RESUMEN

Bergenia ciliata (BC) is a perennial herb that is frequently used as a traditional medicine. Its leaves and rhizomes are reported to have significant antioxidant, metal-reducing, and chelating properties. Although the rhizomes have the potential to synthesize silver nanoparticles (AgNPs), the leaves are yet to be studied for the green synthesis of metal nanoparticles. Likewise, photoirradiation also plays a significant role in the green synthesis of metal nanoparticles. In the current study, we intended to demonstrate the implications of photoirradiation by white light-emitting diode (LED) on the aqueous and methanol extracts (AE and ME, respectively) of BC leaf-mediated green synthesis of AgNPs. In this regard, the AgNP synthesis of the two extracts was performed in the dark and under 250-lumen (lm) and 825 lm LED bulbs. The physicochemical characterization of the synthesized nanoparticles was also performed, wherein percent nanoparticles yield, morphology of the nanoparticles, shape, size, percent elemental composition, crystallinity, and nanoparticle stability were studied. The nanoparticle-synthesizing potential of the two extracts contradicted significantly in the presence and absence of light, while the AE produced a significantly high number of nanoparticles in the dark (17.26%), and increasing light intensities only attenuated the nanoparticle synthesis, whereas ME synthesized comparatively negligible silver nanoparticles in the dark (1.23%). However, increasing light intensities significantly enhanced the number of nanoparticles synthesized in 825 lms (7.41%). The GCMS analysis further gave a comparative insight into the phytochemical composition of both extracts, wherein catechol and pyrogallol were identified as major reducing agents for nanoparticle synthesis. The influence of light intensities on the physiochemical characterization of AgNPs was predominant. While the size of both the AE- and ME-mediated AgNPs increased considerably (20-50 nm diameter) with increasing light intensities, the percent of silver atoms decreased significantly with increasing light intensities in both the AE- and ME-mediated AgNPs with ranges of 13-18% and 14-24%, respectively. The nanoparticle stability studies suggested that both the AE- and ME-mediated AgNPs were stable for up to 15 days when stored at 4 °C. The stability of both nanoparticles was attributed to the presence of a wide range of phytochemicals. In conclusion, the AE of BC leaves was reported to have significantly higher AgNP-synthesizing potential as compared to the ME. However, AE-mediated AgNP synthesis is attenuated by photoirradiation, whereas ME-mediated AgNP synthesis is enhanced by photoirradiation. The photoirradiation by white LED light increases the size of the AgNPs, while the percent silver composition declines, irrespective of the extract type. Both extracts, however, have nanoparticle stabilizing potential, thereby producing stable nanoparticles.

RESUMEN

Here, it is shown that photoirradiation triggered chiral J-aggregates formation of an achiral anionic porphyrin, TPPS (tetrakis(4-sulfonatophenyl) porphyrin), in the presence of chiral triphenylamine (TPA) derivatives. A series of chiral triarylamines linked with aromatic rings is designed through urea or amide bonds. UV-irradiation of self-assembled urea-linked triphenylamine derivatives causes the formation of persistent radical cations in the chlorinated solvents, which subsequently induces the aggregation of TPPS. Transferring chirality of TPA derivatives to achiral TPPS J-aggregates leads to the chiral assemblies with remarkable chiroptical signals. The experimental results demonstrate that, TPA derivatives linked by the urea bond can effectively promote the aggregation of TPPS rather than those with the amide bond although the photo-generated radical cations are both produced. It is suggested that the urea-linked TPA derivatives are more favorable to stable radical cations and thus cause the formation of TPPS chiral J-aggregation. This work may open up an avenue for designing photo-modulated chiral supramolecular assemblies.

