We present a discrete dipole approximation ͑DDA͒ method to determine extinction and Raman intensities for small metal particles of arbitrary shape. The Raman intensity calculation involves evaluation of surface electromagnetic fields, and thus is relevant to surface enhanced Raman scattering ͑SERS͒ intensities. We demonstrate convergence of the method by considering light absorption and scattering from an isolated spheroid, from an isolated tetrahedron, from two coupled spheroids, and from a spheroid on a flat surface. We also examine comparisons with traditional T-matrix methods. Extensions and simplifications of the method in studies of clusters and arrays of particles are presented.
A series of squaramide-based organocatalysts were facilely synthesized and applied as hydrogen bonding organocatalysts in the enantioselective Michael addition of nitroalkanes to chalcones. These organocatalysts promoted the Michael addition with low catalyst loading under high temperature (80 °C), affording the desired R or S enantiomers of the products flexibly in high yields with excellent enantioselectivities (93-96% ee) by the appropriate choice of organocatalysts.
We present theoretical and experimental studies of the infrared (IR) spectroscopy, normal Raman spectroscopy (NRS), surface-enhanced Raman spectroscopy (SERS), and surface-enhanced hyper-Raman (SEHRS) spectroscopy of trans-1,2-bis(4-pyridyl)ethylene (BPE). This centrosymmetric molecule is expected to have no common Raman and hyper-Raman lines provided that it is not strongly perturbed by adsorption on the surface. The measured SERS spectrum, obtained under electrochemical conditions on Ag film over nanosphere (AgFON) electrodes, shows a well defined C=C stretch band that is not seen in the SEHRS spectrum, but many of the other bands overlap closely. We use ab initio calculations for isolated BPE to assign the spectra, and find excellent agreement between the calculated and measured IR and SERS spectra, and good agreement between the calculated and measured SEHRS spectrum. We find that the apparently overlapping IR, SERS, and SEHRS bands are in fact due to modes that have similar vibrational characteristics but different symmetry. Our results indicate that SEHRS spectra are consistent with the expected (three photon) selection rules and intensities. This rules out an alternative mechanism in which the observed spectrum arises from surface second harmonic generation (SHG) followed by SERS excited at the second harmonic frequency.
Although photodynamic therapy (PDT) has served as an important strategy for treatment of various diseases, it still experiences many challenges, such as shallow penetration of light, high‐dose light irradiation, and low therapy efficiency in deep tissue. Here, a low‐dose X‐ray‐activated persistent luminescence nanoparticle (PLNP)‐mediated PDT nanoplatform for depth‐independent and repeatable cancer treatment has been reported. In order to improve therapeutic efficiency, this study first synthesizes W(VI)‐doped ZnGa2O4:Cr PLNPs with stronger persistent luminescence intensity and longer persistent luminescence time than traditional ZnGa2O4:Cr PLNPs. The proposed PLNPs can serve as a persistent excitation light source for PDT, even after X‐ray irradiation has been removed. Both in vitro and in vivo experiments demonstrate that low‐dose (0.18 Gy) X‐ray irradiation is sufficient to activate the PDT nanoplatform and causes significant inhibitory effect on tumor progression. Therefore, such PDT nanoplatform will provide a promising depth‐independent treatment mode for clinical cancer therapy in the future.
Phloem-mobile insecticides are preferred to achieve economically useful activity. However, only a few phloem-mobile synthetic insecticides are available. One approach to converting nonmobile insecticides into phloem-mobile types is introducing sugar to the parent compound. To test whether the addition of a glucose group to a non-phloem-mobile insecticide enables conversion into phloem-mobile, N-[3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazol-5-yl]-1-(β-D-glucopyranosyl)-1H-1,2,3-triazole-4-methanamine (GTF) was prepared through click chemistry. A phloem-mobility test in Ricinus communis L. seedlings confirmed that GTF was mobile in the sieve tubes. Although GTF exhibited lower insecticidal activity against the third-instar larvae of Pzlutella xylostella than fipronil did, it can be reconverted into fipronil in adult plants of castor bean, thereby offsetting the decrease of insecticidal activity. Therefore, the presence of a glucose core confers phloem mobility to fipronil.
Some compounds containing glucose are absorbed via the monosaccharide transporters of the plasma membrane. A glucose-fipronil conjugate, N-[3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazol-5-yl]-1-(β-d-glucopyranosyl)-1H-1,2,3-triazole-4-methanamine (GTF), has been synthesized in our previous work. GTF exhibits moderate phloem mobility in Ricinus communis. In the current paper, we demonstrate that the uptake of GTF by Ricinus seedling cotyledon discs is partly mediated by an active carrier system (K(m)1 = 0.17 mM; V(max)1 = 2.2 nmol cm(-2) h(-1)). Four compounds [d-glucose, sucrose, phloridzin, and carbonyl cyanide m-chlorophenylhydrazone (CCCP)] were examined for their effect on GTF uptake. Phloridzin as well as CCCP markedly inhibit GTF uptake, and d-glucose weakly competes with it. The phloem transport of GTF in Ricinus seedlings is found to involve an active carrier-mediated mechanism that effectively contributes to the GTF phloem loading. The results prove that adding a glucose core is a reasonable and feasible approach to confer phloem mobility to fipronil by utilizing plant monosaccharide transporters.
Multifunctional nanoplatforms with integrated diagnostic and therapeutic functions have attracted tremendous attention. Especially, the second near-infrared (NIR-II) light response-based nanoplatforms hold great potential in cancer theranostic applications, which is because the NIR-II window provides larger tissue penetration depth and higher maximum permissible exposure (MPE) than that of the well-studied first near-infrared (NIR-I) window. Herein, we for the first time present a two-dimensional (2D)-nanoplatform based on Cu2MnS2 nanoplates (NPs) for magnetic resonance imaging (MRI)/multispectral optoacoustic tomography (MSOT) dual-modal imaging-guided photothermal therapy (PTT) of cancer in the NIR-II window. Methods: Cu2MnS2 NPs were synthesized through a facile and environmentally friendly process. A series of experiments, including the characterization of Cu2MnS2 NPs, the long-term toxicity of Cu2MnS2 NPs in BALB/c nude mice, the applications of Cu2MnS2 NPs for in vitro and in vivo MRI/MSOT dual-modal imaging and NIR-II PTT of cancer were carried out. Results: The as-synthesized Cu2MnS2 NPs exhibit low cytotoxicity, excellent biocompatibility as well as high photothermal conversion efficiency (~49.38%) and outstanding photostability. Together with their good T1-shortening effect and strong absorbance in the NIR-I and NIR-II region, the Cu2MnS2 NPs display high-contrast imaging performance both in MRI and MSOT (900 nm laser source). Moreover, the subsequent in vitro and in vivo results demonstrate that the Cu2MnS2 NPs possess excellent PTT efficacy under 1064 nm laser irradiation with a low power density (0.6 W cm-2). In addition, the detailed long-term toxicity studies further confirming the safety of Cu2MnS2 NPs in vivo. Conclusion: We have developed a new 2D Cu2MnS2 NPs as multifunctional theranostic agents for MRI/MSOT dual-modal imaging-guided PTT of cancer in the NIR-II window. Such biocompatible Cu2MnS2 NPs might provide a new perspective for exploring new 2D-based nanoplatforms with improved properties for clinical applications in the future.
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