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Beamline B21 at the Diamond Light Source synchrotron in the UK is a small-angle X-ray scattering (SAXS) beamline that specializes in high-throughput measurements via automated sample delivery systems. A system has been developed whereby a sample can be illuminated by a focused beam of light coincident with the X-ray beam. The system is compatible with the highly automated sample delivery system at the beamline and allows a beamline user to select a light source from a broad range of wavelengths across the UV and visible spectrum and to control the timing and duration of the light pulse with respect to the X-ray exposure of the SAXS measurement. The intensity of the light source has been characterized across the wavelength range enabling experiments where a quantitative measure of dose is important. Finally, the utility of the system is demonstrated via measurement of several light-responsive samples.

Beamline B21 at the Diamond Light Source synchrotron in the UK is a small‐angle X‐ray scattering (SAXS) beamline that specializes in high‐throughput measurements via automated sample delivery systems. A system has been developed whereby a sample can be illuminated by a focused beam of light coincident with the X‐ray beam. The system is compatible with the highly automated sample delivery system at the beamline and allows a beamline user to select a light source from a broad range of wavelengths across the UV and visible spectrum and to control the timing and duration of the light pulse with respect to the X‐ray exposure of the SAXS measurement. The intensity of the light source has been characterized across the wavelength range enabling experiments where a quantitative measure of dose is important. Finally, the utility of the system is demonstrated via measurement of several light‐responsive samples. [ABSTRACT FROM AUTHOR]

A visible‐light‐induced iron‐catalyzed α‐alkylation of ketones with allylic and propargylic alcohols as pro‐electrophiles is reported. The diaminocyclopentadienone iron tricarbonyl complex plays a dual role by harvesting light and facilitating dehydrogenation and reduction steps without the help of any exogenous photosensitizer. γ,δ‐Unsaturated ketones can now be accessed through this borrowing hydrogen methodology at room temperature. Mechanistic investigations revealed that the steric hindrance on the δ‐position of either the dienone or ene‐ynone intermediate is the key feature to prevent or decrease the competitive 1,6‐reduction (and consequently the formation of the saturated ketone) and to favor the synthesis of a set of non‐conjugated enones and ynones. [ABSTRACT FROM AUTHOR]

Pure tin oxide (SnO2) as a typical conductometric hydrogen sulfide (H2S) gas-sensing material always suffers from limited sensitivity, elevated operation temperature, and poor selectivity. To overcome these hindrances, in this work, hollow CuO-SnO2 nanotubes were successfully electrospun for room-temperature (25 °C) trace H2S detection under blue light activation. Among all SnO2-based candidates, a pure SnO2 sensor showed no signal, even toward 10 ppm, while the 1% CuO-SnO2 sensor achieved a limit of detection (LoD) value of 2.5 ppm, a large response of 4.7, and a short response/recovery time of 21/61 s toward 10 ppm H2S, as well as nice repeatability, long-term stability, and selectivity. This excellent performance could be ascribed to the one-dimensional (1D) hollow nanostructure, abundant p-n heterojunctions, and the photoelectric effect of the CuO-SnO2 nanotubes. The proposed design strategies cater to the demanding requirements of high sensitivity and low power consumption in future application scenarios such as Internet of Things and smart optoelectronic systems.

Two ruthenium(II) polypyridyl complexes were prepared with the {Ru(phen)2}2+ moiety and a third sterically non-hindering bidentate ligand, namely 2,2′-dipyridylamine (dpa) and N-benzyl-2,2′-dipyridylamine (Bndpa). Hence, complexes [Ru(phen)2(dpa)](PF6)2 (1) and [Ru(phen)2(Bndpa)](PF6)2 (2) were characterized and their photochemical behaviour in solution (acetonitrile and water) was subsequently investigated. Compounds 1 and 2, which do not exhibit notably distorted octahedral coordination environments, contrarily to the homoleptic "parent" compound [Ru(phen)3](PF6)2, experience two-step photoejection of the dpa and Bndpa ligand upon irradiation (1050–430 nm) for several hours. DNA-binding studies revealed that compounds 1 and 2 affect the biomolecule differently upon irradiation; while 2 solely modifies its electrophoretic mobility, complex 1 is also capable of cleaving it. In vitro cytotoxicity studies with two cancer-cell lines, namely A549 (lung adenocarcinoma) and A375 (melanoma), showed that both 1 and 2 are not toxic in the dark, while only 1 is significantly cytotoxic if irradiated, 2 remaining non-toxic under these conditions. Light irradiation of the complex cation [Ru(phen)2(dpa)]2+ leads to the generation of transient Ru species that is present in the solution medium for several hours, and that is significantly cytotoxic, ultimately producing non-toxic free dpa and [Ru(phen)(OH2)2]2+. [ABSTRACT FROM AUTHOR]

Protic ruthenium complexes using the dihydroxybipyridine (dhbp) ligand combined with a spectator ligand (N,N = bpy, phen, dop, Bphen) have been studied for their potential activity vs. cancer cells and their photophysical luminescent properties. These complexes vary in the extent of π expansion and the use of proximal (6,6′-dhbp) or distal (4,4′-dhbp) hydroxy groups. Eight complexes are studied herein as the acidic (OH bearing) form, [(N,N)2Ru(n,n′-dhbp)]Cl2, or as the doubly deprotonated (O− bearing) form. Thus, the presence of these two protonation states gives 16 complexes that have been isolated and studied. Complex 7A, [(dop)2Ru(4,4′-dhbp)]Cl2, has been recently synthesized and characterized spectroscopically and by X-ray crystallography. The deprotonated forms of three complexes are also reported herein for the first time. The other complexes studied have been synthesized previously. Three complexes are light-activated and exhibit photocytotoxicity. The log(Do/w) values of the complexes are used herein to correlate photocytotoxicity with improved cellular uptake. For Ru complexes 1–4 bearing the 6,6′-dhbp ligand, photoluminescence studies (all in deaerated acetonitrile) have revealed that steric strain leads to photodissociation which tends to reduce photoluminescent lifetimes and quantum yields in both protonation states. For Ru complexes 5–8 bearing the 4,4′-dhbp ligand, the deprotonated Ru complexes (5B–8B) have low photoluminescent lifetimes and quantum yields due to quenching that is proposed to involve the 3LLCT excited state and charge transfer from the [O2-bpy]2− ligand to the N,N spectator ligand. The protonated OH bearing 4,4′-dhbp Ru complexes (5A–8A) have long luminescence lifetimes which increase with increasing π expansion on the N,N spectator ligand. The Bphen complex, 8A, has the longest lifetime of the series at 3.45 μs and a photoluminescence quantum yield of 18.7%. This Ru complex also exhibits the best photocytotoxicity of the series. A long luminescence lifetime is correlated with greater singlet oxygen quantum yields because the triplet excited state is presumably long-lived enough to interact with 3O2 to yield 1O2. [ABSTRACT FROM AUTHOR]

