Micropillar with Radial Gradient Modulus Enables Robust Adhesion and Friction.

The gradient modulus in beetle setae plays a critical role in allowing it to stand and walk on natural surfaces. Mimicking beetle setae to create a modulus gradient in microscale, especially in the direction of setae radius, can achieve reliable contact and thus strong adhesion. However, it remains highly challenging to achieve modulus gradient along radial directions in setae-like structures. Here, polydimethylsiloxane (PDMS) micropillar with radial gradient modulus, (termed GM), is successfully constructed by making use of the polymerization inhibitor in the photosensitive resin template. GM gains adhesion up to 84 kPa, which is 2.3 and 4.7 times of soft homogeneous micropillars (SH) and hard homogeneous micropillars (HH), respectively. The radial gradient modulus facilitates contact formation on various surfaces and shifts stress concentration from contact perimeter to the center, resulting in adhesion enhancement. Meanwhile, GM achieves strong friction of 8.1 mN, which is 1.2 and 2.6 times of SH and HH, respectively. Moreover, GM possesses high robustness, maintaining strong adhesion and friction after 400 cycles of tests. The work here not only provides a robust structure for strong adhesion and friction, but also establishes a strategy to create modulus gradient at micron-scale.

Light-Induced Material Motion Fingerprint - A Tool Toward Selective Interfacial Sensitive Fractioning of Microparticles via Microfluidic Methods.

In this article, a novel strategy is presented to selectively separate a mixture of equally sized microparticles but differences in material composition and surface properties. The principle relies on a photosensitive surfactant, which makes particles under light illumination phoretically active. The latter hovers microparticles from a planar interface and together with a superimposed fluid flow, particles experience a drift motion characteristic to its interfacial properties. The drift motion is investigated as a function of applied wavelength, demonstrating that particles composed of different material show a unique spectrally resolved light-induced motion profile. Differences in those motion profile allow a selective fractioning of a desired particle from a complex particle mixture made out of more than two equally sized different particle types. Besides that, the influence of applied wavelength is systematically studied, and discussed the origin of the spectrally resolved chemical activity of microparticles from measured photo-isomerization rates.

Near-Infrared Fluorescence Imaging Sensor with Laser Diffuser for Visualizing Photoimmunotherapy Effects under Endoscopy.

The drug efficacy evaluation of tumor-selective photosensitive substances was expected to be enabled by imaging the fluorescence intensity in the tumor area. However, fluorescence observation is difficult during treatments that are performed during gastrointestinal endoscopy because of the challenges associated with including the fluorescence filter in the camera part. To address this issue, this study developed a device that integrates a narrow camera and a laser diffuser to enable fluorescence imaging through a forceps port. This device was employed to demonstrate that a laser diffuser with an NIR fluorescence imaging sensor could be delivered through a 3.2 mm diameter port. In addition, fluorescence images of Cetuximab-IR700 were successfully observed in two mice, and the fluorescence intensity confirmed that the fluorescence decayed within 330 s. This device is expected to have practical application as a tool to identify the optimal irradiation dose for tumor-selective photosensitive substances under endoscopy.

Hypersensitivity of Intrinsically Photosensitive Retinal Ganglion Cells in Migraine Induces Cortical Spreading Depression.

Migraine is a complex disorder characterized by episodes of moderate-to-severe, often unilateral headaches and generally accompanied by nausea, vomiting, and increased sensitivity to light (photophobia), sound (phonophobia), and smell (hyperosmia). Photophobia is considered the most bothersome symptom of migraine attacks. Although the underlying mechanism remains unclear, the intrinsically photosensitive retinal ganglion cells (ipRGCs) are considered to be involved in photophobia associated with migraine. In this study, we investigated the association between the sensitivity of ipRGCs and migraines and cortical spreading depression (CSD), which may trigger migraine attacks. The pupillary responses closely associated with the function of ipRGCs in patients with migraine who were irradiated with lights were evaluated. Blue (486 nm) light irradiation elicited a response from ipRGCs; however, red light (560 nm) had no such effect. Melanopsin, a photosensitive protein, phototransduces in ipRGCs following blue light stimulation. Hypersensitivity of ipRGCs was observed in patients with migraine. CSD was more easily induced with blue light than with incandescent light using a mouse CSD model. Moreover, CSD was suppressed, even in the presence of blue light, after injecting opsinamide, a melanopsin inhibitor. The hypersensitivity of ipRGCs in patients with migraine may induce CSD, resulting in migraine attacks.

