Lighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo

Photoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials.     

Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

二芳基乙烯类光致变色化合物的合成及其光电性质研究

在氮气及-78℃条件下,合成了两种二芳基乙烯类光致变色化合物1,2-双(2-甲基-5-(4-N,N-二甲氨基苯基)噻吩-3-基)全氟环戊烯(Ⅰa)和1,2-双(2-甲基-5-萘基噻吩-3-基)全氟环戊烯(Ⅱa),通过紫外-可见吸收光谱、荧光光谱、循环伏安法对其光谱特性和电化学性质进行了初步研究。在254nm紫外光照射下,Ⅰa和Ⅱa的氯仿溶液均由无色变为蓝色,最大吸收峰分别为620和570nm,在适当波长可见光照射下,均从有色态返回到无色态。通过UV-Vis光谱考察了这两种二芳基乙烯类化合物在溶液中的光致变色反应的动力学特征,实验结果表明,二芳基乙烯类光致变色化合物的闭环反应属于零级反应,开环反应为一级。电化学研究表明,在溶液中,Ⅰa和Ⅱa可发生不可逆的阳极氧化反应。     

All-Visible-Light Triggered Photoswitch of Dithienylethene Derivatives with Molecular Conformation Changes Excess 5 Å

Developing new all-visible-light driven fluorescent molecular switches has attracted much interests due to their important application prospects in materials science and life science. Herein, three novel all-visible-light triggered fluorescent molecular photoswitches ( 2P3 , 4F , and 4Cl ) are designed and prepared, which are realized by prolonging π-conjugation length with aggregated-induced emission units. These photoswitches show reversible photochromic and fluorescent switching in dilute solutions and films under 420 nm and 560 nm irradiations. Meanwhile, upon alternating irradiations with 450 nm/560 nm light, effective photochromic and fluorescent switching in powder states are also achieved. More interestingly, two distinct conformations with different photochromic abilities can be altered by solvents polarity. The size difference of the two conformations is over 5 Å in the vertical direction which is one of the largest changes among photochromic molecules based on dithienylethene. The accompanying conformational changes are analysed to understand the relationship between solvent characteristics and crystal structure, as well as the intermolecular interaction in solid state for all-visible-light triggered photoswitching molecules.     

Shrinkable Nanotubes for Duplex Formation of Short Nucleotides

Molecular monolayer nanotubes produced by self‐assembly of an amphiphile modified with a 2‐nitrobenzyl group as a photoresponsive unit are able to encapsulate dinucleotides via electrostatic attraction. Upon photoirradiation, the 18 nm inner diameter of the nanotubes shrinks to less than 2 nm as a result of photochemical cleavage of the 2‐nitrobenzyl group in the amphiphile. This shrinking of the nanotube channels leads to a propulsive release of the dinucleotides into the bulk solution and simultaneously accelerates formation of the dinucleotide duplexes. The larger nanotube channels without photoirradiation merely release each dinucleotide into the bulk solution, indicating that the squeezing via transportation in the narrow nanotube channels is necessary for duplex formation. In addition to the size effect, water with a lower polarity confined within the narrow nanotube channels helps to stabilize the energetically unfavorable hydrogen‐bonded base pair between the dinucleotides. This system should enable researchers to perform biological reactions that occur only in specific environments and conditions in living organisms.     

Droplets Manipulated on Photothermal Organogel Surfaces

A photoresponsive organogel surface (POS), which integrates characteristics of the photothermal property of Fe₃O₄ nanoparticles and the low hysteresis feature of lubricant‐infused organogels, is shown. A photothermally induced dynamic temperature gradient can be formed rapidly at the location of near‐infrared‐light irradiation (NIR) on POS with suitable Fe₃O₄ nanoparticles content. Thus, various droplets (e.g., water, glycerol, ethylene glycol, propylene glycol, and ethanol) can be transported effectively and nimbly (e.g., along desired trajectories with controllable velocity and direction, even run uphill and deliver solid particles). This work reveals a synergistic effect between the asymmetrical droplet deformation and the inside Marangoni flows, which forms a unique driving force for droplet transport with high efficiency. This finding offers insight into the design of novel responsive interface materials for droplet transportation, which would be significant for laboratory‐on‐a‐chip contexts, mass transportation, and microengines.     

光响应型分子的合成及应用研究进展

光响应型分子作为一种刺激性响应分子,因其具有信号稳定、远程控制、瞬时性和环保性等优势,而广泛应用于智能材料、光控器件等领域,其中最典型、研究最广泛的当属光致异构分子。光致异构分子在特定波长光照下会发生结构变化,在宏观上有时会表现出颜色的改变,在另一波长光照下结构会重新变为原来的结构,颜色也会随之褪去。综述了螺吡喃、偶氮苯、二芳基乙烯等几种主流的光致异构分子的合成与制备、光响应机理以及在盐湖资源提取、药物检测、储能材料制备等实际生产生活中的应用,并对光响应分子在低成本环境友好合成、复合功能材料化、智能分子器件等方面的发展趋势进行了展望。     

Photoresponsive polymeric systems: 1. Mixed monomolecular films of some synthetic polymers and indolinospiropyrans

The properties of mixed monolayer films of photochromic indolinospiropyrans and poly(methylmethacrylate) (PMMA), poly(vinyl stearate) (PVSt), and poly(2-vinyl pyridine) (P2VP) have been studied. It was found that reversible photoinduced changes in monolayer surface-pressure with time occurred in collapsed systems and in mixed films in which the photochrome had been forced out of the polymer monolayer. Mixed films of P2VP and a spiropyran of particular structure could have their inherent stability increased under the action of ultraviolet irradiation on aqueous subphases. This effect appeared to be related to the formation of a physically crosslinked photomerocyanine-polymer two-dimensional network.     

含偶氮苯单元光响应多肽的研究进展

综述了含偶氮苯光色性单元的多肽光响应效应，主要包括光诱导的无规线团与右手α-螺旋之间的转变；左、右手-α-螺旋的反转；光激发的聚集-解聚过程以及由多肽形成的单层膜光力学效应。这些效应表明光响应多肽是一类很有前景的光响应化合物，可作为设计光调节传感器等光响应装置的合适材料。     

Photoresponsive optically active polymers—a review

Photoresponsive macromolecules are of interest both as novel organic materials for applications in photodevices and as models for photomodulated biological processes. The presence in polymer chains of photosensitive groups and of chiral groups capable of inducing optical activity into the polymer is very useful for the analysis of photomodulated structural variations and allows storage of the light effect in the form of chiral information. Polypeptides bearing photochromic groups in the side chains are very convenient as the chiroptical properties of the peptide chromophore can be correlated to the backbone conformation. Thus polymers of L-aspartic acid, L-glutamic acid and L-lysine with azobenzene or stilbene groups attached covalently to the side chains are discussed in terms of photoinduced conformational changes and chiroptical information storage in the spectral region of the peptide and of the photoresponsive chromophore. Optically active photochromic macromolecules with hydrocarbon backbone, such as copolymers of (—)-menthyl acrylate with vinyl or acryloyl derivatives of azobenzene, stilbene and indolinospirobenzopyran, also show in some cases photodependence of chiroptical properties with evidence of at least local conformational changes as a consequence of light irradiation which can be used for chiral information.