Objective: To evaluate the effect of a time delay before the light activation of resin composite on the microtensile bond strength (µTBS) of self-etch adhesives under dynamic simulated pulpal pressure. Materials and methods: One hundred twenty crown segments were prepared from human third molars. Dentin surfaces were prepared with coarse diamond burs and connected to a dynamic pulpal pressure device. The self-etch adhesives used were Clearfil SE Bond (CSE), G2-Bond Universal (G2B), Clearfil Universal Bond Quick (CBQ), and G-Premio Bond (GPB). Each adhesive was divided into 3 subgroups: immediate light activation of resin composite (T0), delayed light activation for 150 s (T1), and 300 s (T2). The µTBS data were obtained after 24-h water storage. Scanning electron microscopy was used to evaluate the nanoleakage at the resin–dentin surface. The µTBS data were analyzed using two-way ANOVA and Duncan's multiple comparisons. Results: All adhesives demonstrated a significant reduction in µTBS at T2, except for CBQ where the bond strength was not affected by the delayed light activation times. The two-step self-etch adhesives (CSE and G2B) demonstrated higher bond strength than the one-step adhesives at all conditions. Nanoleakage was observed in all adhesives at T2; however, nanoleakage was detected only in CBQ and GPB at T1. Conclusions: Delayed light activation of resin composite adversely affected the dentin bond strength of self-etch adhesives. Two-step self-etch adhesives had better bonding performance than one-step self-etch adhesives. Clinical relevance: After adhesive application, resin composite should be adapted and cured as soon as possible. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) have emerged as promising selective membranes in oxide semiconductor gas sensors. However, their susceptibility to high temperatures poses significant challenges to the long-term stability of gas sensors. This paper proposes a novel approach for improving long-term stability by employing a light-activated technique on amorphous InGaZnO (a-IGZO) films with a ZIF-8 membrane. Under 360 nm LED illumination, UV light can penetrate the ZIF membrane and be absorbed by a-IGZO, leading to a substantial number of photogenerated carriers in the IGZO film for gas reaction. The a-IGZO film with a ZIF-8 membrane shows an excellent selective response for H 2 over CO, NO 2 , and O 3. This light-activated film maintains a gas response comparable to that of thermal-activated counterparts while significantly improving its long-term stability. Our findings underscore the potential of light-activated a-IGZO sensors as a platform for future integration with an MOF selective membrane, ensuring long-term stability. • The a-IGZO film with a ZIF-8 membrane demonstrates outstanding selectivity in detecting H 2 over CO, NO 2 , and O 3. • UV activation significantly improves the long-term stability of the MOF-integrated a-IGZO gas sensors. • UV light can penetrate through the ZIF-8 membrane and effectively activate gas reactions. [ABSTRACT FROM AUTHOR]

Metal oxide gas sensors are popular chemoresistive sensors. They are used for numerous tasks, including environmental and safety monitoring. Some gas-sensing materials exhibit photo-induced properties that can be utilized for enhanced gas detection by modifying the sensor selectivity and sensitivity when illuminated by light. Here, we present the gas sensing characteristics of highly nanoporous Cu 2 O thin films towards both electrophilic (NO 2) and nucleophilic (C 2 H 5 OH, NH 3) gas molecules under ambient temperature and modulated by visible light illumination of different colors (red: 632 nm, green: 530 nm, blue: 468 nm). Cu 2 O films were fabricated by reactive advanced gas deposition (AGD) technology. The surface and structural analysis of the samples confirm the deposition of nanoporous thin films of mixed copper oxide phases. The gas sensing property of Cu 2 O exhibited expected p -type semiconductor behavior upon electrophilic and nucleophilic gas exposures. Our results show that visible light illumination provides enhanced sensor response. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) printing enables the fabrication of complex, highly customizable structures, which are difficult to fabricate using conventional fabrication methods. Recently, the concept of four-dimensional (4D) printing has emerged, which adds active and responsive functions to 3D-printed structures. Deployable or adaptive structures with desired structural and functional changes can be fabricated using 4D printing; thus, 4D printing can be applied to actuators, soft robots, sensors, medical devices, and active and reconfigurable photonic devices. The shape of 3D-printed structures can be transformed in response to external stimuli, such as heat, light, electric and magnetic fields, and humidity. Light has unique advantages as a stimulus for active devices because it can remotely and selectively induce structural changes. There have been studies on the light activation of nanomaterial composites, but they were limited to rather simple planar structures. Recently, the light activation of 3D-printed complex structures has attracted increasing attention. However, there has been no comprehensive review of this emerging topic yet. In this paper, we present a comprehensive review of the light activation of 3D-printed structures. First, we introduce representative smart materials and general shape-changing mechanisms in 4D printing. Then, we focus on the design and recent demonstration of remote light activation, particularly detailing photothermal activations based on nanomaterial composites. We explain the light activation of 3D-printed structures from the millimeter to sub-micrometer scale.