Hydrogen-Bond-Network Breakdown Boosts Selective CO2 Photoreduction by Suppressing H2 Evolution.

Conventional strategies for highly efficient and selective CO2 photoreduction focus on the design of catalysts and cocatalysts. In this study, we discover that hydrogen bond network breakdown in reaction system can suppress H2 evolution, thereby improving CO2 photoreduction performance. Photosensitive poly(ionic liquid)s are designed as photocatalysts owing to their strong hydrogen bonding with solvents. The hydrogen bond strength is tuned by solvent composition, thereby effectively regulating H2 evolution (from 0 to 12.6 mmol g-1 h-1). No H2 is detected after hydrogen bond network breakdown with trichloromethane or tetrachloromethane as additives. CO production rate and selectivity increase to 35.4 mmol g-1 h-1 and 98.9 % with trichloromethane, compared with 0.6 mmol g-1 h-1 and 26.2 %, respectively, without trichloromethane. Raman spectroscopy and theoretical calculations confirm that trichloromethane broke the systemic hydrogen bond network and subsequently suppressed H2 evolution. This hydrogen bond network breakdown strategy may be extended to other catalytic reactions involving H2 evolution.

Retinal-Based Anion Pump from the Cyanobacterium Tolypothrix campylonemoides.

In this work, TcaR rhodopsin from the cyanobacterium Tolypothrix campylonemoides was characterized. Analysis of the amino acid sequence of TcaR revealed that this protein possesses a TSD motif that differs by only one amino acid from the TSA motif of the known halorhodopsin chloride pump. The TcaR protein was expressed in E. coli, purified, and incorporated into proteoliposomes and nanodiscs. Functional activity was measured by electric current generation through the planar bilayer lipid membranes (BLMs) with proteoliposomes adsorbed on one side of the membrane surface, as well as by fluorescence using the voltage-dependent dye oxonol VI. We have shown that TcaR rhodopsin functions as a powerful anion pump. Our results show that the novel microbial anion transporter, TcaR, deserves deeper investigation and may be of interest both for fundamental studies of membrane proteins and as a tool for optogenetics.

Recent Study Advances in Flexible Sensors Based on Polyimides.

With the demand for healthy life and the great advancement of flexible electronics, flexible sensors are playing an irreplaceably important role in healthcare monitoring, wearable devices, clinic treatment, and so on. In particular, the design and application of polyimide (PI)-based sensors are emerging swiftly. However, the tremendous potential of PI in sensors is not deeply understood. This review focuses on recent studies in advanced applications of PI in flexible sensors, including PI nanofibers prepared by electrospinning as flexible substrates, PI aerogels as friction layers in triboelectric nanogenerator (TENG), PI films as sensitive layers based on fiber Bragg grating (FBG) in relative humidity (RH) sensors, photosensitive PI (PSPI) as sacrificial layers, and more. The simple laser-induced graphene (LIG) technique is also introduced in the application of PI graphitization to graphene. Finally, the prospect of PIs in the field of electronics is proposed in the review.

Two Photosensitive Dermatitis Outbreaks Caused by Cordierites frondosus - Chuxiong Yi Autonomous Prefecture, Yunnan Province, China, 2023.

What is already known about this topic?: Cordierites frondosus (C. frondosus) is a species of toxic mushroom known to induce symptoms of photosensitive dermatitis. What is added by this report?: In the months of May and June 2023, a total of four patients in Chuxiong Yi Autonomous Prefecture, Yunnan Province, were affected by C. frondosus poisoning, occurring over two distinct incidents. The condition of two patients deteriorated after they were re-exposed to sunlight on the seventh day following the initial poisoning. Separately, an additional two patients reported experiencing a mild, needle-like sensation on areas of their skin exposed to the sun, recorded on the twelfth day subsequent to the poisoning. What are the implications for public health practice?: Given that symptoms of photosensitive dermatitis, a potential severe consequence of C. frondosus poisoning, can manifest up to a week post-sun exposure, it is advisable to avoid sunlight for a minimum of two weeks following poisoning.

