Correction: Liquid crystal random lasers.

Correction for 'Liquid crystal random lasers' by Guangyin Qu et al., Phys. Chem. Chem. Phys., 2023, 25, 48-63, https://doi.org/10.1039/D2CP02859J.

Photoswitches with different numbers of azo chromophores for molecular solar thermal storage.

We investigate three azo-chromophore-containing photoswitches (1, 2 and 3) for molecular solar thermal storage (MOST) based on reversible Z-E isomerization. 1, 2 and 3 are photoswitchable compounds that contain one, two and three azo chromophores, respectively. In solution, 1, 2 and 3 were charged via UV-light-induced E-to-Z isomerization. Among these three compounds, 2 exhibited an energy density as high as 272 ± 1.8 J g-1, which showed the best energy storage performance. This result originated from the low molecular weight, a high degree of photoisomerization, and moderate steric hindrance of 2, which demonstrated the advantages of the meta-bisazobenzene structure for MOST. In addition, we studied the performances of these photoswitches in the solvent-free state. Only 1 showed photoinduced reversible solid-to-liquid transitions, which enabled the charging of 1 in a solvent-free state. The stored energy density for 1 in a solvent-free state was 237 ± 1.5 J g-1. By contrast, 2 and 3 could not be charged in the solvent-free state due to the lack of solid-state photoisomerization. Our findings provide a better understanding of the structure-performance relationship for azobenzenebased MOST and pave the way for the development of high-density solar thermal fuels.

Controlling Properties and Functions of Polymer Gels Using Photochemical Reactions.

Photoresponsive polymer gels have attracted increasing interest owing to their potential applications in healable materials, drug release systems, and extracellular matrices. Because polymer gels provide suitable environments for photochemical reactions, their properties and functions can be controlled with light with a high spatiotemporal resolution. Herein, the design of photoresponsive polymer gels based on different types of photochemical reactions is introduced. The mechanism and applications of irreversible photoreactions, such as photoinduced free-radical polymerization, photoinduced click reactions, and photolysis, as well as reversible photoreactions such as photoinduced reversible cycloadditions, reversible photosubstitution of metal complexes, and photoinduced metathesis are reviewed. The remaining challenges of photoresponsive polymer gels are also discussed.

Liquid crystal random lasers.

The enthusiasm for research on liquid crystal random lasers (LCRLs) is driven by their unusual optical properties and promising potential for broad applications in manufacturing, communications, medicine and entertainment. From this perspective, we will summarize the most attractive advances in the development of LCRLs in the last decade and propose future prospects. This article will begin with a fundamental description of LCRLs, including the principle of laser generation and a description of LC substances. Then, we spend several chapters on the lasing performance control methods of LCRLs, including random lasing wavelength, threshold, and polarization properties. In addition, we analyze how the LC chiral agent structures, LC core-shell structures and new light-amplifying materials affect the design of LCRL devices. In the last chapter, we discuss the application of LCRLs in 3D displays, information encryption, biochemical sensing and other optoelectronics devices and finally end the perspective with LCRLs' likely directions in future research.

Impact of a chiral supramolecular nanostructure on the mechanical and electrical performances of triphenylene-based discotic physical gels.

Discotic π-conjugated supramolecular assemblies, especially with chiral supramolecular nanostructures, have been attracting growing research interest due to their significant optoelectronic properties and the possibilities of their applications in the new generation of organic semiconductors. However, the impact of supramolecular chirality on their mechanical and electrical performances remains poorly understood. Herein, a series of optically active supramolecular gels were formed from achiral triphenylene derivatives by introducing limonene as the chiral source. Owing to the well-ordered supramolecular packing, the homochiral supramolecular gels exhibited greater mechanical strength and higher conductivity, compared to heterochiral architectures. The impact of supramolecular packing in homochiral or heterochiral assemblies on their resulting mechanical and electrical performances was investigated in detail, which might be of great fundamental value for the rational design of chiral π-conjugated supramolecular nanostructures for applications in chiral optoelectronics.

