Molecular Engineering of Cyclic Azobenzene-Peptide Hybrid Ligands for the Purification of Human Blood Factor VIII via Photo-Affinity Chromatography

The use of benign stimuli to control the binding and release of labile biologics for their isolation from complex feedstocks is a key goal of modern biopharmaceutical technology. This study introduces cyclic azobenzene-peptide (CAP) ligands for the rapid and discrete photo-responsive capture and release of blood coagulation factor VIII (FVIII). A predictive method—based on amino acid sequence and molecular architecture of CAPs—is developed to correlate the conformation of cis/trans-CAP photo-isomers to FVIII binding and release. Combined in silico - in vitro analysis of FVIII:peptide interactions guide the design of a rational approach to optimize isomerization kinetics and biorecognition of CAPs. A photoaffinity adsorbent, prepared by conjugating selected CAP G-cyclo_AZOB[Lys-YYKHLYN-Lys]-G on translucent chromatographic beads, features high binding capacity (>6 mg of FVIII per mL of resin) and rapid photo-isomerization kinetics (τ < 30 s) when exposed to 420–450 nm light at the intensity of 0.1 W cm⁻². The adsorbent purifies FVIII from a recombinant harvest using a single mobile phase, affording high product yield (>90%), purity (>95%), and blood clotting activity. The CAPs introduced in this report demonstrate a novel route integrating gentle operational conditions in a rapid and efficient bioprocess for the purification of life-saving biotherapeutics.     

Thermal isomerization and degradation of polyacetylene

In this paper, we present an experimental study of the isomerization from cis to trans (CH)_X induced by a thermal treatment of the film. Infrared, Raman, EPR and NMR spectroscopies have been used, in addition to dc conductivity measurements, in order to characterize the kinetics of the isomerization process. All the spectroscopic methods show that the isomerization is thermally activated with an activation energy of ～ 18 kcal/mole. It is also shown that degradation processes are also involved and an activation energy close to 30 kcal/mole is derived from EPR data. Optimal conditions to perform a thermal isomerization of cis(CH)_X, with respect to the extent of conjugation, are suggested.     

偶氮苯衍生物掺杂PMMA薄膜的非共振三阶非线性研究

研究了施受体型偶氮苯衍生物掺杂聚甲基丙烯酸甲酯（ＰＭＭＡ）薄膜的非共振三阶非线性，比较分子结构与材料的三阶非线性关系，得知越大的三阶非线性对应分子内越强的给受电子能力，在苯环上接上一个侧链基团可以增加分子的偶极矩，即增加了材料的三阶非线性。研究结果证明，材料三阶非线性主要源于光致顺反异构过程中偶氮分子的重新取向。     

Optical tristable device by vertical and direct integration ofheterojunction phototransistors and laser diodes

A light-controlled optical tristable device with an optical gain is actualized. The device has a configuration of vertical and direct integration of two heterojunction phototransistors (HPTs) on a laser diode (LD) along the cavity direction. An external optical input causes a bistable operation in one HPT+LD part. With the optical connection between two HPTs through the LD stripe, a bistable operation also occurs in the other HPT+LD part. The light-controlled optical tristability is achieved with the combination of the bistable operation in each HPT+LD part     

Internal optical couplings and functions of vertically and directlyintegrated device of four phototransistors and a laser diode

An optoelectronic integrated device composed of four heterojunction phototransistors and a laser diode has been developed. Optical coupling between constituent devices is investigated, and it is shown that there are three coupling modes between any two phototransistors through the laser diode. Various functions such as optical tristability, light-controlled optical bistability, and light-controlled optical thresholding are demonstrated by utilizing these optical coupling phenomena     

Photoresponsive Ferroelectric Liquid‐Crystalline Polymers

The photoresponse of ferroelectric smectic side‐chain liquid‐crystalline (LC) polymers containing a photoisomerizable azobenzene derivative as a covalently linked photochromic side group is investigated. By static measurements in different photostationary states, the effect of trans–cis isomerization on the material's phase‐transition temperatures and its ferroelectric properties (spontaneous electric polarization P_S and director tilt angle θ) are analyzed. It turns out that the Curie temperature (transition S_C* to S_A) can be reversibly shifted by up to 17 °C. The molecular mechanism of this “photoferroelectric effect” is studied in detail using time‐resolved measurements of the dye's optical absorbance, the director tilt angle, and the spontaneous polarization, which show a direct response of the ferroelectric parameters to the molecular isomerization. The kinetics of the thermal reisomerization of the azo dye in the LC matrix are evaluated. A comparison to the reisomerization reaction in isotropic solution (toluene) reveals a faster thermal relaxation of the dye in the LC phase.     