Light adaptation of photoreceptor cells is mediated by Ca2+-dependent mechanisms. In darkness, Ca2+ influx through cGMP-gated channels into the outer segment of photoreceptors is balanced by Ca2+ extrusion via Na+/Ca2+, K+ exchangers (NCKXs). Light activates a G protein signaling cascade, which closes cGMP-gated channels and decreases Ca2+ levels in photoreceptor outer segment because of continuing Ca2+ extrusion by NCKXs. Guanylate cyclase-activating proteins (GCAPs) then up-regulate cGMP synthesis by activating retinal membrane guanylate cyclases (RetGCs) in low Ca2+ This activation of RetGC accelerates photoresponse recovery and critically contributes to light adaptation of the nighttime rod and daytime cone photoreceptors. In mouse rod photoreceptors, GCAP1 and GCAP2 both contribute to the Ca2+-feedback mechanism. In contrast, only GCAP1 appears to modulate RetGC activity in mouse cones because evidence of GCAP2 expression in cones is lacking. Surprisingly, we found that GCAP2 is expressed in cones and can regulate light sensitivity and response kinetics as well as light adaptation of GCAP1-deficient mouse cones. Furthermore, we show that GCAP2 promotes cGMP synthesis and cGMP-gated channel opening in mouse cones exposed to low Ca2+ Our biochemical model and experiments indicate that GCAP2 significantly contributes to the activation of RetGC1 at low Ca2+ when GCAP1 is not present. Of note, in WT mouse cones, GCAP1 dominates the regulation of cGMP synthesis. We conclude that, under normal physiological conditions, GCAP1 dominates the regulation of cGMP synthesis in mouse cones, but if its function becomes compromised, GCAP2 contributes to the regulation of phototransduction and light adaptation of cones.

• PPE reuse necessitates reliable respiratory and oral human pathogen decontamination. • Equitable decontamination technologies must be available in low-resource settings. • Methylene blue photochemical treatment decontaminates noroviruses on surgical masks. • Norovirus inactivation predicts inactivation of any less resistant viral contaminant. • Role of low-cost – low-tech photochemical decontamination in pandemic preparedness. In the context of the SARS-CoV-2 pandemic, reuse of personal protective equipment, specifically that of medical face coverings, has been recommended. The reuse of these typically single-use only items necessitates procedures to inactivate contaminating human respiratory and gastrointestinal pathogens. We previously demonstrated decontamination of surgical masks and respirators contaminated with infectious SARS-CoV-2 and various animal coronaviruses via low concentration- and short exposure methylene blue photochemical treatment (10 µM methylene blue, 30 minutes of 12,500-lux red light or 50,000 lux white light exposure). Here, we describe the adaptation of this protocol to the decontamination of a more resistant, non-enveloped gastrointestinal virus and demonstrate efficient photodynamic inactivation of murine norovirus, a human norovirus surrogate. Methylene blue photochemical treatment (100 µM methylene blue, 30 minutes of 12,500-lux red light exposure) of murine norovirus-contaminated masks reduced infectious viral titers by over four orders of magnitude on surgical mask surfaces. Inactivation of a norovirus, the most difficult to inactivate of the respiratory and gastrointestinal human viruses, can predict the inactivation of any less resistant viral mask contaminant. The protocol developed here thus solidifies the position of methylene blue photochemical decontamination as an important tool in the package of practical pandemic preparedness. [ABSTRACT FROM AUTHOR]

Pure tin oxide (SnO 2 ) as a typical conductometric hydrogen sulfide (H 2 S) gas-sensing material always suffers from limited sensitivity, elevated operation temperature, and poor selectivity. To overcome these hindrances, in this work, hollow CuO-SnO 2 nanotubes were successfully electrospun for room-temperature (25 °C) trace H 2 S detection under blue light activation. Among all SnO 2 -based candidates, a pure SnO 2 sensor showed no signal, even toward 10 ppm, while the 1% CuO-SnO 2 sensor achieved a limit of detection (LoD) value of 2.5 ppm, a large response of 4.7, and a short response/recovery time of 21/61 s toward 10 ppm H 2 S, as well as nice repeatability, long-term stability, and selectivity. This excellent performance could be ascribed to the one-dimensional (1D) hollow nanostructure, abundant p-n heterojunctions, and the photoelectric effect of the CuO-SnO 2 nanotubes. The proposed design strategies cater to the demanding requirements of high sensitivity and low power consumption in future application scenarios such as Internet of Things and smart optoelectronic systems.

[Display omitted] • Covalent copper-organic frameworks (CuOFs) were fabricated by connecting metal clusters and organic ligands. • CuOFs exhibit excellent light-activable peroxidase-mimetic properties. • The Tpa-Cu 3 shows the best light-activable activity and is used for colorimetrical biomarker detection. • The Tpa-Cu 3 exhibits considerable detection range and sensitivity in the detection of diverse biomarkers. As a popular sensing method, colorimetric biosensing has the advantages of convenient operation, low cost, fast response, and easy readout. However, due to the complex structure of nanomaterials, low catalytic activity, and unclear catalytic mechanisms, constructing efficient, stable, and specific artificial biocatalysts for colorimetric biosensing is still a challenge. In this study, to propose a new colorimetric biosensing system, we synthesize three different types of copper cyclic trinuclear unit-based 2D copper-organic frameworks (CuOFs) with covalent structures and light-activable catalytic centers to serve as smart artificial enzymes for highly sensitive and wide-range biocatalytic diagnosis. By varying the light absorption centers, CuOFs with different band structures, light absorption capacity, photoelectron transfer efficiency, and electron-hole pair separation efficiency can be obtained. Of the three covalent CuOFs, tris(4-aminophenyl)amine (Tpa)-Cu 3 exhibited the widest light absorption range, the narrowest band gap, the smallest electron transfer barrier, and the best-photoinduced charge separation efficiency, which was conducive to improving the light capture ability and eventually improving the photocatalytic properties. Further tests demonstrated that Tpa-Cu 3 exhibited the best peroxidase-like activity under visible light irradiation, which could effectively diagnose the glucose and common antioxidants with a wider detection range and lower detection limit than many previously reported biocatalytic materials. We expect this design will provide new insights into enzyme-like organic framework materials and unique systems for high-sensitive and wide-range colorimetric detection for future biocatalytic applications. [ABSTRACT FROM AUTHOR]

