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1.
J Am Chem Soc ; 145(49): 27095-27102, 2023 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-38016919

RESUMO

Stable luminescent radicals are open-shell emitters with unique doublet emission characteristics. This feature makes stable luminescent radicals exhibit widespread application prospects in constructing optical, electrical, and magnetic materials. In this work, a stable luminescent radical-based X-ray scintillator of AuPP-1.0 was prepared, which exhibited a high X-ray excited luminescence (XEL) efficiency as well as excellent stability. A mechanism study showed that the heavy atom of Au in AuPP-1.0 endowed it with effective absorption of X-rays, and the doublet emission characteristics of AuPP-1.0 significantly increased its exciton utilization rate in the radioluminescence process. Moreover, AuPP-1.0 has good processability to fabricate a flexible screen for high-quality X-ray imaging, whose resolution can reach 20 LP mm-1. This work demonstrates that the doublet emission is beneficial for improving the exciton utilization rate of radioluminescence, providing a brand-new strategy for the construction of high-performance X-ray scintillators.

2.
Angew Chem Int Ed Engl ; 62(40): e202308194, 2023 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-37366600

RESUMO

X-ray imaging technology has achieved important applications in many fields and has attracted extensive attentions. Dynamic X-ray flexible imaging for the real-time observation of the internal structure of complex materials is the most challenging type of X-ray imaging technology, which requires high-performance X-ray scintillators with high X-ray excited luminescence (XEL) efficiency as well as excellent processibility and stability. Here, a macrocyclic bridging ligand with aggregation-induced emission (AIE) feature was introduced for constructing a copper iodide cluster-based metal-organic framework (MOF) scintillator. This strategy endows the scintillator with high XEL efficiency and excellent chemical stability. Moreover, a regular rod-like microcrystal was prepared through the addition of polyvinyl pyrrolidone during the in situ synthesis process, which further enhanced the XEL and processibility of the scintillator. The microcrystal was used for the preparation of a scintillator screen with excellent flexibility and stability, which can be used for high-performance X-ray imaging in extremely humid environments. Furthermore, dynamic X-ray flexible imaging was realized for the first time. The internal structure of flexible objects was observed in real time with an ultrahigh resolution of 20 LP mm-1 .

3.
J Am Chem Soc ; 145(11): 6166-6176, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36912642

RESUMO

Superstructures made from nanoscale clusters with new collective properties are promising in high-tech applications; however, chiral superstructures remain elusive, and the limited intercluster coupling effect at room temperature hampers the tailoring of collective properties. Here, we show that from chiral monomeric copper clusters to two enantiomeric pairs of supercrystals with distinct phases, the absorption band edge red-shifts by over 1.3 eV, with photoluminescence and circularly polarized phosphorescence from visible (572 nm) to near-infrared (NIR, 858 nm). These supercrystals with high NIR quantum yields of up to 45% at room temperature are prototyped for night-vision imaging. In response to solvent and temperature stimuli, chiral supercrystal-to-supercrystal transformations occurred, concomitant with high-contrast optical/chiroptical switching. In situ single-crystal X-ray diffraction (SCXRD), steady-state and time-resolved optical spectroscopy, and response experiments combined with theoretical calculations demonstrate that distance-sensitive intercluster orbital interactions contribute to the exceptional collective optical responses. Such chiral supercrystals built from subnanoscale metal clusters with novel collective chiroptical responses would be useful in the fields of information storage and NIR optical devices.

4.
Nat Commun ; 13(1): 1177, 2022 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-35246541

RESUMO

The origins of the chiroptical activities of inorganic nanostructures have perplexed scientists, and deracemization of high-nuclearity metal nanoclusters (NCs) remains challenging. Here, we report a single-crystal structure of Rac-Ag70 that contains enantiomeric pairs of 70-nuclearity silver clusters with 20 free valence electrons (Ag70), and each of these clusters is a doubly truncated tetrahedron with pseudo-T symmetry. A deracemization method using a chiral metal precursor not only stabilizes Ag70 in solution but also enables monitoring of the gradual enlargement of the electronic circular dichroism (CD) responses and anisotropy factor gabs. The chiral crystals of R/S-Ag70 in space group P21 containing a pseudo-T-symmetric enantiomeric NC show significant kernel-based and shell-based CD responses. The small symmetry breaking of Td symmetry arising from local distortion of Ag-S motifs and rotation of the apical Ag3 trigons results in large chiroptical responses. This work opens an avenue to construct chiral medium/large-sized NCs and nanoparticles, which are promising for asymmetric catalysis, nonlinear optics, chiral sensing, and biomedicine.