Multi-Functional Lanthanide Metallopolymer: Self-Healing and Photo-Stimuli-Responsive Dual-Emitting Luminescence for Diverse Applications.

Photoluminescent metallopolymers displaying photo-stimuli-responsive properties are emerging as promising materials with versatile applications in photo-rewritable patterns, wearable UV sensors, and optical encryption anti-counterfeiting. However, integrating these materials into practical applications that require fast response times, lightweight qualities, fatigue resistance, and multiple encryption capabilities poses challenges. In this study, luminescent photochromic lanthanide (Ln) metallopolymers with rapid self-healing properties are developed by cross-linking terpyridine (Tpy)- and spiropyran (SP)- functionalized polyurethane chains through Ln-Tpy coordination bonds and H-bonds among polymer chains. The resulting products exhibit a range of intriguing features: i) photo-stimuli responsiveness using spiropyran monomers without additional dopants; ii) dual-emitting performance under UV-light due to Ln-Tpy and open-ring spiropyran moieties; iii) satisfactory mechanical properties and self-healing abilities from polymer chains; iv) multiple control switches for luminescence colors through photostimulation or feed ratio adjustments. Leveraging these attributes, the developed material introduces novel opportunities for light-writing applications, advanced information encryption, UV-sensing wearable devices, and insights into designing multifunctional intelligent materials for the future.

A dual-enzyme-like photosensitive nanozyme for remodeling the tumor immunosuppressive microenvironment to enhance immunotherapy.

In "immune-cold" tumors, the upregulation of immunosuppressive cells and insufficient infiltration of lymphocytes contribute to the resistance against immune therapy. Herein, we have developed a dual-enzyme-like photosensitive nanozyme (PBAF) to remodel the tumor immunosuppressive microenvironment (TIME) and induce the tumor infiltration of cytotoxic T lymphocytes (CTLs). Specifically, PBAF exhibits peroxidase (POD)-like activity and glutathione oxidase (GSHOx)-like activity and can be stimulated by 750 nm laser, promoting oxidative stress at the tumor site. Consequently, this process further leads to the reconstruction of TIME in animal experiments, inducing tumor-associated macrophages (TAMs) toward the immunostimulatory M1 phenotype, eliminating myeloid-derived suppressor cells (MDSCs) and regulatory T cells (Tregs). Simultaneously, PBAF also promotes dendritic cells (DCs) maturation to enhance CTLs infiltration into the tumor. The remodeled TIME and enhanced immune responses by PBAF demonstrate significant post-administration inhibition of recurrence and metastasis in the treatment of malignant tumors.

Preparation and characterization of photosensitive methacrylate-grafted sodium carboxymethyl cellulose as an injectable material to fabricate hydrogels for biomedical applications.

Injectable materials have attracted great attention in the manufacture of in situ forming hydrogels for biomedical applications. In this study, a facile method to prepare methacrylic anhydride (MA)-modified sodium carboxymethyl cellulose (CMC) as an injectable material for the fabrication of hydrogels with controllable properties is reported. The chemical structure of the series of MA-grafted CMC (CMCMAs) with different MA contents was confirmed by Fourier transform infrared and nuclear magnetic resonance spectroscopy, and the properties of CMCMAs were characterized. Then, the CMCMAs gel (CMCMAs-G) was fabricated by crosslinking of MA under blue light irradiation. The gelation performances, swelling behaviors, transmittance, surface porous structures and mechanical properties of CMCMAs-G can be controlled by varying the content of MA grafted on the CMC. The compressive strength of CMCMAs-G was measured by mechanical compressibility tests and up to 180 kPa. Furthermore, the in vitro cytocompatibility evaluation results suggest that the obtained CMCMAs-G exhibit good compatibility for cell proliferation. Hence, our strategy provides a facile approach for the preparation of light-sensitive and an injectable CMC-derived polymer to fabricate hydrogels for biomedical applications.