• nHA gel activated via invisible infrared light showed the maximum surface hardness (Ra). • nHA gel activated via invisible infrared light presented the highest µSBS scores. • Cohesive failure was dominant in samples remineralized with nHA gel activated via invisible infrared light. Different remineralizing pretreatments Casein phosphopeptide-amorphous calcium phosphate fluoride (CPP-ACPF), tricalcium phosphate fluoride (TCP-F), self-assembling peptide (SAP) P11-4 and 10 % Nanohydroxyapatite (nHA) gel activation via invisible infrared light on the dentin microhardness (MH) and micro shear bond strength (µSBS) of composite restoration. Seventy-five human molar teeth were collected and the dentinal surface of all the samples was exposed to different demineralizing solutions. (n = 15) Group 1 (demineralized dentin), Group 2 (CPP ACP), Group 3 (TCP-F), Group 4 (SAP P11-4), Group 5 (nHA gel activation via invisible infrared light). MH assessment was performed using Vickers hardness. Each group of 10 samples was subjected to composite restoration buildup and µSBS were tested. The debonded samples were then observed under a stereo-microscope for failure analysis. ANOVA was conducted, along with Tukey's post hoc analysis, to examine the µSBS of composite and MH of the remineralized surface. nHA gel activation via invisible infrared light pretreated specimens showed the maximum outcomes of surface hardness (331.2 ± 77.3) and bond strength (10.38 ± 2.77). However, Group 4 (SAP P11-4) (148.3 ± 29.2) remineralized dentin displayed minimum scores of MH and µSBS (5.88 ± 1.01). Remineralizing pretreatment nHA gel activation via invisible infrared light and casein phosphopeptide-amorphous calcium phosphate fluoride seem to improve the dentin MH and µSBS of the composite restoration. [ABSTRACT FROM AUTHOR]

Protic ruthenium complexes using the dihydroxybipyridine (dhbp) ligand combined with a spectator ligand (N,N = bpy, phen, dop, Bphen) have been studied for their potential activity vs. cancer cells and their photophysical luminescent properties. These complexes vary in the extent of π expansion and the use of proximal (6,6′-dhbp) or distal (4,4′-dhbp) hydroxy groups. Eight complexes are studied herein as the acidic (OH bearing) form, [(N,N)2Ru(n,n′-dhbp)]Cl2, or as the doubly deprotonated (O− bearing) form. Thus, the presence of these two protonation states gives 16 complexes that have been isolated and studied. Complex 7A, [(dop)2Ru(4,4′-dhbp)]Cl2, has been recently synthesized and characterized spectroscopically and by X-ray crystallography. The deprotonated forms of three complexes are also reported herein for the first time. The other complexes studied have been synthesized previously. Three complexes are light-activated and exhibit photocytotoxicity. The log(Do/w) values of the complexes are used herein to correlate photocytotoxicity with improved cellular uptake. For Ru complexes 1–4 bearing the 6,6′-dhbp ligand, photoluminescence studies (all in deaerated acetonitrile) have revealed that steric strain leads to photodissociation which tends to reduce photoluminescent lifetimes and quantum yields in both protonation states. For Ru complexes 5–8 bearing the 4,4′-dhbp ligand, the deprotonated Ru complexes (5B–8B) have low photoluminescent lifetimes and quantum yields due to quenching that is proposed to involve the 3LLCT excited state and charge transfer from the [O2-bpy]2− ligand to the N,N spectator ligand. The protonated OH bearing 4,4′-dhbp Ru complexes (5A–8A) have long luminescence lifetimes which increase with increasing π expansion on the N,N spectator ligand. The Bphen complex, 8A, has the longest lifetime of the series at 3.45 μs and a photoluminescence quantum yield of 18.7%. This Ru complex also exhibits the best photocytotoxicity of the series. A long luminescence lifetime is correlated with greater singlet oxygen quantum yields because the triplet excited state is presumably long-lived enough to interact with 3O2 to yield 1O2.

The misuse of many types of broad-spectrum antibiotics leads to increased antimicrobial resistance. As a result, the development of a novel antibacterial agent is essential. Photodynamic antimicrobial chemotherapy (PACT) is becoming more popular due to its advantages in eliminating drug-resistant strains and providing broad-spectrum antibacterial resistance. Carbon dots (CDs), zero-dimensional nanomaterials with diameters smaller than 10 nm, offer a green and cost-effective alternative to PACT photosensitizers. This article reviewed the synthesis methods of antibacterial CDs as well as the recent progress of CDs and their nanocomposites in photodynamic sterilization, focusing on maximizing the bactericidal impact of CDs photosensitizers. This review establishes the base for future CDs development in the PACT field. [ABSTRACT FROM AUTHOR]

In this work, organic–inorganic hybrids based on nanocrystalline indium oxide and ruthenium (II) heteroleptic complexes were used as sensitive materials for room temperature light-activated NO2 detection. In2O3 was obtained by chemical precipitation method and then annealed at three different temperatures (T = 300, 500, 700 °C) in order to investigate the influence of the microstructure of indium oxide on sensor characteristics of hybrid materials and on kinetics of the rise and fall of photoconductivity. The results of the X-ray phase analysis demonstrated that the obtained materials are single-phase with a cubic bixbyite structure. The Ru (II) heteroleptic complex, which was used as a photosensitizer, made it possible to shift the optical sensitivity range of the hybrids to the low energy region of the spectrum and to use a low-power LED (λmax = 470 nm) source for the photoactivation process. The sensor properties were investigated toward NO2 at sub-ppm range at room temperature. It was found that for pure oxides, the sensor signal correlates with a specific surface area, while for hybrid materials, both the sensor signal and photoresponse increase with increasing the matrix crystallinity. In this case, the main role is played by traps of nonequilibrium charge carriers, which are structural defects in the matrix. [ABSTRACT FROM AUTHOR]