RESUMEN

The increase of bacterial resistance to antibiotics is a growing concern worldwide and the search for new therapies could cost billions of dollars and countless lives. Inert surfaces are major sources of contamination due to easier adhesion and formation of bacterial biofilms, hindering the disinfection process. Therefore, the objective of this study was to develop a photoactivatable and anti-adhesive kappa-carrageenan coating using proanthocyanidin as a photosensitizer. The complete reduction (>5-log10 CFU/cm3) of culturable cells of Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa pathogens was achieved after 30 min of exposure to visible light (420 nm; 30 mW/cm2) with 5 % (w/v) of the photosensitizer. Cell membrane damage was confirmed by measuring potassium leakage, epifluorescence microscopy and bacterial motility analysis. Overall, visible light irradiation on coated solid surfaces mediated by proanthocyanidin showed no cytotoxicity and inactivated clinically important pathogens through the generation of reactive oxygen species, inhibiting bacterial initial adhesion. The developed coating is a promising alternative for a wide range of applications related to surface disinfection and food biopreservation.

Asunto(s)

RESUMEN

Glutamate (Glu) is an excitatory neurotransmitter that plays a critical role in memory. Brain mapping activities of such pathways relied heavily on the ability to release Glu with spatiotemporal precision. Several photo-protecting groups (PPGs), referred to as photocages or cages, were designed to accomplish the release of Glu upon irradiation. Previously reported Glu cages responded to UV upon irradiation with single photons, which limited their use in vivo experiments due to cytotoxicity. Other caged designs suffered from lower quantum efficiency (QE) of release necessitating higher concentrations and/or longer photoirradiation times. There have been limited examples of cages that respond to visible light with single photon irradiation. Herein, we report the efficient preparation of 11 caged Glu examples that respond to two visible wavelengths, 467 nm (thiocoumarin based) and 515-540 nm (BODIPY based). The kinetics of photouncaging were studied for all caged designs, and we report all quantum efficiencies, i.e., quantum yields (Φ), that ranged from 0.0001-0.65. Two of the BODIPY cages are reported here for the first time, and one, Me-BODIPY-Br-Glu, shows the most efficient Glu release with a QE of 0.65. Similar caged designs can be extended to the inhibitory neurotransmitter, GABA. This would enable the use of two visible wavelengths to modulate the release of excitatory and inhibitory neurotransmitters upon demand via optical control.

RESUMEN

In this mini-review, we present our concepts for designing multicomponent reactions with reference to a series of sequential radical reactions that we have developed. Radical reactions are well suited for the design of multicomponent reactions due to their high functional group tolerance and low solvent sensitivity. We have focused on the photolysis of interelement compounds with a heteroatom-heteroatom single bond, which readily generates heteroatom-centered radicals, and have studied the photoinduced radical addition of interelement compounds to unsaturated compounds. First, the background of multicomponent radical reactions is described, and basic concepts and methodology for the construction of multicomponent reactions are explained. Next, examples of multicomponent reactions involving two interelement compounds and one unsaturated compound are presented, as well as examples of multicomponent reactions involving one interelement compound and two unsaturated compounds. Furthermore, multicomponent reactions involving intramolecular cyclization processes are described.

RESUMEN

α-Aminoalkylation of sulfonylarenes with alkylamines was found to be induced by photoirradiation. Here various types of alkylamines, such as trialkylamines, dialkylamines, N,N-dialkylanilines and N-alkylanilines as well as sulfonylarenes containing an azole, azine, heterole or benzene ring are available. The reaction proceeds through a homolytic aromatic substitution (HAS) process consisting of addition of an α-aminoalkyl radical to a sulfonylarene and elimination of the sulfonyl radical to give the α-arylalkylamine, where photoirradiation is considered to induce homolysis of sulfonylarenes leading to the generation of α-aminoalkyl radicals that make a radical chain operative.

