Chiral Au nanoclusters have promising application prospects in chiral sensing, asymmetric catalysis, and chiroptics. However, enantiopure superatomic homogold clusters with crystallographic structures emitting bright circularly polarized luminescence (CPL) remain challenging. In this study, we designed chiral N-heterocyclic carbenes (NHCs), and for the first time enantioselectively synthesized a pair of monovalent cationic superatomic Au13 clusters. This new enantiomeric pair of clusters has a quasi-C2 symmetric core and exhibited CPL with an unprecedent solution-state quantum yield (QY) of 61 % among those of the atomically precise Au nanoclusters. DFT calculations provided insights into the circular dichroism behavior, and revealed the origin of CPL from superatomic Au clusters. This work opens a new avenue for developing novel homochiral nanoclusters using chiral NHC ligands and provides fundamental understanding of the origin of the chiroptics of metal clusters. 相似文献
Four symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril-based compounds have been prepared and characterised by X-ray crystallography. Their crystal structures displayed the acetate anion-selective encapsulating capability of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril. The host–guest interaction between the symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril and the acetate anion in aqueous solution has also been observed by variable temperature 1H NMR spectroscopy. 相似文献
The incorporation of functional groups into the cavity of discrete supramolecular coordination cages (SCCs) will bring unique functions and applications. Here, three dicarboxylate ligands (H2 L1 Cl, H2 L2 Cl and H2 L3 Cl) containing N-heterocyclic carbene (NHC) precursors as linkers were introduced to construct SCCs by combining with two C3-symmertic (CpZr)3(μ3-O)(μ2-OH)3 clusters as three-connect vertices, resulted in a series of rugby-like V2E3 (V=vertex, E=edge) type homoleptic cages ( SCC-1 , SCC-2 and SCC-3 ). However, V4E6-type tetrahedral cages ( SCC-4 and SCC-5 ), incorporating six Au-NHC moieties, were obtained when the corresponding NHC-gold(I) functionalized ligands (H2 L1 Au, H2 L2 Au) were applied. For the first time, we present a trackable CpZr-involved cage to cage conversion to generate a heteroleptic V2E3 cage ( SCC-6 ) from two homoleptic cages ( SCC-2 and SCC-5 ) with different geometries of V2E3 and V4E6. The heteroleptic assembly SCC-6 can also be formed upon a subcomponent displacement strategy. The structural transformation and reassembly processes were detected and monitored by 1H NMR spectroscopy and electrospray-ionization mass spectrometry. The formation of heteroleptic assembly was further supported by single crystal X-ray diffraction analysis. Moreover, homoleptic cage SCC-2 possesses a trigonal bipyramidal cationic cavity allowing the encapsulation of a series of sulfonate anionic guests. 相似文献
We demonstrate here a novel method for the design of liquid crystals (LCs) via the cyclization of mesogens by flexible chains. For two azobenzene-4,4′-dicarboxylate derivatives, the cyclic dimer, cyclic bis(tetraethylene glycol azobenzene-4,4′-dicarboxylate) (CBTAD), shows LC properties with smectic A phase, while its linear counterpart, bis(2-(2′-hydroxyethyloxy)ethyl azobenzene-4,4′-dicarboxylate (BHAD), has no LC phase. The difference is ascribed to the shackling effect from the cyclic topology, which leads to the much smaller entropy change during phase transitions and increases the isotropic temperature greatly for cyclics. In addition, the trans-to-cis isomerization of azobenzene groups under UV-light is also limited in CBTAD. With the reversible isomerization of azobenzene groups, CBTAD showed interesting isothermal phase transition behaviors, where the LC phase disappeared upon photoirradiation of 365 nm UV-light, and recovered when the UV-light was off. Combined with the smectic LC nature, a novel UV-light tuned visible light regulator was designed, by simply placing CBTAD in two glass plates. The scattered phase of smectic LC was utilized as the “OFF” state for light passage, while the UV-light induced isotropic phase was utilized as the “ON” state. The shackling effect outlined here should be applicable for the design of cyclic LC oligomers/polymers with special properties.
In the present study, we reconstructed upper airway and soft palate models of 3 obstructive sleep apnea-hypopnea syndrome(OSAHS) patients with nasal obstruction. The airflow distribution and movement of the soft palate before and after surgery were described by a numerical simulation method. The curative effect of nasal surgery was evaluated for the three patients with OSAHS. The degree of nasal obstruction in the 3 patients was improved after surgery. For 2 patients with mild OSAHS, the upper airway resistance and soft palate displacement were reduced after surgery. These changes contributed to the mitigation of respiratory airflow limitation. For the patient with severe OSAHS, the upper airway resistance and soft palate displacement increased after surgery, which aggravated the airway obstruction. The effcacy of nasal surgery for patients with OSAHS is determined by the degree of improvement in nasal obstruction and whether the effects on the pharynx are beneficial. Numerical simulation results are consistent with the polysomnogram(PSG) test results, chief complaints, and clinical findings, and can indirectly reflect the degree of nasal patency and improvement of snoring symptoms, and further,provide a theoretical basis to solve relevant clinical problems. 相似文献
A simple, rapid method was developed using on-line high-performance liquid chromatography (HPLC)-diode array detection (DAD)/electrospray ionization mass spectrometry (ESI-MS) to simultaneously analyze multiple bioactive constituents in the extract of Rheum tanguticum Maxim. ex Balf. (Dahuang), a traditional Chinese medicine (TCM). Many bioactive constituents gave prominent [M-H]- ions in the negative ion ESI mass spectra. Among them, 41 different constituents including 16 anthraquinone derivatives, 7 phenylbutanone glucopyranosides, 4 stilbenes and 14 tannins were unambiguously identified or tentatively characterized based on their retention times, UV spectra and mass spectra in comparison with the data from standards or references. Meanwhile, some principles of fragmentation behavior for different types of constituents were proposed, which could contribute to the elucidation of these constituents in Rheum tanguticum. 相似文献