Light activation is an effective way to impart spatiotemporal control over oligonucleotide probes that are widely applied for gene expression regulation and target function investigation. Among the major oligonucleotide caging strategies, cyclization with a photocleavable linker is an elegant design, which affords both atom efficiency and stability in many biological environments. Here, we introduce an improved protocol for circular oligonucleotide synthesis requiring only one round of HPLC purification. With a series of poly‐U oligonucleotide strands of different sizes and backbone modifications, the pre‐photolysis caging stability and post‐photolysis target binding affinity were studied through a denaturing gel assay and melting temperature measurements. A 14 U 2'‐OMe RNA probe was selected, with strong potential application in transcriptome in vivo analysis (TIVA) for mRNA isolation. [ABSTRACT FROM AUTHOR]

Aspartate aminotransferase (AAT) is a prototypical pyridoxal 5'-phosphate (PLP) dependent enzyme that catalyzes the reversible interconversion of l-aspartate and α-ketoglutarate with oxalacetate and l-glutamate via a ping-pong catalytic cycle in which the pyridoxamine 5'-phosphate enzyme form is an intermediate. There is a bountiful literature on AAT that spans approximately 60years, and much fundamental mechanistic information on PLP dependent reactions has been gained from its study. Here, we review our recent work on AAT, where we again used it as a test bed for fundamental concepts in PLP chemistry. First, we discuss the role that coenzyme protonation state plays in controlling reaction specificity, then ground state destabilization via hyperconjugation in the external aldimine intermediate is examined. The third topic is light enhancement of catalysis of Cα-H deprotonation by PLP in solution and in AAT, which occurs through a triplet state of the external aldimine intermediate. Lastly, we consider recent advances in our analyses of enzyme multiple sequence alignments for the purpose of predicting mutations that are required to interconvert structurally similar but catalytically distinct enzymes, and the application of our program JANUS to the conversion of AAT into tyrosine aminotransferase.

The field of phosphoinositide signaling has expanded significantly in recent years. Phosphoinositides (also known as phosphatidylinositol phosphates or PIPs) are universal signaling molecules that directly interact with membrane proteins or with cytosolic proteins containing domains that directly bind phosphoinositides and are recruited to cell membranes. Through the activities of phosphoinositide kinases and phosphoinositide phosphatases, seven distinct phosphoinositide lipid molecules are formed from the parent molecule, phosphatidylinositol. PIP signals regulate a wide range of cellular functions, including cytoskeletal assembly, membrane budding and fusion, ciliogenesis, vesicular transport, and signal transduction. Given the many excellent reviews on phosphoinositide kinases, phosphoinositide phosphatases, and PIPs in general, in this review, we discuss recent studies and advances in PIP lipid signaling in the retina. We specifically focus on PIP lipids from vertebrate (e.g., bovine, rat, mouse, toad, and zebrafish) and invertebrate (e.g., Drosophila, horseshoe crab, and squid) retinas. We also discuss the importance of PIPs revealed from animal models and human diseases, and methods to study PIP levels both in vitro and in vivo. We propose that future studies should investigate the function and mechanism of activation of PIP-modifying enzymes/phosphatases and further unravel PIP regulation and function in the different cell types of the retina.

In this work, organic–inorganic hybrids based on nanocrystalline indium oxide and ruthenium (II) heteroleptic complexes were used as sensitive materials for room temperature light-activated NO2 detection. In2O3 was obtained by chemical precipitation method and then annealed at three different temperatures (T = 300, 500, 700 °C) in order to investigate the influence of the microstructure of indium oxide on sensor characteristics of hybrid materials and on kinetics of the rise and fall of photoconductivity. The results of the X-ray phase analysis demonstrated that the obtained materials are single-phase with a cubic bixbyite structure. The Ru (II) heteroleptic complex, which was used as a photosensitizer, made it possible to shift the optical sensitivity range of the hybrids to the low energy region of the spectrum and to use a low-power LED (λmax = 470 nm) source for the photoactivation process. The sensor properties were investigated toward NO2 at sub-ppm range at room temperature. It was found that for pure oxides, the sensor signal correlates with a specific surface area, while for hybrid materials, both the sensor signal and photoresponse increase with increasing the matrix crystallinity. In this case, the main role is played by traps of nonequilibrium charge carriers, which are structural defects in the matrix.

The misuse of many types of broad-spectrum antibiotics leads to increased antimicrobial resistance. As a result, the development of a novel antibacterial agent is essential. Photodynamic antimicrobial chemotherapy (PACT) is becoming more popular due to its advantages in eliminating drug-resistant strains and providing broad-spectrum antibacterial resistance. Carbon dots (CDs), zero-dimensional nanomaterials with diameters smaller than 10 nm, offer a green and cost-effective alternative to PACT photosensitizers. This article reviewed the synthesis methods of antibacterial CDs as well as the recent progress of CDs and their nanocomposites in photodynamic sterilization, focusing on maximizing the bactericidal impact of CDs photosensitizers. This review establishes the base for future CDs development in the PACT field.

Chemoresistive gas sensors made from SnO 2 , ZnO, WO 3 , and In 2 O 3 have been prepared by flame spray pyrolysis. The sensors' response to CO and NO 2 in darkness and under illumination at different wavelengths, using commercially available LEDs, was investigated. Operation at room temperature turned out to be impractical due to the condensation of water inside the porous sensing layers and the irreversible changes it caused. Accordingly, for sensors operated at 70 °C, a characterization procedure was developed and proven to deliver consistent data. The resulting data set was so complex that usual univariate data analysis was intricate and, consequently, was investigated by correlation and principal component analysis. The results show that light of different wavelengths affects not only the resistance of each material, both under exposure to the target gases in humidity and in its absence, but also the sensor response to humidity and the target gases. It was found that each of the materials behaves differently under light exposure, and it was possible to identify conditions that need further investigations.