Enantioselective cytotoxicity of chiral polymer vesicles with linear and hyperbranched structures.

Herein, we study the enantioselective cytotoxicity of vesicles self-assembled by optically active linear polymers (LNPs) and hyperbranched polymers (HBPs). Compared to HBP vesicles, LNP vesicles exhibit properties such as a higher surface charge density and more violent interaction with simulated biomembranes which results in larger cytotoxicity against HeLa cells. Specifically, racemic-LNP vesicles exhibit the largest cytotoxicity of all. More interestingly, there is no significant enantioselective dependence of HBP vesicles on the abovementioned properties. Overall, we proved that the cytotoxicity of vesicles is deeply related to chirality and topological-structures. This research is of great fundamental value for the design of novel bio-interface materials.

Co-assemblies of polydiacetylenes and metal ions for solvent sensing.

We demonstrate an easy and low-cost approach for the colorimetric differentiation of organic solvents using co-assemblies of polydiacetylenes (PDAs) and metal ions. The co-assemblies were prepared by the self-assembly of amphiphilic 10,12-tricosa diynoic acid with different metal ions (Zn2+, Cu2+, Ni2+, Ca2+) and subsequent photopolymerization. Different metal ions underwent different interactions with the carboxyl groups on the side chains of poly(10,12-tricosa diynoic acid), which influenced the stimuli-responsiveness of the PDA/metal ion co-assemblies. As a result, the PDA/metal ion co-assemblies with different metal ions showed different solvatochromism. Based on this property, the co-assemblies were used as sensors to differentiate organic solvents.

Near-Infrared Circularly Polarized Light Triggered Enantioselective Photopolymerization by Using Upconversion Nanophosphors.

Circularly polarized light (CPL) is considered to be a true chiral entity and has been suggested as an explanation for the introduction of initial chiral biases into key biomolecular building blocks. CPL used recently asymmetric photochemical reactions is of wavelengths mainly in the UV and visible regions, whereas natural CPL observed in star-forming regions of the Orion constellation falls in the IR region. Whether CPL in the IR or near-IR region could be utilized to trigger asymmetric photochemical reactions remains to be determined. Herein, it is demonstrated that enantioselective photopolymerization can be realized by using λ=980 nm CPL as the only chiral source. By incorporating NaYF4 nanophosphors as the antenna species, the enantioselective photopolymerization of achiral benzaldehyde-substituted diacetylene monomer can be realized based on an upconversion mechanism upon exposure to λ=980 nm CPL. The screw direction of the helical PDA chains can be completely controlled by the handedness of incident λ=980 nm CPL.

Supramolecular chirality of amphiphilic block copolymer films made through two steps: self-assembling first, and then solution coating.

Supramolecular chirality is achieved in amphiphilic block copolymer films made through two-step fabrication: self-assembling first and then solution coating. The amphiphilic block copolymer is composed of poly(N-isopropyl acrylamide) (pNIPAM) as hydrophilic segments and poly(methyl methacrylate) with chiral side groups as hydrophobic segments. The films fabricated by two steps show sensible circular dichroism (CD) signals around a wavelength of 200 nm. However, CD signals cannot be detected from films made by directly coating the solution of copolymers on the quartz surface. The CD signal at about 200 nm is from supramolecular arrangement of benzene units connected to the chiral group in the hydrophobic segment. This result is thought to be originated from the aggregation of the copolymer during the first step of the film forming process, and the corresponding investigation into factors affecting this process has been performed in this work. It is also found that the films fabricated by two steps can adsorb chiral small molecules enantioselectively, while the films obtained by coating the solution of copolymers directly have no such enatioselective adsorption ability.

Computed tomography lymphangiography findings in 27 cases of lymphangioleiomyomatosis.