“推-拉”型偶氮苯功能化聚酯膜的光学相位共轭和光致异构

研究了2类以4'-(N,N二羟乙基)氨基4-硝基偶氮苯功能化的聚酯膜的光学相位共轭波的产生和光致异构。解释了聚酯膜产生饱和吸收和聚酯膜以顺式异构体的单线基态到单线激发态与反式异构体的单线基态到单线激发态的两个独立二能级系统通过光致异构耦合构成的四能级系统的响应特征。研究了膜厚、聚酯结构与泵浦光强对相位共轭波产生的影响。     

Porous Metal–Organic Framework@Polymer Beads for Iodine Capture and Recovery Using a Gas‐Sparged Column

Iodine (I₂) capture and recovery is an important process in many industrial practices. Conventional materials for I₂ capture include Ag⁰‐based aerogels and zeolites and C‐based aerogels and powders, which suffer from expensive and/or inefficient recovery. Recently, metal–organic frameworks (MOFs) have shown potential as good adsorbents for I₂ capture with high capacity, fast uptake, and good recyclability. The powder form of MOFs, however, often makes them impractical in large‐scale applications. Herein, a versatile method based on the phase inversion technique is presented to fabricate millimeter‐sized spherical MOF@polymer composite beads, and the use of these beads for I₂ capture and recovery is demonstrated. Besides preserving the crystallinity and pore accessibility of the embedded MOFs in the polymeric matrix, the beads exhibit higher capacity and faster uptake rate for I₂ in both vapor and liquid phases compared to the bulk MOF powder. In order to showcase the applicability of these beads, a gas‐sparged column is used as a proof‐of‐concept device that can efficiently capture and recover more than 99% of I₂ from the feeding solution. The beads can be recycled and reused multiple times, which in combination with their easy handling and storage highlights their superiority compared to MOF powders in adsorption applications.     

Reversible photoinduced bi-state polymer solar cells based on fullerene derivatives with azobenzene groups

[6,6]-Phenyl-C61-butyric acid-4′-hydroxyl-azobenzene ester (PCBAb) was synthesized and used as the acceptor in the fabrication of reversible UV–VIS response bi-state polymer solar cells (PSCs) based on the photoinduced cis–trans isomerization of PCBAb. The device can be switched between “active” and “sleep” by the irradiation of UV and visible light, respectively. The active device has a PCE of 2.0%. With UV irradiation, the device goes to “sleep” with a lowered PCE (0.4%), and simultaneously decreased J_sc, V_oc and FF, while after visible light treatment, the device is made “active” again. The mechanism of the bi-state process involves the different electron mobilities of the isomers.     

Parameters to consider in the construction of fiber-optic biosensors as alternative bioanalytical tools

A biosensor is a self-contained, bionic, integrated device that includes a biorecognition element that can respond in a concentration-dependent manner to a biochemical species. This article represents different possible methods of immobilizing biorecognition element used in fiber-optic-based biosensors. The method is chosen according to the analyte and the biorecognition element that will be used to sense it. In this review, two different approaches are represented: one using live organisms (based on bioluminescence) and one using immune reagents (based on chemiluminescence). Whole-cell fiber-optic biosensors have internal Bragg grating information with the potential to analyze samples without any additives in most cases. It includes a photon-counting system to measure a low-light response produced by markers of recognition elements. A flow-through, fiber-optic-based bacterial monitoring system for online monitoring of toxic pollutants in water has been developed. This monitoring system has proved to be a useful next step in the development of a simple online, realtime sensor for relevant human toxicants in flowing water.     

光敏开关器件微波传输特性的研究与分析

高性能的光敏开关器件是实现直接光控有源频率选择表面(AFSS)的关键。文中阐述了硫化镉光敏薄膜的优点和长引脚硫化镉光敏电阻器件的劣势,对四款不同的贴片硫化镉光敏电阻直流特性与微波特性进行了研究与分析。对加载有环保光敏电阻的圆环缝隙频率选择表面(FSS)进行实验验证,确定了单缝型微带线光控开关作为直接光控AFSS基础模型的有效性。同时,对直接光控AFSS中常用半导体硅和同族体锗进行了微波微带开关测试,表明锗并不适用于光控微波开关。最后对潜在可用于直接光控的新型半导体材料进行了展望。     