Carbon dots (CDots) are strongly absorptive over the visible spectrum, with the effective photon-harvesting driving rich excited state processes and properties. In this work, spectroscopic probing of these processes and properties is coupled with the evaluation of the photoinduced bactericidal function of CDots, aimed toward making correlations among the findings from the former and those from the latter on the inactivation of bacterial pathogens. Within the general mechanistic framework for CDots, the observed effective and efficient antibacterial activities of the CDots under visible light are attributed to major contributions by the initially photo-generated electrons and holes that are trapped at passivated surface defect sites of the dots, in addition to the traditional reactive oxygen species (ROS) produced in the emissive excited states from the recombination of the redox pairs. Such major contributions to the inactivation of the bacteria by the separated redox species in CDots can not be quenched by ROS scavengers commonly used in the study of photodynamic effects with classical molecular photosensitizers, thus making light-activated CDots uniquely potent antimicrobial agents. The characteristic features of photoexcited CDots and their related mechanistic implications are discussed in reference to the similar behaviors and mechanistic model of conventional semiconductor quantum dots. Image 1 [ABSTRACT FROM AUTHOR]

A general method for efficiently hatching sexually produced diapausing embryos of the microcrustacean Daphnia is valuable for establishing Daphnia as a genetic model system. In this study, we examine the effect of ultraviolet light and different amounts of storage time in darkness on the hatching efficiency in two species of the Daphnia pulex species complex, D. pulex and Daphnia pulicaria. We identified a set of lighting conditions that can trigger 80% to ~100% hatching rate for embryos produced through selfing, outcrossing, and obligate parthenogenesis. Furthermore, we found that a storage time of at least 2 weeks in the dark before exposing embryos to ultraviolet light is critical for achieving high hatching rate. The identification of these key factors for hatching diapausing embryos can greatly facilitate future Daphnia research involving complex breeding designs as well as investigating the genetic switch that activates the hatching of diapausing embryos. Research highlights: This study examines the effect of ultraviolet light on activating diapausing embryos of Daphnia pulex and Daphnia pulicaria. The identified optimal conditions can induce hatching efficiency of 80–100% in different geographical isolates of Daphnia. [ABSTRACT FROM AUTHOR]

In the present work, we report the use of regioregular poly(3-hexyltiophene) polymer (RR-P3HT) as a potential light-activated material for sensing the chemical nerve agent simulant dimethyl methylphosphonate (DMMP). The electrical response of thick films of RR-P3HT, deposited by spray-coating method onto a porous laminate substrate at room temperature, to DMMP vapours was investigated. The studied material was activated by light-emitting diodes that emitted light of different wavelengths. The sensing properties of RR-P3HT are considerably enhanced upon exposure to blue and yellow light. However, excitation by the low wavelength light (blue) caused degeneration of the material, resulting in lowered stability. In the case of the yellow light, degeneration was much slower and the limit of detection was 0.4 ppm. The studied material exhibited high selectivity, as it did not respond to 6 ppm of acetone and methanol vapours. [ABSTRACT FROM AUTHOR]

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[Display omitted] • Strategies to develop photo-activatable (e.g., photoswitchable and photocleavable) inhibitors for metalloenzymes. • Approaches to tune the photophysical properties of photo-activatable inhibitors and increase biocompatibility. • Inhibitory properties of photo-activatable inhibitors in isolated metalloenzymes, in cells, and in vivo systems. • Challenges facing the application of photo-activatable metalloenzyme inhibitors in cells, in vivo , and in the clinic. Metalloenzymes are responsible for numerous physiological and pathological processes in living organisms; however, there are very few FDA-approved metalloenzyme-targeting therapeutics (only ∼ 67 FDA-approved metalloenzyme inhibitors as of 2020, less than ∼ 5 % of all FDA-approved therapeutics). Most metalloenzyme inhibitors have been developed to target the catalytic metal centers in metalloenzymes via the incorporation of metal-binding groups. Light-controlled inhibition of metalloenzymes has been used as a means to specifically activate and inactivate inhibitor engagement at a desired location and time via light irradiation, allowing for precise spatiotemporal control over metalloenzyme activity. In this review, we summarize the strategies that have been employed to develop biocompatible light-sensitive inhibitors for metalloenzymes via the incorporation of different photo-activatable moieties (including photoswitchable and photocleavable groups), and the application of photo-activateable inhibitors both in vitro and in vivo. We also discuss the photophysical mechanisms of different photo-activatable groups, their action under physiological conditions, and the different modes of interaction between inhibitors and proteins (i.e., inhibition mechanisms) in the presence and absence of light. Finally, we discuss considerations for the future development of light-responsive metalloenzyme inhibitors and the challenges limiting their application in vivo. [ABSTRACT FROM AUTHOR]

Objectives: To determine the minimum exposure times consistent with optimized surface microhardness numbers (VHN) for the top and bottom surfaces, respectively, of a resin composite (1.5-mm depth) cured using a quartz-halogen activation lamp. Additionally, to determine the conditions appropriate to achieve optimized bottom/top hardness ratios. Method and materials: Disk specimens of a commercial resin composite restorative (Spectrum TPH) were exposed to a quartz-halogen lamp, and VHNs were measured for the top and bottom surfaces at elapsed times of 1 hour and 24 hours. Results: Data were dependent on exposure time, time elapsed alter exposure, and the surface involved. Exposure time featured limiting values in excess of which no significant increase in microhardness took place. All microhardness data increased significantly over an elapsed time interval between 1 hour and 24 hours postexposure. Microhardness ratios (bottom/top) were dependent on exposure time only and were not influenced by time elapsed after exposure. Conclusion: Minimum exposure time may be considered as the greater of the times to achieve optimized top hardness and optimized hardness ratio, respectively. (Quinlssssnce Int 2004:35:795-800) [ABSTRACT FROM AUTHOR]

Objectives: To compare the surface microhardness of a resin composite following exposure to a pulse-delayed activation routine and a standard continuous routine using a quartz-halogen lamp. Additionally, to assess the effect of increasing the distance between the activator light and the specimen using a continuous exposure routine. Method and materials: Disk specimens of a commercial resin composite restorative material were exposed to a quartz-halogen lamp in a three-step pulse-delayed routine. A continuous exposure was used as a control. Surface microhardness was recorded at the end of each step and at 1 hour after initial exposure. The data yielded four groups and the control (n = 15). Further specimens were exposed to the activator light held at a predetermined distance from the specimen. Results: The pulse-delayed routine yielded a progressive and significant increase in mean microhardness at the end of each step, and the maximum mean value was significantly lower than the control. The effect of increasing the exposure distance yielded a significant decrease in mean hardness number with increasing distance for the distances selected. Regression analysis mediated a positive linear relationship between microhardness and the natural logarithm of time and a negative correlation between microhardness and distance, respectively. Conclusion: The modified activation routines investigated resulted in significantly reduced surface microhardness numbers compared with the controls. (Quintessence Int 2003:34:468-472) [ABSTRACT FROM AUTHOR]

