The optical properties of plasmonic nanoparticle ensembles are determined not only by the particle shape and size but also by the nanoantenna arrangement. To investigate the influence of the spatial ordering on the far-field optical properties of nanoparticle ensembles, we introduce a disorder model that encompasses both "frozen-phonon" and correlated disorder. We present experimental as well as computational approaches to gain a better understanding of the impact of disorder. A designated Fourier microscopy setup allows us to record the real- and Fourier-space images of plasmonic metasurfaces as either RGB images or fully wavelength-resolved data sets. Furthermore, by treating the nanoparticles as dipoles, we calculate the electric field based on dipole-dipole interaction, extract the far-field response, and convert it to RGB images. Our results reveal how the different disorder parameters shape the optical far field and thus define the optical appearance of a disordered metasurface and show that the relatively simple dipole approximation is able to reproduce the far-field behavior accurately. https://www.selleckchem.com/products/plumbagin.html These insights can be used for engineering metasurfaces with tailored disorder to produce a desired bidirectional reflectance distribution function.Autophagy is an essential cellular degradation process. Impaired autophagy has been linked to multiple disorders, including cancer and neurodegeneration. Tracking the autophagic flux in living cells will provide mechanistic insights into autophagy and will allow rapid screening of autophagy modulators as potential therapeutics. Imaging autophagy to track the autophagic flux demands a cell-permeable probe that can specifically target autophagic vesicles and report on the extent of autophagy. Existing fluorescent protein-based probes for imaging autophagy target autophagic vesicles but are cell-impermeable and degrade with the progress of autophagy resulting in ambiguous information on the later stages of autophagy. Although small-molecule-based autophagy probes can be cell-permeable, they are mostly water-insoluble and often target lysosomes instead of autophagic vesicles leading to incomplete evidence of the early stages of the process. Hence, there is a major gap in the ability to link the imaging data obtained by applying fluorescent sensors to the real extent of autophagy in living cells. To address these challenges, we have combined the desirable features of targetability and cell permeability to develop a novel water-soluble, cell-permeable, visible-light excitable, peptide-based, fluorescent sensor, HCFP, for imaging autophagy and tracking the autophagic flux. The probe readily enters living cells within 30 min of incubation, distinctly targets autophagic vesicles, and spatio-temporally tracks the entire autophagy pathway in living cells via a ratiometric pH-sensitive detection scheme. The salient features of the probe combining targetability with cell permeability should provide an edge in high-throughput screening of autophagy modulators by tracking autophagy live.Cyanodiarylethene chromophores are able to undergo constitutional exchange via dynamic covalent chemistry (DCC). During this process, the central ethylene bridge of the molecular scaffold can be broken and thereby enables the assembly of a new combination of aryl moieties around the reformed ethylene bridge. The reversible C═C double bond exchange has exemplarily been investigated using α-cyanostilbenes. Establishing a dynamic equilibrium reaction from α-cyanodiarylethene with arylacetonitriles under mild conditions has been the basis to access constitutional libraries of new photoswitches with potentially improved properties. When subject to irradiation with light of adequate wavelength, α-cyanodiarylethenes undergo Z/E isomerization followed by ring-closure. By screening the thus accessible dynamic chromophore libraries using a desired detection wavelength, we could identify specific dithienyl analogues that exhibit three-state photochromism. The combination of dynamic constitutional libraries of functional chromophores in combination with the light-guided screening and selection should lead to more rapid exploration of structural diversity dye chemistry.In this study, we addressed an important drawback of our previously reported tetraplatinated (metallo)porphyrin-based photosensitizers (PSs) for photodynamic therapy (PDT), namely, the poor solubility in aqueous media. We aimed to create tetraplatinated porphyrin-based PSs that are soluble in aqueous media modified with polysorbate (Tween) and do not need to be pre-dissolved in organic solvents. A structural optimization of the previously reported PSs