Emerging Design Principle of Near-Infrared Upconversion Sensitizer Based on Mitochondria-Targeted Organic Dye for Enhanced Photodynamic Therapy

Upconversion luminescent (UCL) triggered photodynamic therapy (PDT) affords superior outcome for cancer treatment. However, conventional UCL materials which all work by a multiphoton absorption (MPA) process inevitably need extremely high power density far over the maximum permissible exposure (MPE) to laser. Here, a one-photon absorption molecular upconversion sensitizer Cy5.5-Br based on frequency upconversion luminescent (FUCL) is designed for PDT. The unusual super heavy atom effect (SHAE) in Cy5.5-Br strongly enhances its spin-orbit coupling (0.23 cm⁻¹), triplet quantum yield (11.1 %) and triplet state lifetime (18.8 μs) while the potential hot-band absorption of Cy5.5-Br is well maintained. Importantly, Cy5.5-Br can efficiently target the tumour site and kill cancer cells by destroying mitochondria under a biosafety MPE to 808 nm laser. The photostability and antitumor results are obviously superior to that of a Stokes process. This work provides a design criterion for FUCL dyes to realize effective PDT upon a biosafety optical density, possibly bringing more clinical benefits than conventional MPA materials.     

Mechanistic investigation of imine formation in ruthenium‐catalyzed N‐alkylation of amines with alcohols

Imines are observed frequently in ruthenium‐catalyzed N‐alkylation of amines with alcohols. Herein, nitrogen–phosphine functionalized carbene ligands were developed and used in ruthenium‐catalyzed N‐alkylation to explore the mechanism of imine formation. The results showed that strongly electron‐donating ligands were beneficial for imine formation and alcohol dehydrogenation to generate acid. In addition, with an increase of electron density of nitrogen atom in substituted amines, the yield of imines in N‐alkylation was improved. At the same time, with electron‐rich imines as substrates, the transfer hydrogenation of imines became difficult. It is suggested that strongly electron‐donating ligands and substrates caused an increase of electron density on the ruthenium center, which resulted in the elimination of hydrogen atoms in active species [LRuH₂] as hydrogen gas rather than transfer onto the imine coordinated with the ruthenium center.     

Preparation of BiVO4/MIL‐125(Ti) composite with enhanced visible‐light photocatalytic activity for dye degradation

Because of their desired features, including very specific surface areas and designable framework architecture together with their possibility to be functionalized, Metal Framework (MOF) is a promising platform for supporting varied materials in respect of catalytic applications in water treatment. In this work, a novel visible‐light‐responsive photocatalyst that comprised BiVO₄ together with MIL‐125(Ti), was synthesized by a two‐step hydrothermal approach. The characterization of as‐obtained samples as performed by X‐ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscope, X‐ray photoelectron spectroscopy and ultraviolet‐visible diffuse reflection spectra. Rhodamine B was selected being a target for the evaluation of the photocatalytic function of as‐developed photocatalyst. The photocatalytic reaction parameters, for example, the content of BiVO₄ as well as initial concentration of Rhodamine B was researched. The composite photocatalyst possessing Bi:Ti molar ratio of 3:2 brought to light the fact that the greatest photocatalytic activity had the ability to degrade 92% of Rhodamine B in 180 min. In addition to that, the BiVO₄/MIL‐125(Ti) composite could keep its photocatalytic activity during the recycling test. The phenomenon of disintegration of the photo‐generated charges in the BiVO₄/MIL‐125(Ti) composite was brought to discussion as well.     

Rare-earth Doped Nanoparticles with Narrow NIR-II Emission for Optical Imaging with Reduced Autofluorescence

Fluorescence imaging in the second near-infrared region(900-1700 nm, NIR-II) with a high resolution and penetration depth due to the significantly reduced tissue scattering and autofluorescence has emerged as a useful tool in biomedical fields. Recently, many efforts have been devoted to the development of fluorophores with an emission band covering the long-wavelength end of NIR-II region(1500-1700 nm) to eliminate the autofluorescence. Alternatively, we believe imaging with a narrow bandwidth could also reduce the autofluorescence. As a proof of concept, NaYF₄:Yb,Nd@NaYF₄ downconversion nanoparticles(DCNPs) with sharp NIR-II emission were synthesized. The luminescence of DCNPs showed a half-peak width of 49 nm centered at 998 nm, which was perfectly matched with a (1000±25) nm bandpass filter. With this filter, we were able to retain most of the emissions from the nanoparticles, while the autofluorescence was largely reduced. After PEGylation, the DCNPs exhibited great performance for blood vessel and tumor imaging in living mice with significantly reduced autofluorescence and interference signals. This work provided an alternative way for the low-autofluorescence imaging and emphasized the importance of narrow emitting rare-earth doped nanoparticles for NIR-II imaging.     

Preclinical development of a novel [68Ga]Ga-/[177Lu]Lu-labeled agent for PSMA-targeted imaging and therapy

Journal of Radioanalytical and Nuclear Chemistry - Prostate-specific membrane antigen (PSMA)-targeted radiolabeled agents have been developed to diagnose and treat prostate cancer. In this study,...     

Antioxidant product analysis of Folium Hibisci Mutabilis

Folium Hibisci Mutabilis, a new member of Chinese Pharmacopoeia, can treat some diseases induced by reactive oxygen species. The study prepared a lyophilized aqueous extract of Folium Hibisci Mutabilis (LAFHM). LAFHM was found to enrich eight flavonoids (i.e., quercetin, luteolin, hyperoside, isoquercitrin, rutin, kaempferol, tiliroside, and vitexin) by HPLC analysis. These flavonoids were further compared using antioxidant assays, where triliroside and vitexin always exhibited higher IC₅₀ values than the others. In ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry analysis, these flavonoids could basically give two characteristic m/z values (226 and 196) and their corresponding double m/z values (i.e., 602, 570, 926, 926, 570, 1186, and 862), when treated by 1,1-diphenyl-2-picryl-hydrazl radical (DPPH^?). Finally, the coupling products of DPPH^?-treated triliroside were investigated using computational chemistry. It was found that the –OH in para-coumaroyl moiety to have the lowest bond disassociation energy among all phenolic -OHs in the triliroside. In conclusion, Folium Hibisci Mutabilis contains the above eight antioxidant flavonoids. Despite of the different antioxidant levels, they can generally produce flavonoid-radical coupling product and flavonoid-flavonoid homodimer during antioxidant process. Especially, tiliroside uses para-coumaroyl as linker to construct a tiliroside-radical coupling product at the meta-carbon atom.     

The preparation and adsorption properties of electrospun aramid nanofibers

The focus of this work is the preparation of aramid nanofibers via electrospinning technology and the study of their adsorption properties. In this article, aramid nanofibers were prepared by electrospinning aramid fibers solution with the addition of lithium chloride (LiCl). It showed a good adsorption capacity when methylene blue (MB) was used as the model target. There were much larger adsorption amounts and faster kinetics of uptaking target species of electrospun aramid nanofibers to MB than that of electrospun polyethersulfone (PES) nanofibers. Compared with activated carbon, aramid nanofibers also have a much faster adsorption rate to MB. Aramid nanofibers were subsequently used to effectively remove endocrine disruptors such as bisphenol A (BPA), phenol (Phe), and p‐hydroquinone (BPhe) from their aqueous solutions. Additionally, molecule imprinted technology enhances aramid nanofibers with much higher adsorption amounts and special adsorption property for endocrine disruptors. These results showed that aramid nanofibers have the potential to be used in environmental applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012