Asymmetric [4 + 2] Annulation of Cyclobutenones and Pyrazolone 4,5-Diones: Access to Novel δ-Lactone-Fused Spiropyrazolones.

Although numerous chiral pyrazolones with a six-membered spirocyclic center at the C4 position have been developed, the asymmetric construction of six-membered oxa-spiropyrazolones is still a challenging task in organic synthesis. Herein, we describe the [4 + 2] annulation of cyclobutanones and pyrazoline-4,5-diones for the efficient synthesis of δ-lactone-fused spiropyrazolone derivatives with generally high yields and good enantioselectivities under mild conditions. The successful scale-up synthesis and further transformation of the final product highlight the practicality and reliability of this reaction.

The Role of α7nAChR-Mediated Cholinergic Anti-Inflammatory Pathway in Vagal Nerve Regulated Atrial Fibrillation.

The aim was to investigate the role of the α7nAChR-mediated cholinergic anti-inflammatory pathway in vagal nerve regulated atrial fibrillation (AF).18 beagles (standard dogs for testing) were used in this study, and the effective refractory period (ERP) of atrium and pulmonary veins and AF inducibility were measured hourly during rapid atrial pacing at 800 beats/minute for 6 hours in all beagles. After cessation of 3 hours of RAP, the low-level vagal nerve stimulation (LL-VNS) group (n = 6) was given LL-VNS and injection of salinne (0.5 mL/GP) into four GPs, the methyllycaconitine (MLA, the antagonist of α7nAChR) group (n = 6) was given LL-VNS and injection of MLA into four GPs, and the Control group (n = 6) was given saline into four GPs and the right cervical vagal nerve was exposed without stimulation. Then, the levels of the tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6), acetylcholine (ACh), STAT3, and NF-κB proteins were measured. During the first 3 hours of RAP, the ERPs gradually decreased while the dispersion of ERPs (dERPs) and AF inducibility gradually increased in all three groups. During the last 3 hours of 6 hours' RAP in this study, the ERPs in the LL-VNS group were higher, while the dERPs and AF inducibility were significantly lower when compared with the Control and MLA groups at the same time points. The levels of ACh in the serum and atrium in the LL-VNS and MLA groups were higher than in the Control group, and the levels of TNF-α and IL-6 were higher in the Control and MLA groups than in the LL-VNS group. The concentrations of STAT3 in RA and LA tissues were higher in the LL-VNS group while those of NF-κB were lower.In conclusion, the cholinergic anti-inflammatory pathway mediated by α7nACh plays an important role in low-level vagal nerve-regulated AF.

Laser acupuncture-induced analgesic effect and molecular alterations in an incision pain model: a comparison with electroacupuncture-induced effects.

Low-level laser acupuncture (LLLA) produces photobiomodulation through acupuncture point and is an alternative to low-level laser therapy. Although the analgesic effect of LLLA on chronic pain has been proven, its effect on acute postincisional pain has yet to be investigated. A plantar incision (PI) model was used to mimic human postsurgical pain. Male adult rats received GaAlAs laser irradiation at the right ST36 acupoint immediately after operation and on the following 4 days. Three laser treatment groups (two red laser groups with a 30- or 15-min treatment duration and one 30-min near-infrared laser group) were compared with sham LLLA and naive groups and an electroacupuncture (EA) group (separate study). Behavioral withdrawal thresholds of both hind paws were measured before and after incision. Expression of mitogen-activated protein kinases (p-ERK and p-p38), inducible nitric oxide synthase (iNOS), and tumor necrosis factor (TNF) in the spinal cord was analyzed. All three LLLA treatments attenuated post-PI tactile allodynia in the ipsilateral paw, but only the 30-min red laser treatment affected the contralateral paw and had similar efficacy to that of EA. All laser treatments barely reduced heat hyperalgesia in both hind paws. At 3 days after PI, the 30-min red laser group showed reversed increases of PI-induced p-ERK, p-p38, and iNOS but not TNF expression in the spinal cord. Repetitive LLLA treatments ameliorated PI-induced mechanical pain. The inhibition of multiple sensitization signals highlights the unique clinical role of LLLA. Thus, LLLA is an alternative to EA as an adjuvant for postoperative pain control.

Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation.

The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2.

Facile synthesis of pentacle gold-copper alloy nanocrystals and their plasmonic and catalytic properties.

The combination of gold and copper is a good way to pull down the cost of gold and ameliorate the instability of copper. Through shape control, the synergy of these two metals can be better exploited. Here, we report an aqueous phase route to the synthesis of pentacle gold-copper alloy nanocrystals with fivefold twinning, the size of which can be tuned in the range from 45 to 200 nm. The growth is found to start from a decahedral core, followed by protrusion of branches along twinning planes. Pentacle products display strong localized surface plasmon resonance peaks in the near-infrared region. Under irradiation by an 808-nm laser, 70-nm pentacle nanocrystals exhibit a notable photothermal effect to kill 4T1 murine breast tumours established on BALB/c mice. In addition, 70-nm pentacle nanocrystals show better catalytic activity than conventional citrate-coated 5-nm Au nanoparticles towards the reduction of p-nitrophenol to p-aminophenol by sodium borohydride.

Screw-dislocation-driven bidirectional spiral growth of Bi2Se3 nanoplates.

Bi2Se3 attracts intensive attention as a typical thermoelectric material and a promising topological insulator material. However, previously reported Bi2Se3 nanostructures are limited to nanoribbons and smooth nanoplates. Herein, we report the synthesis of spiral Bi2Se3 nanoplates and their screw-dislocation-driven (SDD) bidirectional growth process. Typical products showed a bipyramid-like shape with two sets of centrosymmetric helical fringes on the top and bottom faces. Other evidence for the unique structure and growth mode include herringbone contours, spiral arms, and hollow cores. Through the manipulation of kinetic factors, including the precursor concentration, the pH value, and the amount of reductant, we were able to tune the supersaturation in the regime of SDD to layer-by-layer growth. Nanoplates with preliminary dislocations were discovered in samples with an appropriate supersaturation value and employed for investigation of the SDD growth process.

A new nanobiocatalytic system based on allosteric effect with dramatically enhanced enzymatic performance.

We report a rational design of CaHPO(4)-α-amylase hybrid nanobiocatalytic system based on allosteric effect and an explanation of the increase in catalytic activity when certain enzymes are immobilized in specific nanomaterials. Employing a calcification approach in aqueous solutions, we acquired such new nanobiocatalytic systems with three different morphologies, i.e., nanoflowers, nanoplates, and parallel hexahedrons. Through studying enzymatic performance of these systems and free α-amylase with/without Ca(2+), we demonstrated how two factors, allosteric regulation and morphology of the as-synthesized nanostructures, predominantly influence enzymatic activity. Benefiting from both the allosteric modulation and its hierarchical structure, CaHPO(4)-α-amylase hybrid nanoflowers exhibited dramatically enhanced enzymatic activity. As a bonus, the new system we devised was found to enjoy higher stability and durability than free α-amylase plus Ca(2+).