resulted in the synthesis of an extremely potent novel porphyrin-based PS. The novel PS displays effective phototoxicity upon light irradiation against multicellular tumor spheroids and has a phototoxic index (PI) of 6030 in HeLa cells. This PI value is, to the best of our knowledge, the highest value reported for any porphyrin so far.A series of nine RuII arene complexes bearing tridentate naphthoquinone-based N,O,O-ligands was synthesized and characterized. Aqueous stability and their hydrolysis mechanism were investigated via UV/vis photometry, HPLC-MS, and density functional theory calculations. Substituents with a positive inductive effect improved their stability at physiological pH (7.4) intensely, whereas substituents such as halogens accelerated hydrolysis and formation of dimeric pyrazolate and hydroxido bridged dimers. The observed cytotoxic profile is unusual, as complexes exhibited **** higher cytotoxicity in SW480 colon cancer cells than in the broadly chemo- (incl. platinum-) sensitive CH1/PA-1 teratocarcinoma cells. This activity pattern as well as reduced or slightly enhanced ROS generation and the lack of DNA interactions indicate a mode of action different from established or previously investigated classes of metallodrugs.The construction of a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) substrate is the key factor that restricts its practical application. In this paper, a three-dimensional (3D) SERS substrate based on ordered micropyramid array and silver nanoparticles (MPA/AgNPs 3D-SERS) was constructed using the roll-to-plate embossing technology and a hydrothermal method, which provided an efficient and low-cost preparation process for the SERS substrate. Using rhodamine 6G (R6G) as a probe molecule, the performance of an MPA/AgNP 3D-SERS substrate was studied in detail, whose minimum detection limit was 10-12 M and the enhancement factor was calculated as 8.8 × 109, indicating its high sensitivity. In addition, the minimum relative standard deviation (RSD) for the MPA/AgNP 3D-SERS substrate was calculated as 4.99%, and SERS performance basically had no loss after 12 days of placement, which indicated that the prepared SERS substrate had excellent stability and repeatability. At last, the thiram detection application of the MPA/AgNP 3D-SERS substrate was also investigated.
The optical properties of plasmonic nanoparticle ensembles are determined not only by the particle shape and size but also by the nanoantenna arrangement. To investigate the influence of the spatial ordering on the far-field optical properties of nanoparticle ensembles, we introduce a disorder model that encompasses both "frozen-phonon" and correlated disorder. We present experimental as well as computational approaches to gain a better understanding of the impact of disorder. A designated Fourier microscopy setup allows us to record the real- and Fourier-space images of plasmonic metasurfaces as either RGB images or fully wavelength-resolved data sets. Furthermore, by treating the nanoparticles as dipoles, we calculate the electric field based on dipole-dipole interaction, extract the far-field response, and convert it to RGB images. Our results reveal how the different disorder parameters shape the optical far field and thus define the optical appearance of a disordered metasurface and show that the relatively simple dipole approximation is able to reproduce the far-field behavior accurately. https://www.selleckchem.com/products/plumbagin.html These insights can be used for engineering metasurfaces with tailored disorder to produce a desired bidirectional reflectance distribution function.Autophagy is an essential cellular degradation process. Impaired autophagy has been linked to multiple disorders, including cancer and neurodegeneration. Tracking the autophagic flux in living cells will provide mechanistic insights into autophagy and will allow rapid screening of autophagy modulators as potential therapeutics. Imaging autophagy to track the autophagic flux demands a cell-permeable probe that can specifically target autophagic vesicles and report on the extent of autophagy. Existing fluorescent protein-based probes for imaging autophagy target autophagic vesicles but are cell-impermeable and degrade with the progress of autophagy resulting in ambiguous information on the later stages of autophagy. Although small-molecule-based autophagy probes can be cell-permeable, they are mostly water-insoluble and often target lysosomes instead of autophagic vesicles leading to incomplete evidence of the early stages of the process. Hence, there is a major gap in the ability to link the imaging data obtained by applying fluorescent sensors to the real extent of autophagy