RESUMEN

Organic persistent luminescence (pL) systems with photoresponsive dynamic features have valuable applications in the fields of data encryption, anticounterfeiting, and bioimaging. Photoinduced radical luminescent materials have a unique luminous mechanism with the potential to achieve dynamic pL. It is extremely challenging to obtain radical pL under ambient conditions; on account of it, it is unstable in air. Herein, a new semialiphatic polyimide-based polymer (A0) is developed, which can achieve dynamic pL through reversible conversion of radical under photoexcitation. A "joint-donor-spacer-acceptor" molecular design strategy is applied to effectively modulate the intramolecular charge-transfer and charge-transfer complex interactions, resulting in effective protection of the radical generated under photoirradiation. Meanwhile, polyimide-based polymers of A1-A4 are obtained by doping different amine-containing fluorescent dyes to modulate the dynamic afterglow color from green to red via the triplet to singlet Förster resonance energy-transfer pathway. Notably, benefiting from the structural characteristics of the polyimide-based polymer, A0-A4 have excellent processability, thermal stability, and mechanical properties and can be applied directly in extreme environments such as high temperatures and humidity.

RESUMEN

Glycan metabolic engineering is a powerful tool for studying the glycosylation in living plant cells. The use of modified monosaccharides such as deoxy or fluorine-containing glycosides has been reported as a powerful pharmacological approach for studying the carbohydrate metabolism. 1,3,4-tri-O-acetyl-2-fluoro-l-fucose (2F-Fuc) is a potent inhibitor of the plant cell elongation. After feeding plant seedlings with 2F-Fuc, this monosaccharide derivative is deacetylated and converted by the endogenous metabolic machinery into the corresponding nucleotide-sugar, which then efficiently inhibits Golgi-localized fucosyltransferases. Among plant cell wall polymers, defects in the fucosylation of the pectic rhamnogalacturonan-II cause a decrease in RG-II dimerization, which in turn induce the arrest of the cell elongation. In order to perform the inhibition of the cell elongation process in a spatio-temporal manner, we synthesized a caged 3,4-di-O-acetyl-1-hydroxy-2-fluoro-l-fucose (1-OH-2F-Fuc) derivative carrying a photolabile ortho-nitrobenzyl alcohol function at the anomeric position: 3,4-di-O-acetyl-1-ortho-nitrobenzyl-2-fluoro-l-fucose (2F-Fuc-NB). The photorelease of the trapped 1-OH-2F-Fuc was performed under a 365 nm LED illumination. We demonstrated that the in planta elimination by photoexcitation of the photolabile group releases free 2F-Fuc in plant cells, which in turn inhibits in a dose-dependent manner and, reversibly, the root cell elongation.

Asunto(s)

RESUMEN

Arylboronic acid/esters and phenyl selenides-based quinone methide (QM) precursors were reported to induce DNA interstrand crosslink (ICL) formation upon reaction with the inherently high concentrations of H2O2 in cancer cells. However, some normal cells (such as macrophages) also contain high-levels of H2O2, which may interfere with precursors' selectivity. In order to enhance the spatiotemporal specificity by the photolysis, we developed photo- and H2O2- dual-responsive DNA ICL precursors 1-3, bearing a photo-responsive coumarin moiety and a H2O2 inducible phenyl selenide group. Precursors 1-3 are efficiently activated by photoirradiation and H2O2 to generate reactive QMs crosslinking DNA. Moreover, the reactivity of precursors can be modulated by the introduction of aromatic substituents (OMe, F), and the electron donating group (OMe) displays a more pronounced promoting effect on DNA ICL formation. A subsequent piperidine heat stability study confirmed that the formed QMs primarily alkylate dAs, dGs and dCs in DNA. Furthermore, 1-3 inhibit lung cancer cell (H1299) growth by inducing DNA damage and producing toxic reactive oxygen species (ROS) upon photolysis of released coumarin. This study illustrates the potent cytotoxicity achieved by novel photo/H2O2 dual-responsive QM precursors 1-3, affording a novel strategy for the development of inducible DNA interstrand cross-linkers.