Extensive research has been conducted on cationic light-activated thermosensitive liposomes (CLTSLs) as a means for site-specific and controlled drug release; however, less attention has been given to the stability of these nanoparticles. Selecting the appropriate lipids is crucial for the development of a stable and responsive system. In this study, we investigated the impact of various lipids on the physical properties of cationic light-activated liposomes. Incorporating poly(ethylene glycol) PEG molecules resulted in uniform liposomes with low polydispersity index, while the addition of unsaturated lipid (DOTAP) resulted in extremely leaky liposomes, with almost 80% release in just 10 min of incubation at body temperature. Conversely, the inclusion of cholesterol in the formulation increased liposome stability too much and decreased their sensitivity to stimuli-responsive release, with only 14% release after 2 min of light exposure. To achieve stable and functional CLTSL, we substituted an equivalent amount of unsaturated lipid with a saturated lipid (DPTAP), resulting in stable liposomes at body temperature that were highly responsive to light, releasing 90% of their content in 10 s of light exposure. We also conducted two atomistic molecular dynamics simulations using lipid compositions with saturated and unsaturated lipids to investigate the effect of lipid composition on the dynamical properties of the liposomal lipid bilayer. Our findings suggest that the nature of lipids used to prepare liposomes significantly affects their properties, especially when the drug loading needs to be stable but triggered drug release properties are required at the same time. Selecting the appropriate lipids in the right amount is therefore essential for the preparation of liposomes with desirable properties.

Protein tyrosine kinases and protein phosphatases play a critical role in cellular regulation. The length of a cellular response depends on the interplay between activating protein kinases and deactivating protein phosphatases. Protein tyrosine phosphatase 1B (PTP1B) and growth factor receptor-bound protein 14 (Grb14) are negative regulators of receptor tyrosine kinases. However, in the retina, we have previously shown that PTP1B inactivates insulin receptor signaling, whereas phosphorylated Grb14 inhibits PTP1B activity. In silico docking of phosphorylated Grb14 and PTP1B indicate critical residues in PTP1B that may mediate the interaction. Phosphoinositides (PIPs) are acidic lipids and minor constituents in the cell that play an important role in cellular processes. Their levels are regulated by growth factor signaling. Using phosphoinositide binding protein probes, we observed increased levels of PI(3)P, PI(4)P, PI(3,4)P2, PI(4,5)P2, and PI(3,4,5)P3 in PTP1B knockout mouse retina and decreased levels of these PIPs in Grb14 knockout mouse retina. These observations suggest that the interplay between PTP1B and Grb14 can regulate PIP metabolism.

The review deals with issues related to the principle of operation of resistive semiconductor gas sensors and the use of light activation instead of thermal heating when detecting gases. Information on the photoelectric and optical properties of nanocrystalline oxides SnO2, ZnO, In2O3, and WO3, which are the most widely used sensitive materials for semiconductor gas sensors, is presented. The activation of the gas sensitivity of semiconductor materials by both UV and visible light is considered. When activated by UV light, the typical approaches for creating materials are (i) the use of individual metal oxides, (ii) chemical modification with nanoparticles of noble metals and their oxides, (iii) and the creation of nanocomposite materials based on metal oxides. In the case of visible light activation, the approaches used to enhance the photo- and gas sensitivity of wide-gap metal oxides are (i) doping; (ii) spectral sensitization using dyes, narrow-gap semiconductor particles, and quantum dots; and (iii) addition of plasmon nanoparticles. Next, approaches to the description of the mechanism of the sensor response of semiconductor sensors under the action of light are considered.

Objectives: A systematic review and a network meta-analysis were performed to answer the following research question: "Is there any light-activation protocol capable of improving color change efficacy when associated with an in-office bleaching gel in adults?"Material and methods: A search was performed in PubMed, Scopus, Web of Science, LILACS, BBO, Cochrane Library, and SIGLE without date and/or language restrictions in April 23, 2017 (updated on March 30, 2018). IADR abstracts (1990-2018), unpublished and ongoing trial registries, dissertations, and theses were also searched. Only randomized clinical trials conducted in adults that included at least one group treated with in-office dental bleaching with light activation were included. The risk of bias (RoB) was evaluated using the Cochrane Collaboration tool. A random-effects Bayesian-mixed treatment comparison (MTC) model was used to combine light-activated versus light-free in-office bleaching with direct light-free comparison trials. A meta-analysis with independent analysis (high- and low-concentrate hydrogen peroxide [HP]) was conducted for color change (∆E*, ∆SGU).Results: After the removal of duplicates, title, and abstract screening, 28 studies remained. Nine were considered to be at a low RoB, five were at a high RoB, and the remaining were at an unclear RoB. The MTC analysis showed no significant difference in color change (ΔE* and ΔSGU) between light-activation protocols and light-free in-office bleaching, regardless of the HP concentration in the efficacy of the bleaching.Conclusion: No type of light-activated in-office bleaching was superior to light-free in-office bleaching for both high- and low-concentrate in-office bleaching gels (PROSPERO—CRD42017078743).Clinical relevance: Although many times dental professionals use "laser whitening" as a form of marketing, this study confirmed that no type of light-activation for in-office bleaching can improve the bleaching efficacy. [ABSTRACT FROM AUTHOR]