Background Lymphangioleiomyomatosis (LAM) is a rare disease involving the bronchi, lymphatic vessels, and veins. However, there are few reports about lymphatic vessel abnormalities associated with LAM. Purpose To evaluate computed tomography (CT) lymphangiography findings in cases of LAM, especially lymphatic vessel abnormalities. Material and Methods Twenty-seven patients with LAM underwent direct lymphangiography (DLG), followed by a post-procedural thoracoabdominal CT examination. Results All 27 patients were diagnosed with LAM, including 25 (93%) with chylothorax, eight (30%) with chyloperitoneum, seven (26%) with chylous fluid in the chest and abdomen, and one (4%) with lower-limb lymphedema. The CT lymphangiography showed that 27/27 (100%) patients presented iliac or retroperitoneal lymphatic vessel dilation; 20/27 (74%) presented thoracic duct outlet obstruction; 9/27 (33%) presented pleural lymph leakage; and 13/27 (48%) presented an abnormal distribution of contrast agent in the contralateral lumbar trunk, 3/27 (11%) in the pulmonary field, 1/27 (4%) in the abdominal cavity, and 4/27 (15%) in the pelvic cavity. Five of the 27 patients (19%) had retroperitoneal lymphangioleiomyomas, with contrast agent accumulation in three cases during CT lymphangiography. Two of the 27 (7%) patients had enlarged lymph nodes in the retroperitoneum. All 27 patients (100%) diagnosed with LAM displayed various lung cysts on thoracic high-resolution CT scans. Conclusion CT lymphangiography findings can be used to diagnose most LAM cases accurately. Moreover, these findings also display the various lymphatic vessel abnormalities associated with LAM.

Fabrication of Polymer Optical Fibre (POF) Gratings.

Gratings inscribed in polymer optical fibre (POF) have attracted remarkable interest for many potential applications due to their distinctive properties. This paper overviews the current state of fabrication of POF gratings since their first demonstration in 1999. In particular we summarize and discuss POF materials, POF photosensitivity, techniques and issues of fabricating POF gratings, as well as various types of POF gratings.

Enantioselective assembly of amphipathic chiral polymer and racemic chiral small molecules during preparation of micro-scale polymer vesicles.

Enantioselective assembly is observed during preparation of vesicles from a solution mixture of an amphipathic block copolymer bearing pendent chiral L- or D-phenylalanine groups in hydrophobic segments and racemic chiral small molecules. Primary experimental results reveal that racemic chiral small molecules have been enantioselectively encapsulated into the hydrophobic shells of assembled vesicles with homochiral bilayer membrane structure, showing reverse CD signals compared with the original vesicles. A further study shows that the enantiomeric excess obtained through the enantioselective assembly is directly dependent on the molecular weight of the hydrophobic chiral chain segments, implying both the hydrophobic interaction and chirality are key points during the assembly of vesicles. Other factors, such as hydrogen-bonding interactions and π-π stacking interaction, are also found to be responsible for the enantioselective assembly phenomenon during the formation of the vesicles.

Optically binary liquid crystalline blue phases induced by one-armed cholesterol-linked azobenzene molecules.

A series of one-armed cholesterol-linked azobenzene molecules named CholXAzo with different spacers were synthesized, in which Chol6Azo was found to have induced blue phases (BPs) with a concentration of 4.0 wt%. Under irradiation of 385 nm UV light with a density of 15.0 mW cm(-2), photo-responsive behaviour of the 4.0 wt% Chol6Azo doped sample named B3 shows a sensitive temperature dependence, which means that at 38.0 °C a phase transition from BPs to the isotropic phase is induced; however, at 33.0 °C, this phase transition does not take place. Results from the research show that the optically binary phase transition behaviour of B3 is sensitive to the isomerization degree of Chol6Azo, which is closely related to the stability of the BP structure and there is a critical isomerization degree of 13.7% for the phase transition of the B3 liquid crystals. Further POM observation shows that the liquid crystal samples doped with different concentrations of Chol6Azo have an increasing transition temperature for photo-induced phase transition from the BP to the isotropic phase along with the increasing concentration of Chol6Azo, which are found to have the same changing tendency with phase transition temperature from the isotropic phase to BPs and a phase diagram is made to map the optically binary behaviour of Chol6Azo doped blue phase liquid crystals. At last, a simple pattern with the BP and the isotropic phase arranged at an interval was made in this optically binary liquid crystalline blue phase under a suitable photomask.