Asunto(s)

RESUMEN

A robust method to prepare silver nanoclusters (AgNCs) inside a methacrylic acid-ethyl acrylate (MAA-EA) nanogel is proposed, where AgNCs were produced within the nanogel scaffold via UV-photoreduction. The impact of UV irradiation time on the formation of AgNCs and their application in biolabeling and antimicrobial properties were examined. The AgNCs formation is described by two stages; (1) Agn (n = 2-8) nanoclusters formation between 0 and 25 min, and (2) larger silver nanoparticles (AgNPs) formed via aggregation inside the nanogel. The antimicrobial performance depended on the size and concentration of silver ions (Ag+). A maximum inhibitory concentration (MIC) of 1.1 ppm was observed for antimicrobial test with yeast, and a MIC of 11 and 22 ppm was recorded for Escherichia. coli and Staphylococcus aureus respectively. Combining with the green illumination property of AgNCs (emitted at 525 nm) with dead yeast, it could be used for biolabeling. By tuning the size through photoirradiation, the nanogel templated AgNCs is a promising candidate for antimicrobial and biolabeling applications.

Asunto(s)

RESUMEN

Bacteriorhodopsin (BR) functions as a light-driven proton pump that transitions between different states during the photocycle, such as all-trans (AT; BR568) and 13-cis, 15-syn (CS; BR548) state and K, L, M1, M2, N, and O intermediates. In this study, we used in situ photoirradiation 13C solid-state NMR to observe a variety of photo-intermediates and photoreaction pathways in [20-13C]retinal-WT-BR and its mutant [20-13C, 14-13C]retinal-D96N-BR. In WT-BR, the CS state converted to the CS* intermediate under photoirradiation with green light at -20 °C and consequently converted to the AT state in the dark. The AT state converted to the N intermediate under irradiation with green light. In D96N-BR, the CS state was converted to the CS* intermediate at -30 °C and consequently converted to the AT state. Simultaneously, the AT state converted to the M and L intermediates under green light illumination at -30 °C and subsequently converted to the AT state in the dark. The M intermediate was directly excited to the AT state by UV light illumination. We demonstrated that short-lived photo-intermediates could be observed in a stationary state using in situ photoirradiation solid-state NMR spectroscopy for WT-BR and D96N-BR, enabling insight into the light-driven proton pump activity of BR.

RESUMEN

In this study, the reactivity of organochalcogen compounds toward a representative alkyl-lead bond compound under light was investigated in detail. Under light irradiation, the Cy-Pb bond of Cy6Pb2 (Cy = cyclohexyl) undergoes homolytic cleavage to generate a cyclohexyl radical (Cy•). This radical can be successfully captured by diphenyl diselenide, which exhibits excellent carbon-radical-capturing ability. In the case of (PhS)2 and (PhTe)2, the yields of the corresponding cyclohexyl sulfides and tellurides were lower than that of (PhSe)2. This probably occurred due to the low carbon-radical-capturing ability of (PhS)2 and the high photosensitivity of the cyclohexyl-tellurium bond.

RESUMEN

Developing radical emission at ambient conditions is a challenging task since radical species are unstable in air. In the present work, we overcome this challenge by coassembling a series of tricarbonyl-substituted benzene molecules with polyvinyl alcohol (PVA). The strong hydrogen bonds between the guest dopants and the PVA host matrix protect the free radicals of carbonyl compounds after light irradiation, leading to strong solid state free radical emission. Changing temperature and peripheral functional groups of the tricarbonyl-substituted benzenes can influence the intensity of the radical emission. Quantum-chemical calculations predict that such free radical fluorescence originates from anti-Kasha D2 →D0 vertical emission by the anion radicals. The photoinduced radical emission by the tricarbonyl-substituted benzenes was successfully utilized for information encryption application.