Friction Reduction Achieved by Ultraviolet Illumination on TiO2 Surface.

Controlling friction by light field is a low-cost, low-energy, non-polluting method. By applying ultraviolet light on the surface of photosensitive materials, the properties of the friction pairs or lubricant can be influenced, thus achieving the purpose of reducing friction. In this study, TiO2, an inorganic photosensitive material, was selected to investigate the modulating effect of light fields on friction lubrication when using polyalphaolefin (PAO) base oil as a lubricant, and the modulation law of light fields on the friction lubrication behavior was investigated under different loads (1-8 N), different speeds (20-380 mm/s), and different viscosities (10.1-108.6 mPa·s) of PAO base oil. The experimental results showed that light treatment could reduce the friction coefficient of PAO4 base oil lubrication from 0.034 to 0.016, with a reduction of 52.9% under conditions of 3 N-load and 56.5 mm/s-speed, and the best regulation effect could be achieved under the mixed lubrication condition. After TiO2 was treated with ultraviolet light, due to its photocatalytic property, PAO molecules were oxidized and adsorbed on the TiO2 surface to form an adsorption layer, which avoided the direct contact of rough peaks and thus reduced the friction coefficient. This study combines photosensitivity, photocatalysis, and friction, presenting a method to reduce the friction coefficient by applying a light field without changing the friction pairs or lubricants, which provides a new direction for friction modulation and gives new ideas for practical applications.

Development of a Smartphone-Based System for Intrinsically Photosensitive Retinal Ganglion Cells Targeted Chromatic Pupillometry.

Chromatic Pupillometry, used to assess Pupil Light Reflex (PLR) to a coloured light stimulus, has regained interest since the discovery of melanopsin in the intrinsically photosensitive Retinal Ganglion Cells (ipRGCs). This technique has shown the potential to be used as a screening tool for neuro-ophthalmological diseases; however, most of the pupillometers available are expensive and not portable, making it harder for them to be used as a widespread screening tool. In this study, we developed a smartphone-based system for chromatic pupillometry that allows targeted stimulation of the ipRGCs. Using a smartphone, this system is portable and accessible and takes advantage of the location of the ipRGCs in the perifovea. The system incorporates a 3D-printed support for the smartphone and an illumination system. Preliminary tests were carried out on a single individual and then validated on eleven healthy individuals with two different LED intensities. The average Post-Illumination Pupil Light Response 6 s after the stimuli offsets (PIPR-6s) showed a difference between the blue and the red stimuli of 9.5% for both intensities, which aligns with the studies using full-field stimulators. The results validated this system for a targeted stimulation of the ipRGCs for chromatic pupillometry, with the potential to be a portable and accessible screening tool for neuro-ophthalmological diseases.

Light-Driven Sign Inversion of Circularly Polarized Luminescence Enabled by Dichroism Modulation in Cholesteric Liquid Crystals.

Stimuli-responsive circularly polarized luminescence (CPL) materials show great promise in applying information encryption and anticounterfeiting. Herein, light-driven CPL sign inversion is achieved by combining a photoresponsive achiral negative dichroic dye (KG) and a static achiral positive dichroic dye (NR) as dopants at the 0.5:0.5 weight ratio into the cholesteric liquid crystal (CLC) host. The side chains of KG undergo trans/cis isomerization after 365 nm UV light irradiation, leading to the dichroism (SF) decrease. The |glum| value of CLC doping with KG (CLC-KG) weakens from 0.67 to 0.28 in response to the order degree change. Taking advantage of its unique CPL response property, the light-driven CPL sign inversion is achieved (from -0.20/0.14 to 0.02/-0.04) by incorporating NR (0.5:0.5) into the CLC-KG with helical superstructure static. Based on the synergistic use of circular polarization and responsiveness state as cryptographic primitives, the multidimensional information encryption CLC system can be realized.

Effects of omitting titanium dioxide from the film coating of a pharmaceutical tablet - An industrial case study of attempting to comply with EU regulation 2022/63.