Chirality Transfer and Modulation in LB Films Derived From the Diacetylene/Melamine Hydrogen-Bonded Complex.

Introduction of hydrogen-bonding interaction into π-conjugated systems is a promising strategy, since the highly selective and directional hydrogen-bonding can increase the binding strength, provide enhanced stability to the assemblies, and position the π-conjugated molecules in a desired arrangement. The helical packing of the rigid melamine cores seems to play a dominating role in the subsequent formation of the peripheral helical PDA backbone. The polymerized Langmuir-Blodgett (LB) films exhibited reversible colorimetric and chiroptical changes during repeated heating-cooling cycles, which should be ascribed to the strong hydrogen-bonding interaction between the carboxylic acid and the melamine core. Further, the closely helical packing of the melamine cores could be destroyed upon exposure to HCl or NH(3) gas, whereas the peripheral helical polyaniline and polydiacetylene (PDA) backbone exhibited excellent stability. Although similar absorption changes could be observed for the films upon exposure to HCl or NH(3) gas, their distinct circular dichroism (CD) responses enabled us to distinguish the above two stimuli.

A reversible multi-stimuli-responsive fluorescence probe and the design for combinational logic gate operations.

Here, a novel multi-stimuli-responsive fluorescence probe is developed by incorporating spiropyran group into the coumarin-substituted polydiacetylene (PDA) vesicles. The fluorescence of PDA can be turned on upon heating, and can be quenched upon exposure to UV light irradiation or pH stimuli owing to the fluorescene resonance energy transfer (FRET) between the red-phase PDA and the open merocyanine (MC) form of spiropyran. Moreover, we have designed and experimentally realized a set of logic gate operations for the first time based on the fluorescence modulation of the designed system upon thermal, photo, and pH stimuli. This novel type of resettable logic gates augur well for practical applications in information storage, optical recording, and sensing in complicated microenvironments.

Disordered microstructure polymer optical fiber for stabilized coherent random fiber laser.

We have demonstrated the realization of a random polymer fiber laser (RPFL) based on laser dye Pyrromethene 597-doped one-dimensional disordered polymer optical fiber (POF). The stabilized coherent laser action for the disordered POF has been obtained by the weak optical multiple scattering of the polyhedral oligomeric silsesquioxanes nanoparticles in the core of the POF in situ formed during polymerization, which was enhanced by the waveguide confinement effect. Meanwhile, the threshold of our RPFL system is almost one order of magnitude lower than that of the liquid core random fiber laser reported previously, which promotes the development of random lasers.

Photo-controlled hierarchical assembly and fusion of coumarin-containing polydiacetylene vesicles.

Herein, we synthesize a coumarin-substituted diacetylene monomer (CODA) and report the novel photo-controlled reversible assembly and disassembly behavior of the polymerized CODA (PCODA) vesicles. The photo-triggered dimerization and cleavage reactions of the coumarin groups within the surface of the adjacent PCODA vesicles can be utilized as the driving force to induce assembly and disassembly of PCODA vesicles. Moreover, the boundary of PCODA vesicles in the aggregates becomes more obscure when the irradiation time exceeds 30 min. Fusion occurs upon close docking of target membranes, driven by sufficient dimerization of the coumarin groups within the surface of PCODA vesicles.

Quantifying emission fluxes of atmospheric pollutants from mobile differential optical absorption spectroscopic (DOAS) observations.

