trapped by the focused evanescent waves, whereas many beads are simultaneously attracted to the center of the excited region by focused plasmonic waves. This difference in trapping behavior is analyzed from the electric field intensity distributions of these two kinds of focused surface waves and the difference in trapping behavior is attributed to photothermal effects due to the light absorption by the gold film.     

Transition-Metal-Free Multiple Functionalization of Piperidines to 4-Substituted and 3,4-Disubstituted 2-Piperidinones

Remote and multiple functionalization of piperidines without the use of transition-metal catalysts and elaborate directing groups is one of the major challenges in organic synthesis. Herein is reported an unprecedented two-step protocol that enables the multiple functionalization of piperidines to either 4-substituted or trans-3,4-disubstituted 2-piperidones. First, by exploiting the duality of TEMPO reactivity, which under oxidative and thermal conditions fluctuates between cationic and persistent-radical form, a novel multiple C(sp³)-H oxidation of piperidines to α,β-unsaturated 2-piperidones was developed. Second, the intrinsic low reactivity of the unsaturated piperidones toward conjugated Grignard additions was overcome by using trimethylsilyl chloride (TMSCl) as Lewis acid. Subsequently, conjugated Grignard addition/electrophilic trapping protocol provided substituted 2-piperidone intermediates, some of which were then transformed into pharmaceutical alkaloids.     

Intramolecular orbital engineered hetero bimetallic Ce-Fe MOF with reduced transition energy and enhanced visible light property

A structurally stable, 3d-4f heterometallic coordination polymer has been solvothermally synthesised and evaluated for its accomplished materials properties. The light absorption activity in the visible band was higher for unique Ce-Fe MOF than that of the homometallic Ce-MOF or Fe- MOF. The intimate overlap of two different metal clusters in heterometallic environmental induced the formation of low line conduction orbital, which ultimately lowered the transition energy. The heterometallic acquired an additional sensitisation from a Fe-μ3-oxo cluster that had vibrantly enhanced the light uptake activity. The vacancy created in the 6s, 5d orbital of Ce in Ce-Fe MOF contributed to the photo-excitation of electrons and reduced the recombination time. This distinct intramolecular arrangement assisted the exciton trapping characteristic. Also, the presence of multiple metal cores in the framework aided to confine the increased number of excitons for a redox reaction. The solar photocatalysis study with acetaminophen revealed these improved materialistic features by degrading it 94.6% with a rate constant of 0.0137 min⁻¹. The recycle studies confirmed the robust stability of the synthesised MOF.     

Power-of-two sampling in redundancy systems: The impact of assignment constraints

A classical sampling strategy for load balancing policies is power-of-two, where any server pair is sampled with equal probability. This does not cover practical settings with assignment constraints which force non-uniform sampling. While intuition suggests that non-uniform sampling adversely impacts performance, this was only supported through simulations, and rigorous statements have remained elusive. Building on product-form distributions for redundancy systems, we prove the stochastic dominance of uniform sampling for a four-server system as well as arbitrary-size systems in light traffic.     

Halogen‐bonded adduct of 1,2‐dibromo‐1,1,2,2‐tetrafluoroethane and 1,4‐diazabicyclo[2.2.2]octane

Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen‐bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour‐phase diffusion of 1,4‐diazabicyclo[2.2.2]octane (DABCO) with 1,2‐dibromotetrafluoroethane results in crystals of the 1:1 adduct, C₂Br₂F₄·C₆H₁₂N₂, which crystallizes as an infinite one‐dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

基于捕集柱阵列的制备型二维液相色谱纯化烟草中的4个组分

二维液相色谱(2D-LC)因具有较高的峰容量,在复杂样品的分离分析中获得了广泛的关注。然而,制备型2D-LC以纯化高纯单体为目标,在方法开发和设备构成等方面与分析型2D-LC有较大的不同,目前尚未得到充分的开发,在大规模的制备纯化中应用较少。本文以一套制备液相色谱模块为分离系统,以稀释泵、切换阀和捕集柱阵列为接口,构建了新型的制备型2D-LC系统,旨在规模化纯化多个活性成分。以烟叶中可以用作医药原料的烟碱、绿原酸、芦丁和茄尼醇等组分为目标物,考察了不同类型填料对样品的捕集效率、过载条件下的色谱保留行为等,优化了制备色谱条件。进而利用在线2D-LC系统实现了烟叶提取物的纯化,通过一次运行获得了4个高纯化合物。该系统具有中压色谱纯化成本低、系统在线运行自动化程度高、稳定性好及容易放大等优点。烟叶中活性化学成分的回收利用对促进烟草行业的发展及带动地方农业经济开发具有重大的意义。     

Turn-on Circularly Polarized Luminescence in Chiral Indium Chlorides by 5s2 Metal Centers

Introducing chirality into the metal-halide hybrids has enabled many emerging properties including chiroptical activity, spin-dependent transport, and ferroelectricity. However, most of the chiral metal-halide hybrids to date are non-emissive, and the underlying mechanism remains elusive. Here, we show a new strategy to turn on the circularly polarized luminescence (CPL) in chiral metal-halide hybrids. We demonstrate that alloying Sb³⁺ into chiral indium-chloride hybrids dramatically increases the photoluminescence quantum yield in two new series of chiral indium-antimony chlorides. These materials exhibit strong CPL signals with tunable energy and a high dissymmetry factor up to 1.5×10⁻². Mechanistic studies reveal that the emission originates from the self-trapped excitons centered in 5s² Sb³⁺. Moreover, near-ultraviolet pumped white light is demonstrated with a polarization up to 6.0 %. Our work demonstrates new strategies towards highly luminescent chiral metal-halide hybrids.     

Basics of optical force

Light possesses momentum, and hence, force is exerted on materials if they absorb and/or scatter light. Laser techniques that use optical forces are currently attracting considerable attention. Optical manipulation for trapping, transporting small particles, and measuring the interparticle force is a representative technique. In addition, photoinduced force microscopy is a promising scanning type of microscopy using optical force. Optical force techniques have recently been used in various fields of research, such as molecular bioscience, organic photochemistry, materials engineering, and molecular fluid dynamics. In these techniques, several types of optical forces such as scattering, absorption, and gradient forces play their respective roles. In this article, we summarize the basics of optical forces and present their elementary expressions for using simplified models of light and matter systems. This will help the readers of this Special Issue to understand how different types of forces are distinguished in the basic expressions used for analyzing the optical force phenomena that appear depending on the light geometry and matter systems. After observing simplified cases of scattering and absorption forces, we introduce general formulae for the optical force and then discuss how different components appear in particular cases of laser geometry and materials.     

Photo-Induced Switching of CO2 Hydrogenation Pathway towards CH3OH Production over Pt@UiO-66-NH2(Co)

It is highly desired to achieve controllable product selectivity in CO₂ hydrogenation. Herein, we report light-induced switching of reaction pathways of CO₂ hydrogenation towards CH₃OH production over actomically dispersed Co decorated Pt@UiO-66-NH₂. CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH₃OH via the formate pathway with the assistance of light irradiation. Impressively, the space-time yield of CH₃OH in photo-assisted thermocatalysis (1916.3 μmol g_cat⁻¹ h⁻¹) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO-66-NH₂ can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO₂-to-*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH₃OH selectivity.