Recently, concerns have been raised about the safety of titanium dioxide (TiO2), a commonly used component of pharmaceutical film coatings. The European Union has recently prohibited the application of this material in the food industry, and it is anticipated that the same will happen in the pharmaceutical industry. For this reason, pharmaceutical manufacturers have to consider the possible impact of removing TiO2 from the film coating of tablets. In this paper, we present a case study of a commercially produced tablet where the film coating containing TiO2 was replaced with a coating using calcium carbonate (CaCO3) or with a transparent coating. The performance of the coatings was compared by measuring the moisture absorption rate and the dissolution profile of the tablets. In these regards, there were negligible differences between the coating types. The tablets contained a highly photosensitive drug, the ability of the coatings to protect the drug was evaluated through environmental stability and photostability measurements. The HPLC results showed that the inclusion of TiO2 does not provide additional benefits, when humidity and thermal stress is applied, however its role was vital in protecting the drug from external light. There were several decomposition products which appeared in large quantities when TiO2 was missing from the coating. These results imply that photosensitivity is an issue, replacing TiO2 will be challenging, though its absence can be tolerated when the drug does not need to be protected from light.

Increase in choroidal thickness after blue light stimulation of the blind spot in young adults.

BACKGROUND: Blue light activates melanopsin, a photopigment that is expressed in intrinsically photosensitive retinal ganglion cells (ipRGCs). The axons of ipRGCs converge on the optic disc, which corresponds to the physiological blind spot in the visual field. Thus, a blue light stimulus aligned with the blind spot captures the ipRGCs axons at the optic disc. This study examined the potential changes in choroidal thickness and axial length associated with blue light stimulation of melanopsin-expressing ipRGCs at the blind spot. It was hypothesized that blue light stimulation at the blind spot in adults increases choroidal thickness. METHODS: The blind spots of both eyes of 10 emmetropes and 10 myopes, with a mean age of 28 ± 6 years (SD), were stimulated locally for 1-minute with blue flickering light with a 460 nm peak wavelength. Measurements of choroidal thickness and axial length were collected from the left eye before stimulation and over a 60-minute poststimulation period. At a similar time of day, choroidal thickness and axial length were measured under sham control condition in all participants, while a subset of 3 emmetropes and 3 myopes were measured after 1-minute of red flickering light stimulation of the blind spot with a peak wavelength of 620 nm. Linear mixed model analyses were performed to examine the light-induced changes in choroidal thickness and axial length over time and between refractive groups. RESULTS: Compared with sham control (2 ± 1 µm, n = 20) and red light (-1 ± 2 µm, n = 6) stimulation, subfoveal choroidal thickness increased within 60 min after blue light stimulation of the blind spot (7 ± 1 µm, n = 20; main effect of light, p < 0.001). Significant choroidal thickening after blue light stimulation occurred in emmetropes (10 ± 2 µm, p < 0.001) but not in myopes (4 ± 2 µm, p > 0.05). Choroidal thickening after blue light stimulation was greater in the fovea, diminishing in the parafoveal and perifoveal regions. There was no significant main effect of light, or light by refractive error interaction on the axial length after blind spot stimulation. CONCLUSIONS: These findings demonstrate that stimulating melanopsin-expressing axons of ipRGCs at the blind spot with blue light increases choroidal thickness in young adults. This has potential implications for regulating eye growth.

Phototherapy for age-related brain diseases: Challenges, successes and future.

Brain diseases present a significant obstacle to both global health and economic progress, owing to their elusive pathogenesis and the limited effectiveness of pharmaceutical interventions. Phototherapy has emerged as a promising non-invasive therapeutic modality for addressing age-related brain disorders, including stroke, Alzheimer's disease (AD), and Parkinson's disease (PD), among others. This review examines the recent progressions in phototherapeutic interventions. Firstly, the article elucidates the various wavelengths of visible light that possess the capability to penetrate the skin and skull, as well as the pathways of light stimulation, encompassing the eyes, skin, veins, and skull. Secondly, it deliberates on the molecular mechanisms of visible light on photosensitive proteins, within the context of brain disorders and other molecular pathways of light modulation. Lastly, the practical application of phototherapy in diverse clinical neurological disorders is indicated. Additionally, this review presents novel approaches that combine phototherapy and pharmacological interventions. Moreover, it outlines the limitations of phototherapeutics and proposes innovative strategies to improve the treatment of cerebral disorders.