一种可调式声光控灯头的制作

针对一些家庭或场所出现了“长明灯”,为提倡节能且无需改装原线路的基础上,制作一种可调式声光控灯头。考虑到方便使用和不同用户需求,声光控灯头设计了卡口与螺口转换以及光强和声强感应调节装置,具有人性化、模块化特征。     

Ultrahigh and Tunable Negative Photoresponse in Organic-Gated Carbon Nanotube Film Field-Effect Transistors

Negative photoconductance (NPC) detectors have attracted continuous attention for constructing advanced and novel optoelectronic devices, including reconfigurable image sensors and optosynaptic systems, especially by combining NPC with positive photoconductance (PPC). However, NPC devices suffer from much lower photosensitivity, slower response speed, and poor stability, especially in the infrared range. In this work, controllable NPC detectors based on organic-gated carbon nanotube field-effect transistors (OG-CNT FETs) are reported and the strong influence of light-induced electrostatic doping on the nonconventional photoresponse is demonstrated. The PM6/Y6-based heterojunction allows efficient near-infrared light absorption and facilitates exciton diffusion. By introducing a floating gate structure with an ultrathin dielectric layer, the OG-CNT FET shows an enhanced NPC effect owing to in situ signal amplification. Compared to other device configurations, the optimal  OG-CNT FETs exhibit high responsivity of 72.6 A W⁻¹ at 880 nm, along with improved response/recovery times of 7 and 5 ms. Impressively, gate-tunable switching between NPC and PPC is observed under the same light illumination. The reversible switching can be attributed to the competition between the light-controlled electrostatic coupling and the PM6/Y6 photovoltaic effect, which offers a new approach to achieve bidirectional photoresponses and paves the way for the development of future multifunctional optoelectronic systems.     

Homopolymeric Protein Phosphors: Overpassing the Stability Frontier of Deep-Red Bio-Hybrid Light-Emitting Diodes

Although protein-polymer phosphors are an emerging photon-management filter concept for hybrid light-emitting diodes, deep-red-emitting devices based on archetypal fluorescent proteins (FPs; mCherry) are still poorly performing with lifetimes <50 h under high photon-flux excitation and ambient conditions. Here, the challenge is two-fold: i) understanding the deactivation mechanism of red-emitting FP-polymer coatings and, in turn, ii) identifying the best polymer design for highly stable devices. This study first provides comprehensive photophysical/thermal/structural studies and device degradation (ambient/inert) analysis, revealing the presence of photo-induced cis–trans isomerization and the effect of oxygen and water on the deactivation of mCherry in reference polymer coatings. Based on these findings, a new bio-phosphor configuration using polyvinyl alcohol derivatives, in which crystallinity and amount of trapped water (stiffness and oxygen/moisture barriers) are easily controlled by the hydroxylation degree, is successfully achieved. Compared to the prior art, these devices significantly outperform the reference stability (>50-fold enhancement), showing a brightness loss of <5% over the first 2000 h and a final device lifetime of 2600 h. Hence, this study describes a unique rationale toward designing polymers to stabilize FPs for lighting, overpassing stability frontiers in deep-red hybrid light-emitting diodes (HLEDs) going from hours to months.     

Ultracytochemistry of glycoconjugates in rat Brunner's gland with labeled lectins

Mucous glycoproteins of rat Brunner's gland were examined ultracytochemically to elucidate the intracellular localization and sites of glycosylation in relation to the functional polarity of the cell organellae using a combination of hydrophilic resin embedment and postembedding staining with labeled lectins. A few cis cisternae were stained with HPA (Helix pomatia agglutinin, specific for terminal alpha-N-acetylgalactosamine) and DBA (Dolichos biflorus aggulutinin, specific for terminal alpha-N-acetylgalactosamine). Trans cisternae as well as cisternae following secretory granules were stained with HPA and RCA-I (Recinus communis agglutinin I, specific for terminal beta-galactose). UEA-I (Ulex europaeus agglutinin I, specific for terminal alpha-L-fucose) seemed to bind to transmost cisternae rather than trans cisternae. HPA bound to the whole cisternae, but to the cis or trans cisternae depending on a cell type. Apical mucous granules were stained with UEA-I, RCA-I, and HPA, but not with DBA. DGA seemed to be a good marker of the cis side of the Golgi apparatus and cell membrane. The glycosylation of mucous glycoprotein in rat Brunner's gland was partly clarified electron microscopically.     

Precise Dielectric Measurements of Low-Loss Materials at Millimeter and Submillimeter Wavelengths

Transmission dispersive Fourier transform, spectrometry (DFTS) has been used for the measurements of both real and imaginary parts of the complex relative permittivity of low-loss materials at millimeter and submillimeter wavelengths. The materials investigated include cis and trans decalin and polypropylene.     