RESUMEN

Titanium (Ti)-based implants are broadly applied in the medical field, but their related infections can lead to implant failure. Photo-irradiation of metal materials to generate antimicrobial agents, an alternative to antibiotics, is a promising method to reduce bacterial infection and antibiotic usage. It is therefore important to understand how bacterial pathogens respond to Ti surfaces. Here, Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus, the most prevalent pathogens linked to healthcare-associated infections, were used as model strains. Two different kinds of Ti surfaces respectively stored in dry condition and 0.9 % NaCl solution were applied. Upon UV irradiation and in the absence of bacteria, both tested surfaces exhibited similar bactericidal activity, even though the surfaces stored in 0.9 % NaCl solution generated a slightly higher level of reactive oxygen species (ROS). Interestingly, P. aeruginosa and S. aureus responded to the irradiated Ti surfaces differently regarding interaction time: the number of viable P. aeruginosa was reduced up to 90 % after 30 min interaction with the treated surfaces compared to the untreated ones, but this reduction is lessened to 69 %-81 % after 240 min. By contrast, UV treatment of surfaces did not impact the viability of S. aureus after 30 min interaction, however, led to more than 99 % reduction after 240 min incubation. These results provide first experimental evidence that Gram negative and positive bacterial species respond to ROS with different inactivation kinetics. This work also demonstrated that treatment with photo-irradiation in the absence of bacteria conferred Ti surfaces with efficient bactericidal activity.

Asunto(s)

RESUMEN

The direct incorporation of a trifluoromethyl group on an aromatic ring using a radical pathway has been extensively investigated. However, the direct highly para-selective C-H trifluoromethylation of a class of arenes has not been achieved. In this study, we report a light-promoted 4,5-dichlorofluorescein (DCFS)-enabled para-selective C-H trifluoromethylation of arylcarbamates using Langlois reagent. The preliminary mechanistic study revealed that the activated organic photocatalyst coordinated with the arylcarbamate led to para-selective C-H trifluoromethylation. Ten-gram scale reaction performs well highlighting the synthetic importance of this new protocol.

RESUMEN

Particulate matter (PM) has long-term effects on water quality compared to dissolved matter (DM) during downstream transfer after inflows into an aquatic environment. In the present study, the characteristics, behavior, and effects of PM from an urban watershed under photo-irradiation were investigated through sequential resuspensions before being compared. Changes in the organic matter content, heavy metals (Mn, Fe, Zn, Pb), spectroscopic indices (SUVA254, slope ratio (SR), humidification index (HIX), fluorescence index (FI), and biological index (BIX)), excitation-emission matrix combined with parallel factor analysis components (EEM-PARAFAC), and disinfection by-product formation potential (DBPFP) were analyzed. According to our results, light enhanced the release of organic matter from PM but reduced dissolved heavy metals. The PMU affected by urban-derived pollutants (i.e., rainfall particles, road-deposited sediment, sewer-pipeline-deposited sediment) exhibited higher quantities of terrestrial humic-like organic matter than PMR, which contains base particles from riverines (i.e., soil, sediments). For the PMU, the humic-like fluorescent components (C1 and C2) enhanced under light conditions with every resuspension, whereas the components decreased in the PMR. Consistent with the PARAFAC results, the trihalomethane formation potential (THMFP) of the PMU was enhanced by approximately 2.8 times more than that of the PMR, and exhibited a high correlation with the fluorescent components (C1, r = 0.81, p < 0.001). The principal component analysis results also confirmed that the characteristics of dynamic exchanges between PM and DM were distinguished by PM sources and light, and the photo-released DM and their spectral characteristics displayed opposite behaviors depending on the PM sources during the sequential resuspensions.

Asunto(s)

RESUMEN

Direct photopatterning of PDMS (Polydimethylsiloxane) through benzophenone photo-inhibition has received great interest in recent years. Indeed, the simplicity and versatility of this technique allows for easy processing of micro-canals, or local control of PDMS mechanical properties. Surprisingly, however, the chemical reactions between silicone hydride and/or silicone vinyl groups and benzophenone have only been assessed through qualitative methods (e.g., Attenuated total reflection fourier transform infrared). In this communication, the previously proposed reaction pathways are challenged, using nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC) monitoring. A different mechanism depicting the role of benzophenone irradiation on the polyaddition reaction of silicone formulations is proposed, and a simplified procedure involving aromatic solvent is finally disclosed.