Synthesis and Characterization of Negative-Tone Photosensitive Polyimides with Low Coefficient of Thermal Expansion for Packaging Applications.

Negative-tone photosensitive polyimides (PSPIs) with a low coefficient of thermal expansion (CTE) were prepared by dissolving polyimide precursor-poly(amide ester) (PAE) resins, photoinitiators, photocrosslinkers and other additives in organic solvents. Using triamine as a monomer and dianhydride and diamine as polycondensates, tri-branched structure PAE resins with different molecular weights named PAE-1~5 were prepared. A series of corresponding PSPI films named PSPI-1~5 were prepared from PAE-1~5 resins with the same formulation, respectively. The PSPI-1~5 films prepared from resins of this structure have excellent mechanical, thermal and electrical properties after being thermally cured at 350 °C/2 h in nitrogen. The PSPI-1~5 films' coating solution also show good photolithographic performance and are able to obtain photolithographic patterns with a resolution of about 10 µm after homogenization, exposure and development. Among the PSPI-1~5 films, PSPI-2 has the most excellent lithographic properties with a weight average molecular weight (Mw) of 2.9 × 104 g/mol, a CTE of 41 ppk/°C, a glass transition temperature (Tg) of 343 °C and a 5% weight loss temperature (Td5) of 520 °C, making it suitable for industrial scale-up. The mechanical properties of elongation at breakage of 42.4%, tensile moduli of 3.4 GPa and tensile strength of 153.7 MPa were also measured.

Digital Light Processing Route for 3D Printing of Acrylate-Modified PLA/Lignin Blends: Microstructure and Mechanical Performance.

In this study, digital light processing (DLP) was utilized to generate 3D-printed blends composed of photosensitive acrylate-modified polylactic acid (PLA) resin mixed with varying weight ratios of lignin extracted from softwood, typically ranging from 5 wt% to 30 wt%. The microstructure of these 3D-printed blends was examined through X-ray microtomography. Additionally, the tensile mechanical properties of all blends were assessed in relation to the weight ratio and post-curing treatment. The results suggest that post-curing significantly influences the tensile properties of the 3D-printed composites, especially in modulating the brittleness of the prints. Furthermore, an optimal weight ratio was identified to be around 5 wt%, beyond which UV light photopolymerization experiences compromises. These findings regarding acrylate-modified PLA/lignin blends offer a cost-effective alternative for producing 3D-printed bio-sourced components, maintaining technical performance in reasonable-cost, low-temperature 3D printing, and with a low environmental footprint.

Effects of post-curing duration on the mechanical properties of complex 3D printed geometrical parts.

This study aims to assess the efficacy of post-curing guidance supplied by 3D printing resin manufacturers. Current guidance applies generically to all geometries with the caveat that post-curing should be extended for 'large' or 'complex' geometries but specific guidance is not provided. Two vat-polymerisation 3D printers (Form3B, Figure 4 Standalone) were used to print test models in 6 biocompatible resins (Pro Black, Med White, Med Amber, Biomed Black, Biomed White, Biomed Amber). The test model is of a complex geometry whilst also housing ISO 527 test specimens in concentric layers. Two separate intervals of curing were applied (100%, 500% stated guidance) creating different curing treatments of the specimens throughout the model. Post processed test models were disassembled and pull testing performed on each of the specimens to assess the mechanical properties. The analysis showed that extending the curing duration had significant effects on the mechanical properties of some materials but not all. The layers of the model had a significant effect except for elongation at break for the Med Amber material. This research demonstrates that generic post-curing guidance regarding UV exposures is not sufficient to achieve homogenous material strength properties for complex geometries. Large variations in mechanical properties throughout the models suggest some material was not fully-cured. This raises a query if such materials as originally marketed as biocompatible are fully cured and therefore safe to use for medical applications involving complex geometries.