in living cells. To address these challenges, we have combined the desirable features of targetability and cell permeability to develop a novel water-soluble, cell-permeable, visible-light excitable, peptide-based, fluorescent sensor, HCFP, for imaging autophagy and tracking the autophagic flux. The probe readily enters living cells within 30 min of incubation, distinctly targets autophagic vesicles, and spatio-temporally tracks the entire autophagy pathway in living cells via a ratiometric pH-sensitive detection scheme. The salient features of the probe combining targetability with cell permeability should provide an edge in high-throughput screening of autophagy modulators by tracking autophagy live.Cyanodiarylethene chromophores are able to undergo constitutional exchange via dynamic covalent chemistry (DCC). During this process, the central ethylene bridge of the molecular scaffold can be broken and thereby enables the assembly of a new combination of aryl moieties around the reformed ethylene bridge. The reversible C═C double bond exchange has exemplarily been investigated using α-cyanostilbenes. Establishing a dynamic equilibrium reaction from α-cyanodiarylethene with arylacetonitriles under mild conditions has been the basis to access constitutional libraries of new photoswitches with potentially improved properties. When subject to irradiation with light of adequate wavelength, α-cyanodiarylethenes undergo Z/E isomerization followed by ring-closure. By screening the thus accessible dynamic chromophore libraries using a desired detection wavelength, we could identify specific dithienyl analogues that exhibit three-state photochromism. The combination of dynamic constitutional libraries of functional chromophores in combination with the light-guided screening and selection should lead to more rapid exploration of structural diversity dye chemistry.In this study, we addressed an important drawback of our previously reported tetraplatinated (metallo)porphyrin-based photosensitizers (PSs) for photodynamic therapy (PDT), namely, the poor solubility in aqueous media. We aimed to create tetraplatinated porphyrin-based PSs that are soluble in aqueous media modified with polysorbate (Tween) and do not need to be pre-dissolved in organic solvents. A structural optimization of the previously reported PSs resulted in the synthesis of an extremely potent novel porphyrin-based PS. The novel PS displays effective phototoxicity upon light irradiation against multicellular tumor spheroids and has a phototoxic index (PI) of 6030 in HeLa cells. This PI value is, to the best of our knowledge, the highest value reported for any porphyrin so far.A series of nine RuII arene complexes bearing tridentate naphthoquinone-based N,O,O-ligands was synthesized and characterized. Aqueous stability and their hydrolysis mechanism were investigated via UV/vis photometry, HPLC-MS, and density functional theory calculations. Substituents with a positive inductive effect improved their stability at physiological pH (7.4) intensely, whereas substituents such as halogens accelerated hydrolysis and formation of dimeric pyrazolate and hydroxido bridged dimers. The observed cytotoxic profile is unusual, as complexes exhibited much higher cytotoxicity in SW480 colon cancer cells than in the broadly chemo- (incl. platinum-) sensitive CH1/PA-1 teratocarcinoma cells. This activity pattern as well as reduced or slightly enhanced ROS generation and the lack of DNA interactions indicate a mode of action different from established or previously investigated classes of metallodrugs.The construction of a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) substrate is the key factor that restricts its practical application. In this paper, a three-dimensional (3D) SERS substrate based on ordered micropyramid array and silver nanoparticles (MPA/AgNPs 3D-SERS) was constructed using the roll-to-plate embossing technology and a hydrothermal method, which provided an efficient and low-cost preparation process for the SERS substrate. Using rhodamine 6G (R6G) as a probe molecule, the performance of an MPA/AgNP 3D-SERS substrate was studied in detail, whose minimum detection limit was 10-12 M and the enhancement factor was calculated as 8.8 × 109, indicating its high sensitivity. In addition, the minimum relative standard deviation (RSD) for the MPA/AgNP 3D-SERS substrate was calculated as 4.99%, and SERS performance basically had no loss after 12 days of placement, which indicated that the prepared SERS substrate had excellent stability and repeatability. At last, the thiram detection application of the MPA/AgNP 3D-SERS substrate was also investigated.
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