This study demonstrates a mobile passive differential optical absorption spectroscopy (DOAS) based remote sensing method for quantifying the emission fluxes of soot pollutants. First, the mobile DOAS system scans the plume emitted from urban sources. Then, the DOAS method retrieves the total columns of pollutant gases along the measurement path. Combining the longitude, latitude, and mobile speed recorded by vehicle GPS, the net emission fluxes of NO2 and SO2 in the measurement area are calculated by coupling with the wind field data. The NO2 flux in the region is combined with the NO to NO2 concentration ratio in the Copernicus Atmospheric Monitoring Service (CAMS) model to calculate NOx net emission flux in the measurement period. We conducted the mobile DOAS measurements in the coal production area and obtained the distribution of pollutant gases along the measurement path. Meanwhile, the NO2 concentration distribution of the city and surrounding areas were reconstructed by using TROPOMI satellite data. During the mobile measurement, the net NO2 emission flux measured by mobile DOAS are in good agreement with satellite observations (R2 = 0.66). This study verified that the flux calculation method based on mobile DOAS can be used to detect urban soot pollutant gas emissions.

A comparison review of Hehuan flowers and Hehuan bark on the traditional applications, phytochemistry and pharmacological effects.

ETHNOPHARMACOLOGICAL RELEVANCE: Albizia julibrissin Durazz is a well-known medicinal plant with the Chinese name Hehuan []. Hehuan bark and Hehuan flowers have long been recognized as traditional Chinese herbal medicine for treating anxiety, melancholy, insomnia, bruises, pulmonary abscess, fractures, carbuncle, amnesia, acute conjunctivitis, blurred vision, neonatal tetanus and stroke for thousands of years. They are recorded in Chinese Pharmacopoeia separately with different properties. Until now, new chemical constituents and pharmacological activities of Hehuan have been continuously studied and revealed. THE AIM OF THE REVIEW: This review aims to provide a comprehensive summary of traditional applications, phytochemistry, pharmacology effects, and toxicology of Hehuan bark and Hehuan flowers, and give critical assessment and point out the promising direction for further research on Hehuan. MATERIAL AND METHODS: A literature search was undertaken on Hehuan bark and Hehuan flowers by analyzing the information from scientific databases (SciFinder, Pubmed, Elsevier, Google Scholar, Web of Science, and Baidu Scholar). We also gathered the information of Hehuan from classic herbal literatures and conference papers on ethnopharmacology. RESULTS: According to Chinese and English documents, the medicinal history of Hehuan in China can be traced back to ad 25. Meanwhile, its medicinal history as a kind of herbal medicine can also be found in other Asian countries. So far about 140 compounds have been isolated from Hehuan bark and Hehuan flowers, including triterpenoids, flavonoids, lignans, phenolic acids, alkaloids, etc. Among them, flavonoids mainly exist in Hehuan flowers, while Hehuan bark contains lignans and saponins. The composition differences between the barks and flowers of Hehuan account for the different effects and applications. Modern pharmacological studies have indicated that crude extracts and pure compounds of Hehuan flowers and Hehuan bark have multiple pharmacological activities, such as antineoplastic, immunomodulatory, anti-inflammatory, anxiolytic, antidepressant, metabolic regulation, anti-insomnia, neuroprotective, hepatoprotective, sedative, and anti-osteolytic activities. CONCLUSIONS: Hehuan (Albizia julibrissin Durazz) is traditionally used to relieve depression, calm nerves, promote blood circulation and reduce swelling. Modern pharmacological studies have revealed that natural products from Hehuan bark and Hehuan flowers possess extensive pharmacological activities in treating cancer, enhancing immunity, regulating metabolism, improving mental state, etc. These properties make it great clinical application potential. Further research on natural pharmaceutical chemistry, pharmacology, toxicology, pharmacokinetics, and quality standards of Hehuan are still required to verify the efficacy and safety for future clinical applications.

Coherent random fiber laser based on nanoparticles scattering in the extremely weakly scattering regime.

We demonstrate the realization of a coherent random fiber laser (RFL) in the extremely weakly scattering regime, which contains a dispersive solution of polyhedral oligomeric silsesquioxanes nanoparticles (NPs) and laser dye pyrromethene 597 in carbon disulfide that was injected into a hollow optical fiber. Multiple scattering of polyhedral oligomeric silsesquioxanes NPs greatly enhanced by the waveguide confinement effect was experimentally verified to account for coherent lasing observed in our RFL system. This Letter extends the NPs-based RFLs from the incoherent regime to the coherent regime.