5.
Nanoscale ; 14(5): 1538-1565, 2022 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-35060593

RESUMO

Atomically precise metal nanoclusters with specific chemical compositions have become a popular research topic due to their precise structures, attractive properties, and wide range of applications in various fields. Currently, among more than 100 reported metal nanoclusters with precise formulas, 38-atom coinage metal nanoclusters stand out due to their unique structural diversities, such as face-centered cubic (FCC) and body-centered cubic (BCC) arrangements. Among them, the formation of the metal cores includes vertex-sharing, face-fusion, and FCC cubes fusion. Due to their geometrical features, 38-atom coinage metal nanoclusters exhibit attractive properties, making them an ideal model for exploring structure-property relationships. Therefore, 38-atom coinage metal nanoclusters are a universal key to the treasure trove of nanoclusters, which can open almost all fields and are of great research significance. This paper focuses on the structure of 38-atom coinage metal nanoclusters and reviews the preparation and crystallization methods, excellent properties, and practical applications. Finally, future research prospects and development opportunities are provided.

6.
Artigo em Chinês | WPRIM (Pacífico Ocidental) | ID: wpr-886757

RESUMO

Objective To investigate the population dynamics and Echinococcus infections in small rodents around human settlement in Yushu City, Qinghai Province. Methods Rodents were captured using the mouse trap method in pastures from Batang Township and Longbao Township of Yushu City, Qinghai Province on May, August and October, 2018. The body weight and snout-vent length of all captured rodents were measured, and the species was identified according to the rodent morphology. Genomic DNA was extracted from rodent liver specimens and lesion specimens, and the mitochondrial cox1 gene of Echinococcus was amplified using PCR assay for identification of parasite species. In addition, the tissue specimens positive for PCR assay were sampled for pathological examinations. The prevalence of Echinococcus infections was estimated in rodents, and a phylogenetic tree was created based on Echinococcus cox1 gene sequences. Results A total of 285 small rodents were captured, including 143 Ochotona curzoniae (50.2%), 141 Lasiopodomys fuscus (49.5%), and 1 Neodon irene (0.3%), and there was a remarkable variation in habitat selection among these three rodent species. The number of L. fuscus correlated positively with vegetation coverage (r = 0.350, P = 0.264), with the greatest number seen in August, and the number of O. curzoniae negatively with vegetation coverage (r = −0.371, P = 0.235), with the highest number seen in August and the lowest number in May. The female/male ratios of O. curzoniae and voles were 1:0.96 and 0.82:1, respectively. The body weight (r = 0.519, P < 0.01) and snout-vent length (r = 0.578, P < 0.01) of O. curzoniae showed a tendency towards a rise with month, while the body weight (r = −0.401, P < 0.01) and snout-vent length (r = −0.570, P < 0.01) of voles presented a tendency towards a reduction with month. No Echinococcus infection was detected in voles, while 2.1% prevalence of E. shiquicus infection was seen in O. curzoniae. Phylogenetic analysis revealed consistent sequences of cox1 gene from E. shiquicus in Yushu City of Qinghai Province and Shiqu County, Ganzi Tibetan Autonomous Prefecture of Sichuan Province. Conclusions The small rodents around the human settlement in Yushu City of Qinghai Province mainly include O. curzoniae and L. fuscus, with the greatest numbers seen in May and August, respectively. Following the concerted efforts for echinococcosis control, the prevalence of Echinococcus infections is low in small rodents around the human settlement in Yushu City; however, there is still a risk of echinococcosis transmission.

7.
Artigo em Chinês | WPRIM (Pacífico Ocidental) | ID: wpr-668327

RESUMO

BACKGROUND: Bone marrow mesenchymal stem cells (BMSCs) are a kind of pluripotent stem cells in the bone marrow. Drug-containing serum treatment may be followed by a variation in the expression of genes involved in multiple signaling pathways. OBJECTIVE: To study the effect of compound Jiegu Tablets and Zhuanggu Tablets on the differentiation of BMSCs in vitro. METHODS: Sixty Sprague-Dawley rats were randomized into Jiegu group, Zhuanggu group, combined group and blank control group. Different drug-containing sera were prepared and used to culture BMSCs isolated from the rat bone marrow. RT-PCR and western blot assay were used to detect the expression of BMP-2, Runx2, VEGF and Akt at mRNA and protein levels, respectively, at 24 hours after culture.RESULTS AND CONCLUSION: Compared with the blank control group, the expression levels of Akt and VEGF mRNA and protein were significantly increased in the Jiegu group and combined group (P < 0.05 or P < 0.01), but showed no difference in the Zhuanggu group (P > 0.05). Compared with the blank control group, the expression levels of BMP-2 and Runx2 mRNA and protein were significantly increased in the Jiegu group (P < 0.05) and very significantly increased in the Zhuanggu group and combined group (P < 0.01). These findings indicate that compound Jiegu Tablets and Zhuanggu Tablets containing sera lead to synergistic effects on the BMSCs differentiation into vascular endothelial cells and osteoblasts in vitro.

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