Heat capacities and thermodynamic properties of a Zn-based zeolitic imidazolate framework

Journal of Thermal Analysis and Calorimetry - The molar heat capacities of one–three-dimensional zeolitic imidazolate frameworks Zn(C4H6N2)2 (ZIF-8) were measured by temperature-modulated...     

A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

Demonstration of joule-level chirped pulse amplification based on tiled Ti:sapphire amplifier

A novel tiled Ti:sapphire(Ti:S)amplifier was experimentally demonstrated with>1 J amplified chirped pulse output.Two Ti:S crystals having dimensions of 14 mm×14 mm×25 mm were tiled as the gain medium in a four-pass amplifier.Maximum output energy of 1.18 J was obtained with 2.75 J pump energy.The energy conversion efficiency of the tiled Ti:S amplifier was comparable with a single Ti:S amplifier.The laser pulse having the maximum peak power of 28 TW was obtained after the compressor.Moreover,the influence of the beam gap on the far field was discussed.This novel tiled Ti:S amplifier technique can provide a potential way for 100 PW or EW lasers in the future.     

Samarium(II) Monoalkyl Complex Supported by a β-Diketiminato-Based Tetradentate Ligand: Synthesis,Structure, and Catalytic Hydrosilylation of Internal Alkynes

The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe₃)₂] (L=[MeC(NDipp)CHC(Me)NCH₂CH₂N(Me)CH₂CH₂NMe₂]⁻, Dipp=2,6-(iPr)₂C₆H₃). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]₂ and KCH(SiMe₃)₂ in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields.     

Similar or different: the same Spiro-core but different alkyl chains with apparently improved device performance of perovskite solar cells

By intelligently utilizing the odd-even effect existing in the melting points of alkanes as presented in the basic textbook of Organic Chemistry, different alkoxy groups were introduced to modify the structure of commercial Spiro-OMeTAD to give new Spiro derivatives of Spiro-OEtTAD, Spiro-OPrTAD, Spiro-OiPrTAD and Spiro-OBuTAD, with the aim to adjust the molecular packing status in perovskite solar cells as hole transporting compounds. Excitedly, with the introduction of ethoxy groups instead of the methoxy ones in Spiro-OMeTAD, Spiro-OEtTAD-based perovskite solar cells demonstrated the highest device performance of 20.16%, higher than that of Spiro-OMeTAD(18.64%).     

Crystal structures and magnetic properties of nitroxide radical-coordinated copper(II) and cobalt(II) complexes

Transition Metal Chemistry - The crystal structures and magnetic properties of three coordination compounds constructed from various nitroxide radicals L and MII(hfac)2(H2O)2 building blocks...     

Transition-metal-free synthesis of polysubstituted pyrrole derivatives via [4 + 1] annulation of β-keto acids (C1 synthon) and α,β-unsaturated imines

A novel [4 + 1] annulation protocol for the synthesis of polysubstituted pyrrole derivatives from β-keto acids and α,β-unsaturated imines via a tandem Michael addition, decarboxylation and TBAI-catalyzed oxidative annulation has been developed. This method provides a new and facile application of β-keto acids as 1,1-nucleophilic/electrophilic type C1 synthons.     

Potential Role of Melatonin as an Adjuvant for Atherosclerotic Carotid Arterial Stenosis

Carotid artery stenosis (CAS) is an atherosclerotic disease characterized by a narrowing of the artery lumen and a high risk of ischemic stroke. Risk factors of atherosclerosis, including smoking, hypertension, hyperglycemia, hyperlipidemia, aging, and disrupted circadian rhythm, may potentiate atherosclerosis in the carotid artery and further reduce the arterial lumen. Ischemic stroke due to severe CAS and cerebral ischemic/reperfusion (I/R) injury after the revascularization of CAS also adversely affect clinical outcomes. Melatonin is a pluripotent agent with potent anti-inflammatory, anti-oxidative, and neuroprotective properties. Although there is a shortage of direct clinical evidence demonstrating the benefits of melatonin in CAS patients, previous studies have shown that melatonin may be beneficial for patients with CAS in terms of reducing endothelial damage, stabilizing arterial plaque, mitigating the harm from CAS-related ischemic stroke and cerebral I/R injury, and alleviating the adverse effects of the related risk factors. Additional pre-clinical and clinical are required to confirm this speculation.