RESUMEN

Limited therapeutic efficacy to hypoxic and refractory solid tumors has hindered the practical application of photodynamic therapy (PDT). Two new benzothiophenylisoquinoline (btiq)-derived cyclometalated IrIII complexes, IrL1 and MitoIrL2, were constructed as potent photosensitizers, with the latter being designed for mitochondria accumulation. Both complexes demonstrated a type I PDT process and caused photoinduced ferroptosis in tumor cells under hypoxia. This ferroptosis featured lipid peroxide accumulation, mitochondria shrinkage, down-regulation of glutathione peroxidase 4 (GPX4), and ferrostatin-1 (Fer-1)-inhibited cell death. Upon photoirradiation under hypoxia, mitochondria targeting MitoIrL2 caused mitochondria membrane potential (MMP) collapse, ATP production suppression, and induced cell apoptosis. The synergetic effect of ferroptosis and apoptosis causes MitoIrL2 to outperform IrL1 in inhibiting the growth of MCF-7, PANC-1, MDA-MB-231 cells and multicellular spheroids. This study demonstrates the first example of ferroptosis induced by photosensitizing IrIII complexes. Moreover, the synergism of ferroptosis and apoptosis provides a promising approach for combating hypoxic solid tumors through type I PDT processes.

Asunto(s)

RESUMEN

This study investigated the effect of pH of bleaching agent, photo-irradiation time or application times on bleaching action using hematoporphyrin-stained papers (HSPs) and artificially stained bovine-teeth (BT). 23% H2O2 with pH 5.5, 6.0, 7.0, 8.0 and 9.0 were applied on the specimens. HSP was photo-irradiated for 1, 3 and 5 min. BT were photo-irradiated for 10 min and the bleaching was repeated ten times (n=10). CIE L*a*b* of the specimens were measured before and after the procedure. Data were analyzed by repeated-measures ANOVA followed by multiple comparisons with Bonferroni correction. For the HSP, longer irradiation time and higher pH yielded significantly higher color difference (ΔE). As for BT, increasing application times and higher pH resulted in higher ΔE. It was concluded that the pH of the bleaching agent significantly improved the bleaching effect with increased photo-irradiation time for HSP and with an increase of repeated application times for BT.

Asunto(s)

RESUMEN

The photooxidative degradation process of plastics caused by ultraviolet irradiation leads to bond breaking, crosslinking, the elimination of volatiles, formation of free radicals, and decreases in weight and molecular weight. Photodegradation deteriorates both the mechanical and physical properties of plastics and affects their predicted life use, in particular for applications in harsh environments. Plastics have many benefits, while on the other hand, they have numerous disadvantages, such as photodegradation and photooxidation in harsh environments and the release of toxic substances due to the leaching of some components, which have a negative effect on living organisms. Therefore, attention is paid to the design and use of safe, plastic, ultraviolet stabilizers that do not pose a danger to the environment if released. Plastic ultraviolet photostabilizers act as efficient light screeners (absorbers or pigments), excited-state deactivators (quenchers), hydroperoxide decomposers, and radical scavengers. Ultraviolet absorbers are cheap to produce, can be used in low concentrations, mix well with polymers to produce a homogenous matrix, and do not alter the color of polymers. Recently, polyphosphates, Schiff bases, and organometallic complexes were synthesized and used as potential ultraviolet absorbers for polymeric materials. They reduced the damage caused by accelerated and natural ultraviolet aging, which was confirmed by inspecting the surface morphology of irradiated polymeric films. For example, atomic force microscopy revealed that the roughness factor of polymers' irradiated surfaces was improved significantly in the presence of ultraviolet absorbers. In addition, the investigation of the surface of irradiated polymers using scanning electron microscopy showed a high degree of homogeneity and the appearance of pores that were different in size and shape. The current work surveys for the first time the use of newly synthesized, ultraviolet absorbers as additives to enhance the photostability of polymeric materials and, in particular, polyvinyl chloride and polystyrene, based mainly on our own recent work in the field.