Steering Electron Density of Zr Sites Using Ligand Effect in Bio-Beads for Efficient Defluoridation

Because of spontaneous agglomeration effect and undesirable electronic state of Zr sites on the surface, zirconium (hydro)oxides generally exhibit suboptimal defluoridation capacity. Herein, a template confinement-ligand anchoring strategy is developed by utilizing confined growth of zirconium hydroxide (ZH) inside chitosan hydrogel beads (CHB) and subsequent anchoring of fumaric acid (fm) on its surface Zr sites in a monodentate mononuclear coordination mode. This technique leads to uniform dispersion of ultrafine fmZH (≈3.4 nm) and tunable electron density at the Zr sites. Due to the electron-withdrawing ability of fm, electron-delocalized Zr sites increase the orbital energy level matching and vacate Zr 4d orbitals to promote hybridization with the F 2p orbitals. Ultimately, robust Zr F bond can be formed as a result of reduced the adsorption energy toward fluoride ions. The defluoridation capacity shows positive linear relationship with the electron extraction ability of ligands. The saturation adsorption capacity and dynamic treatment capacity of CHB@fmZH are 10.8 and 45.9 times higher than that of CHB@ZH, respectively, owing to high electron extraction (0.098 e⁻) of fm. This study offers a novel insight into the design and synthesis of high-efficiency metal oxide adsorbents by steering its surface metal sites’ electronic state through ligand effect.     

基于空间型调制器的太赫兹波快速成像技术

为解决主流太赫兹成像技术在成像速度、分辨力、清晰度以及制造成本等方面存在相互制约的问题,提出一种基于光控型空间调制器的太赫兹波快速成像技术。这一技术利用新型硅基太赫兹调制材料与数字微镜阵列器件(DMD)的集成,实现了基于单像素太赫兹探测器的快速成像,进一步分析了太赫兹波束分布特性和高斯背景对成像效果的影响,并提出了有效的优化方法。实验结果证实这种新型技术能够显著提高成像分辨力和清晰度。     

NIR Laser-Triggered Microneedle-Based Liquid Band-Aid for Wound Care

Microneedles (MNs) have attracted widespread scientific and industrial interest in the past decade as an efficient, painless, low-cost, and relatively safe transdermal drug delivery device. However, their drawbacks such as insufficient dose accuracy and limited penetration depth may limit the clinical applications. Here, a light-controlled liquid band-aid based on MNs is developed for antibacterial applications. Metal–organic framework-derived peroxidase-like nanozyme loaded in MNs can not only convert light energy into heat to enhance drug permeation but also decompose hydrogen peroxide into hydroxyl radicals for antibacteria. The heat generated by the nanozyme can facilitate MNs to melt and form a liquid band-aid, which is beneficial to insulate the wound from the surrounding bacterial environment. These studies in a Staphylococcus aureus-infected mice model also prove that this laser-triggered liquid band-aid can efficiently reduce skin inflammation and promote wound healing. Together, these results demonstrate that the rational design of MNs can enhance antibacterial and wound healing efficiency.     

18.9% Efficiency Ternary Organic Solar Cells Enabled by Isomerization Engineering of Chlorine-Substitution on Small Molecule Donors

Ternary organic solar cells (OSCs) represent an efficient and facile strategy to further boost the device performance. However, the selection criteria and rational design of the third guest small molecule (SM) material still remain less understood. In this study, two new SM donor isomers, with α-chlorinated thiophene (αBTCl) and β-chlorinated thiophene (βBTCl) as side chains, are systematically designed, synthesized and incorporated as a third component in PM6:L8-BO binary blends. It is noticed that introducing the SM donors guest has extended the absorption of photo-active layer, induced desired component distribution vertically with enhanced crystallinity and reduced recombination process, leading to increased short-circuit current (J_SC) and improved fill factor. Moreover, due to the synergetic suppressed nonradiative loss and preferable morphology, the ternary OSCs feature improves open-circuit voltage (V_OC). Consequently, an impressive champion power conversion efficiency of 18.96% and 18.55% is achieved by αBTCl-based and βBTCl-based ternary OSCs, respectively. Furthermore, a record efficiency of 17.46% is obtained with a 330 nm thickness of αBTCl-based ternary OSCs. This study demonstrates that molecular isomerization can be a promising design approach for SM donors to construct high-performance ternary OSCs with simultaneous enhancement of all photovoltaic parameters.