Abstract Light-illumination assistance has emerged as an important strategy to develop metal oxide semiconductor (MOS) based gas sensor with low working temperature. Here, we report a facile and reliable sacrificial template method for novel ZnO porous octahedrons (POHs), in which ZnC 2 O 4 ·2H 2 O solid octahedrons were pre-synthesized through a simple precipitation reaction at room temperature and then used as sacrificial template for ZnO POHs. Au-decorated ZnO POHs were also prepared by introducing Au species in the precipitation step. The two kinds of POHs are about 2–4 μm in size and constructed by a great number of loosely stacked nanoparticles with the size about 30–50 nm. Numerous nanometer-sized pores are in situ created in the POHs during the decomposition of oxalate sacrificial template. Under the UV-light (∼365 nm) irradiation, the sensor fabricated with Au-decorated ZnO POHs exhibits an enhanced response towards formaldehyde at room temperature as compared with pure ZnO POHs. Besides of higher response, the Au/ZnO sensor also exhibits a good linearity within 50–800 ppm formaldehyde, as well as good selectivity and repeatability, demonstrating its promising application in formaldehyde detection. The UV-light activated gas-sensing mechanism is also discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] Previously we have demonstrated that light can be used to control the release of insulin in diabetic animals, followed by a reduction in blood glucose. This is accomplished using a photoactivated depot (PAD) of insulin injected into the skin, and irradiated by a small external LED light source. In this work for the first time we demonstrate dose–response, showing that we can vary insulin release and commensurate blood glucose reduction by varying the amount of light administered. In addition to demonstrating dose–response, we have shown multi-day depot response, with insulin being released on two different days from the same depot. The material used in these studies was CD-insulin, a form of insulin that has a highly non-polar cyclododecyl group attached, markedly reducing the solubility of the modified material, and allowing it to form a depot upon injection. Upon photolysis, the cyclododecyl group is removed, releasing fully native, soluble insulin. Variable response and multi-day response as demonstrated strongly support the potential utility of the PAD approach for the variable and extended release of therapeutic peptides. [ABSTRACT FROM AUTHOR]

Thanks to its innocuousness and high spatiotemporal resolution, light is used in several established and emerging applications in biomedicine. Among them is the modulation of magnetic resonance imaging (MRI) contrast agents’ relaxivity with the aim to increase the sensitivity, selectivity and amount of functional information obtained from this outstanding whole-body medical imaging technique. This approach requires the development of molecular contrast agents that show high relaxivity and strongly pronounced photo-responsiveness. To this end, we report here the design and synthesis of a light-activated MRI contrast agent, together with its evaluation using UV–vis spectroscopy, Fast Field Cycling (FFC) relaxometry and relaxometric measurements on clinical MRI scanners. The high relaxivity of the reported agent changes substantially upon irradiation with light, showing a 17% decrease in relaxivity at 0.23T upon irradiation with λ = 400 nm (violet) light for 60 min. On clinical MRI scanners (1.5T and 3.0T), irradiation leads to a decrease in relaxivity of 9% and 19% after 3 and 60 min, respectively. The molecular design presents an important blueprint for the development of light-activatable MRI contrast agents.

Light-activated liposomes permit site and time-specific drug delivery to ocular and systemic targets. We combined a light activation technology based on indocyanine green with a hyaluronic acid (HA) coating by synthesizing HA–lipid conjugates. HA is an endogenous vitreal polysaccharide and a potential targeting moiety to cluster of differentiation 44 (CD44)-expressing cells. Light-activated drug release from 100 nm HA-coated liposomes was functional in buffer, plasma, and vitreous samples. The HA-coating improved stability in plasma compared to polyethylene glycol (PEG)-coated liposomes. Liposomal protein coronas on HA- and PEG-coated liposomes after dynamic exposure to undiluted human plasma and porcine vitreous samples were hydrophilic and negatively charged, thicker in plasma (~5 nm hard, ~10 nm soft coronas) than in vitreous (~2 nm hard, ~3 nm soft coronas) samples. Their compositions were dependent on liposome formulation and surface charge in plasma but not in vitreous samples. Compared to the PEG coating, the HA-coated liposomes bound more proteins in vitreous samples and enriched proteins related to collagen interactions, possibly explaining their slightly reduced vitreal mobility. The properties of the most abundant proteins did not correlate with liposome size or charge, but included proteins with surfactant and immune system functions in plasma and vitreous samples. The HA-coated light-activated liposomes are a functional and promising alternative for intravenous and ocular drug delivery.

In the present work, we report the use of regioregular poly(3-hexyltiophene) polymer (RR-P3HT) as a potential light-activated material for sensing the chemical nerve agent simulant dimethyl methylphosphonate (DMMP). The electrical response of thick films of RR-P3HT, deposited by spray-coating method onto a porous laminate substrate at room temperature, to DMMP vapours was investigated. The studied material was activated by light-emitting diodes that emitted light of different wavelengths. The sensing properties of RR-P3HT are considerably enhanced upon exposure to blue and yellow light. However, excitation by the low wavelength light (blue) caused degeneration of the material, resulting in lowered stability. In the case of the yellow light, degeneration was much slower and the limit of detection was 0.4 ppm. The studied material exhibited high selectivity, as it did not respond to 6 ppm of acetone and methanol vapours.

The concept of light activation for triggering hydrogen release or uptake in hydrogen storage materials was investigated with the aid of gold (Au) nanoparticles dispersed at the surface of typical hydrides including magnesium hydride (MgH2), lithium hydride (LiH) and sodium alanate (NaAlH4). Upon Xe lamp illumination, the overall temperature of the materials reached ca. 100 °C owing to the plasmonic heating effect of the Au nanoparticles. Direct‐heat‐driven hydrogen storage at the same temperature with a conventional electrical furnace was found to be less effective with a smaller fraction of hydrogen released from Au/LiH and no phase conversion for Au/NaAlH4 or for Au/Mg under hydrogen pressure. The better efficiency of the observed light‐driven hydrogen storage is attributed to the higher temperature in the vicinity of the Au nanoparticles owing to their plasmonic effect. With further improvements, light‐activated hydrogen storage could lead to an effective approach for hydrogen uptake and release from hydrides at low temperatures. In the spotlight: For some hydrogen storage materials, hydrogen uptake and release is temperature dependent. When Au nanoparticles, which display local plasmonic heating upon light illumination, are dispersed on the surface of hydrogen storage materials such as Mg, LiH and NaAlH4, these materials display light‐activated hydrogen uptake and release (see figure). [ABSTRACT FROM AUTHOR]