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Limited light absorption beyond the UV region and rapid photocarrier recombination are critical impediments for the improved photocatalytic performance of carbon quantum dots (CQDs) under visible-light irradiation. Herein, we demonstrate single-step microwave-assisted syntheses of O-CQDs (typical CQDs terminated by carboxylic and hydroxyl functional groups) from a sucrose precursor and Cl-doped CQDs (Cl-CQDs) from a sucralose precursor in short reaction times and without using obligatory strong acids for Cl doping. The doping of Cl into the CQDs is observed to widen the absorption range and facilitate an enhanced separation of photoexcited charge carriers, which is confirmed by the results of optical absorption, photothermal response, and pump-probe ultrafast transient absorption spectroscopy measurements of the O-CQDs and Cl-CQDs. The photoexcited charge carriers with their longer lifetimes in Cl-CQDs enabled the quick degradation of methylene blue dye, rapid conversion of Ag + ions to metallic Ag nanoparticles on the CQD surfaces, and reduction of GO to a welldispersed rGO through the photoelectron transfer reactions under visible-light irradiation. The facile Cl doping strategy, hybridization of Ag nanoparticles or rGO to CQDs, and the elevated charge separation mechanism would open up new avenues in designing CQD-based materials for futuristic applications.

[Purpose] The effects of various rhythmic auditory stimulation tempos on stroke gait pattern changes when training patients with a smartphone-based rhythmic auditory stimulation application were investigated. [Subjects and Methods] Fifteen patients with chronic stroke were included. Cadence during comfortable walking was measured (baseline). After the baseline findings were recorded, rhythmic auditory stimulation with five different tempos (i.e., −10%, −5%, 0%, +5%, and +10% change from baseline) was randomly applied. Finally, comfortable walking without rhythmic auditory stimulation was initiated to evaluate gait pattern changes. [Results] As the tempo increased, the spatiotemporal gait parameters of the stroke patients changed significantly. Gait speed, cadence, and gait cycle duration showed the greatest improvement in the +10% rhythmic auditory stimulation condition compared to baseline. After gait training with rhythmic auditory stimulation, gait speed, cadence, stride length, gait cycle duration, and step length of the affected and unaffected sides improved significantly compared to baseline. [Conclusion] Significant changes in the gait pattern of stroke patients were noted for various tempos after training with rhythmic auditory stimulation. These findings could be used to customize rehabilitative gait training for patients who experience stroke with hemiplegia.

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The direct use of conventional photosensitizers in photodynamic therapy (PDT) of cancer cells has been thwarted by their low solubility, poor photostability, and aggregation tendency. Hence, complex and hectic synthetic procedures, such as developing nanomaterials and subsequently loading them with photosensitizers, have become mandatory for the effective use of photosensitizers in PDT. In this study, we have avoided complex procedures and produce hematoporphyrin (HP) photosensitizer-encapsulated carbon quantum dots (CQDs) (HP-CQDs) facilely through a well-controlled one-step microwave reaction by using the HP monomer as one of the precursors. The as-synthesized HP-CQDs retained all intrinsic optical and chemical properties of HP, while displaying excellent solubility in water. Importantly, the excellent reactive oxygen species generation ability of HP-CQDs under the illumination of deep red light favored their applicability in PDT-assisted efficient eradication of human breast cancer cells (MCF-7). Compared to HP, HP-CQDs exhibited very high phototoxicity and low dark toxicity toward MCF-7 cells. Overall, this study offers a proof of concept that photosensitizer-implanted CQDs, having excellence in PDT-assisted cancer treatment, can be easily designed by strategically exploiting the diversity available in the selection of precursors and synthesis conditions to produce CQDs.

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Reaction of secondary phosphine (+/-)-(2-aminophenyl)phenylphosphine, (+/-)-app, with PCl(5) in toluene gives the hydrochloride salt of the expected chlorophosphine (+/-)-(2-aminophenyl)chlorophenylphosphine, (+/-)-acpp.HCl, however, this is not the case with triphosgene. Rather the first example of a 1,3-azaphosphol-2-one is isolated, viz. (+/-)-3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one, (+/-)-pbap. The hydrochloride salt (+/-)-acpp.HCl readily reacts with excess vinyl-, 2-methylphenyl- or 2-methoxyphenyl magnesium bromide to give the corresponding tertiary phosphines (+/-)-(2-H(2)NC(6)H(4))PPhR (where R = CH=CH(2), 2-C(6)H(4)Me or 2-C(6)H(4)OMe). Hydrophosphination of the vinyl substituted tertiary phosphine with (+/-)-app in the presence of KOBu(t) provides a synthetic route to the elusive P(2)N(2) quadridentate ligand (R(P)*,R(P)*)- and (R(P)*,S(P)*)-(CH(2))(2)(PPhC(6)H(4)NH(2)-2)(2), albeit in low yield. The azaphospholone (+/-)-pbap can be readily deprotonated with KOBu(t) in thf and subsequently alkylated with methyl iodide or benzyl bromide to give the analogous N-methyl or N-benzyl derivatives. Alkylation with 1,3-dibromopropane gives the bis(azaphospholone) (R(P)*,R(P)*)- and (R(P)*,S(P)*)-1,3-bis[1-{3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one}]propane. The latter and the N-methyl substituted azaphospholone can also be synthesised by the reaction of the corresponding secondary phosphine, viz. (R(P)*,R(P)*)- and (R(P)*,S(P)*)-(CH(2))(3)(NHC(6)H(4)PHPh-2)(2) and (+/-)-(2-methylaminophenyl)phenylphosphine, with triphosgene. All three azaphospholones react with [PtClMe(1,5-cyclooctadiene)] in thf to give complexes of the type cis-[PtClMeL(2)] in which ligand L is coordinated via the P atom of the azaphospholones. The ligand (+/-)-pbap has also been complexed to palladium(II) via the reaction with Li(2)[PdCl(4)] in methanol to give cis-[PdCl(2){(+/-)-pbap}(2)]. The structures of cis-[PtClMe{(+/-)-pbap}(2)] and cis-[PdCl(2){(+/-)-pbap}(2)] have been confirmed by X-ray analysis.