Nanowires (NWs), high-aspect-ratio nanomaterials, are increasingly used in technological materials and consumer products and may have toxicological characteristics distinct from nanoparticles. We carried out a comprehensive evaluation of the physico-chemical stability of four silver nanowires (AgNWs) of two sizes and coatings and their toxicity to Daphnia magna. Inorganic aluminum-doped silica coatings were less effective than organic poly(vinyl pyrrolidone) coatings at preventing silver oxidation or Ag+ release and underwent a significant morphological transformation within one-hour following addition to low ionic strength Daphnia growth media. All AgNWs were highly toxic to D. magna but less toxic than ionic silver. Toxicity varied as a function of AgNW dimension, coating and solution chemistry. Ag+ release in the media could not account for observed AgNW toxicity. Single-particle inductively coupled plasma mass spectrometry (spICPMS) distinguished and quantified dissolved and nanoparticulate silver in microliter-scale volumes of Daphnia magna hemolymph with a limit of detection of approximately 10 ppb. The silver levels within the hemolymph of Daphnia exposed to both Ag+ and AgNW met or exceeded the initial concentration in the growth medium, indicating effective accumulation during filter feeding. Silver-rich particles were the predominant form of silver in hemolymph following exposure to both AgNWs and Ag+. Scanning electron microscopy (SEM) imaging of dried hemolymph found both AgNWs and silver precipitates that were not present in the AgNW stock or the growth medium. Both organic and inorganic coatings on the AgNW were transformed during ingestion or absorption. Pathway, gene ontology and clustering analyses of gene expression response indicated effects of AgNWs distinct from ionic silver on Daphnia magna.
High two-photon photolysis cross sections and water solubility of probes are important to avoid toxicity in biomedical applications of photolysis. Systematic variation of the position of a carboxyl electron-withdrawing group (EWG) on photolysis of 8-dimethylaminoquinoline protecting groups identified the C5-substituted isomer as a privileged dipole. The 5-benzoyl-8-DMAQ substitution yields a caging group with an enhanced two-photon uncaging cross section (δu = 2.0 GM) and good water solubility (c ≤ 50 mM, pH 7.4).
The systematic SAR study of a "caging" group showed a strong influence of the position of the donor dimethylamino group on the efficiency of photolysis of the DMAQ (2-hydroxymethylene-(N,N-dimethylamino)quinoline) caged acetate under one-photon near-UV or two-photon near-IR excitation. Photorelease of l-glutamate by the most efficient 8-DMAQ derivative strongly and efficiently activated glutamate receptors, generating large, fast rising responses similar to those elicited by glutamate photoreleased from the widely used MNI-caged glutamate.
Synthetic studies on hemicalide, a recently isolated marine natural product displaying highly potent antiproliferative activity and a unique mode of action, have highlighted a reliable Horner-Wadsworth-Emmons olefination to create the C6-C7 alkene and a remarkable efficient Suzuki-Miyaura coupling to form the C15-C16 bond, resulting in the development of a convergent approach toward the C1-C25 fragment.
Synthesis and application of allenylboronic acids is presented. The successful synthetic applications are based on the possibility of the versatile transformations of the unprotected B(OH)2 group in situ under the propargylboration conditions.
Anomeric C-H bond activation is an unsolved long-standing synthetic challenge. Herein we report a diastereoselective Pd-catalyzed anomeric C(sp 3 )-H activation methodology that allows the synthesis of elusive C-(hetero)arylglycosides with an exclusive α-selectivity.a Reactions were performed an oven dried re-sealable tube using sugar 1a (0.1 mmol), ArX 2 (3 equiv), Pd(OAc)2 (0.01 mmol), Ag2CO3 (3 equiv) in tAmOH (1.0 mL) at 120 °C. b Yield of isolated product.
Quadrupolar probes derived from 8-dimethylamino-quinoline (8-DMAQ) having a pegylated fluorene core were prepared and studied under "one-photon" (λ=365 nm) and "two-photon" (TP) (λ=730 nm) irradiation conditions. Compound 1 a was identified as the most efficient probe by UV activation that showed sequential release of acetic acid as a model. Although the probe showed high two-photon absorption it stayed inert under femtosecond irradiation conditions. Fast and selective photolysis was observed, however, by using picosecond irradiation conditions with a remarkably high TP uncaging cross-section (δ =2.3 GM).
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