Coupling Photoresponsive Transmembrane Ion Transport with Transition Metal Catalysis.

Artificial ion transporters have been explored both as tools for studying fundamental ion transport processes and as potential therapeutics for cancer and channelopathies. Here we demonstrate that synthetic transporters may also be used to regulate the transport of catalytic metal ions across lipid membranes and thus control chemical reactivity inside lipid-bound compartments. We show that acyclic lipophilic pyridyltriazoles enable Pd(II) cations to be transported from the external aqueous phase across the lipid bilayer and into the interior of large unilamellar vesicles. In situ reduction generates Pd(0) species, which catalyze the generation of a fluorescent product. Photocaging the Pd(II) transporter allows for photoactivation of the transport process and hence photocontrol over the internal catalysis process. This work demonstrates that artificial transporters enable control over catalysis inside artificial cell-like systems, which could form the basis of biocompatible nanoreactors for applications such as drug synthesis and delivery or to mediate phototargeted catalyst delivery into cells.

Sourness impacts envy and jealousy in Chinese culture.

In the present study, five experiments (N = 233) were designed to explore whether sourness as a sensory experience could implicitly impact social emotions of envy and jealousy in Chinese culture. Experiment 1 (n = 63) explored the implicit conceptual association between sourness words (vs. bitterness words) and envy/jealousy words. Experiment 2 (n = 70) and 3 (n = 20) examined the priming effects of imagined and tasted sourness (vs. bitterness and sweetness) on self-rated emotional intensity in envy- and jealousy-arousing situations, respectively. Experiment 4 (n = 40) and 5 (n = 40) further testified the priming effects of imagined and tasted sourness (vs. bitterness and sweetness) on self-rated emotional intensity in four types of social situations (i.e., envy, jealousy, sad and happy events), respectively. In the results, sourness was found as the only taste that not only conceptually associated with envy/jealousy, but also significantly primed envy/jealousy feelings. The possible mechanism underlying the association of sourness-envy/jealousy was discussed.

Dendronized Arm Snowflake Polymer as a Highly Branched Scaffold for Cellular Imaging and Delivery.

Incorporation of branched structures is a major pathway to build macromolecules with desired three-dimensional (3D) structures, which are of high importance in the rational design of functional polymeric scaffolds. Dendrimers and hyperbranched polymers have been extensively studied for this purpose, but proper gain-of-function for these structures usually requires large enough molecular weights and a highly branched interior so that a spherical 3D core-shell architecture can be obtained, yet it is generally challenging to achieve precise control over the structure, high molecular weight, and high degree of branching (DoB) simultaneously. In this article, we present a set of snowflake-shaped star polymers with functional cores and dendronized arms, which ensure a high DoB and an overall globular conformation, thus facilitating the introduction of functional moieties onto the easily achieved scaffold without the need for high-generation dendrons. Using a polyglycerol dendron (PGD) as a proof of concept, we propose that this dendronized arm snowflake polymer (DASP) structure can serve as a better performing alternative to high-generation PGDs. DASPs with molecular weights of 750, 1220, 2120, and 3740 kDa were prepared with >85% yields in all cases, and we show that these DASPs have high encapsulating efficiency of Nile Red due to their high DoB and high biocompatibility due to their hydroxyl-rich nature after ketal removal, as well as high cell permeability that is molecular-weight-dependent. Introduced fluorophores such as fluorescein and difluoroboron 1,3-diphenylaminophenyl ß-diketonate with suitable excitation wavelengths may turn the DASPs into stable, endosome-staining fluorophores with ultra-large Stokes shifts, narrowed emission bands, and suitability for long-term cellular tracing. Moreover, the scaffold can encapsulate antibiotic molecules and deliver them into phagolysosomes for efficient elimination of intracellular Staphylococcus aureus, which is insensitive toward many antibiotics but is a key target for the clinical success of methicillin-resistant Staphylococcus aureus infection treatment. Elimination of Staphylococcus aureus could be improved to >99.9% for chloramphenicol at 32 µg/mL with 450 µg/mL DASP.

Molecularly pure miktoarm spherical nucleic acids: preparation and usage as a scaffold for abiotic intracellular catalysis.

We present a fullerene-based strategy that allows the synthesis of molecularly pure miktoarm spherical nucleic acids (SNAs) with diverse structures, which, with post-functionalization, could serve as efficient scaffolds for intracellular catalysis. The SNA structure promotes cell permeability, nucleic acid stability, and catalytic efficiency, making the platform ideal for in cellulo reactions. Consequently, the tris(triazole)-bearing miktoarm SNA was able to effectively mediate intracellular copper-catalyzed alkyne-azide cycloaddition at nanomolar level of copper, and facilitate the same reaction in live zebrafish.

[Reconstruction of calcaneal thalamus by bone autograft and subtalar arthrodesis for antiquated intra-articular calcaneal fractures].

OBJECTIVE: To introduce a clinical treatment for the reconstruction of calcaneal thalamus by bone autograft and subtalar arthrodesis for antiquated intra-articular calcaneal fractures. METHODS: From July 2000 to October 2003, 11 cases with antiquated intra-articular calcaneal fractures were treated. Of the 11 cases, 9 were males and 2 females,whose ages ranged from 21 to 48 years. All unilateral calcanei were involved in the 11 cases. The modified extended L-shaped approach lateral to calcaneus was adopted. The primary treatment was manipulation and immobilization with the reconstruction of calcaneal thalamus by bone autograft and subtalar arthrodesis. The average volume of the ilium for the autograft was 3.0 cm x 2.5 cm x 1.8 cm. Protruded osteophyte from the lateral wall of calcaneus were ablated in all 11 cases. RESULTS: All the 11 cases were followed up for 3 to 18 months, 11.5 months on average. The reconstructed calcaneal thalamus was healed 10 to 12 weeks after the operation. Some of the patients could walk with load 8 weeks after the operation, and the average time for all the patients to walk with load was 13.2 weeks. There were 4 cases of excellent result, 5 cases of good result, and 2 cases of fair result, according to ZHANG Tieliang's foot score system. Plain radiograph showed that Böhler angle, width of calcaneus and height of calcaneal thalamus were nearly restored to normal. CONCLUSION: With the improvement of calcaneal abnormality and restoration of the shape and function of hind foot, reconstruction of calcaneal thalamus by bone autograft combined with subtalar arthrodesis is effective in treating antiquated intra-articular calcaneal fractures.