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1.
2.
Inorg Chem ; 63(13): 5945-5951, 2024 Apr 01.
Article in English | MEDLINE | ID: mdl-38502918

ABSTRACT

Alkali-metal rare-earth carbonates (ARECs) find great potential in nonlinear optical applications. As the most common method, the hydrothermal reaction is widely used in synthesizing ARECs. The black-box nature of the hydrothermal reaction makes it difficult for understanding the formation processes and therefore may slow down the pace of structural discovery. Here, by simply soaking the rare-earth carbonates in Na2CO3 solutions, we successfully obtain a series of noncentrosymmetric Na3RE(CO3)3·6H2O (RE = Tb 1, Sm 2, Eu 3, Gd 4, Dy 5, Ho 6, and Er 7) compounds without using the high-temperature hydrothermal method. The transformation process, investigated by powder X-ray diffraction and scanning electron microscopy, is governed by the concentration of the soaking solutions. Na3Tb(CO3)3·6H2O, as an example, is studied structurally, and its physical properties are characterized. It exhibits a second harmonic generation effect of 0.5 × KDP and a short UV cutoff edge of 222 nm (5.8 eV). Our study provides insights for exploring new AREC structures, which may further advance the development of carbonate nonlinear optical crystals.

3.
Angew Chem Int Ed Engl ; 63(4): e202315691, 2024 Jan 22.
Article in English | MEDLINE | ID: mdl-38038694

ABSTRACT

Calixarenes are among the most useful and versatile macrocycles in supramolecular chemistry. The one thing that has not changed in the 80 years since their discovery, despite numerous derivatizations, is their fully organic, covalent scaffolds. Here, we report a new type of organic-inorganic hybrid "calixarenes" constructed by means of coordination-driven assembly. Replacing acetate ligands on the {SiW10 Cr2 (OAc)2 } clusters with 5-hydroxyisophthalates allows these 95° inorganic building blocks to be linked into bowl-shaped, hybrid "calix[n]arenes" (n=3, 4). With a large concave cavity, the metal-organic calix[4]arene can accommodate nanometer-sized polyoxoanions in an entropically driven process. The development of hybrid variants of calixarenes is expected to expand the scope of their physicochemical properties, guest/substrate binding, and applications on multiple fronts.

4.
Theranostics ; 13(15): 5305-5321, 2023.
Article in English | MEDLINE | ID: mdl-37908718

ABSTRACT

Background: The CRISPR/Cas13a system offers the advantages of rapidity, precision, high sensitivity, and programmability as a molecular diagnostic tool for critical illnesses. One of the salient features of CRISPR/Cas13a-based bioassays is its ability to recognize and cleave the target RNA specifically. Simple and efficient approaches for RNA manipulation would enrich our knowledge of disease-linked gene expression patterns and provide insights into their involvement in the underlying pathomechanism. However, only a few studies reported the Cas13a-based reporter system for in vivo molecular diagnoses. Methods: A tiled crRNA pool targeting a particular RNA transcript was generated, and the optimally potential crRNA candidates were selected using bioinformatics modeling and in vitro biological validation methods. For in vivo imaging assessment of the anti-GBM effectiveness, we exploited a human GBM patient-derived xenograft model in nude mice. Results: The most efficient crRNA sequence with a substantial cleavage impact on the target RNA as well as a potent collateral cleavage effect, was selected. In the xenografted GBM rodent model, the Cas13a-based reporter system enabled us in vivo imaging of the tumor growth. Furthermore, systemic treatments using this approach slowed tumor progression and increased the overall survival time in mice. Conclusions: Our work demonstrated the clinical potential of a Cas13a-based in vivo imaging method for the targeted degradation of specific RNAs in glioma cells, and suggested the feasibility of a tailored approach like Cas13a for the modulation of diagnosis and treatment options in glioma.


Subject(s)
Clustered Regularly Interspaced Short Palindromic Repeats , Glioma , Humans , Animals , Mice , Mice, Nude , Precision Medicine , CRISPR-Cas Systems/genetics , RNA , Glioma/diagnosis , Glioma/genetics , Glioma/therapy
5.
Animals (Basel) ; 13(9)2023 Apr 24.
Article in English | MEDLINE | ID: mdl-37174483

ABSTRACT

With the demand for standardized large-scale livestock farming and the development of artificial intelligence technology, a lot of research in the area of animal face detection and face identification was conducted. However, there are no specialized studies on livestock face normalization, which may significantly reduce the performance of face identification. The keypoint detection technology, which has been widely applied in human face normalization, is not suitable for animal face normalization due to the arbitrary directions of animal face images captured from uncooperative animals. It is necessary to develop a livestock face normalization method that can handle arbitrary face directions. In this study, a lightweight angle detection and region-based convolutional network (LAD-RCNN) was developed, which contains a new rotation angle coding method that can detect the rotation angle and the location of the animal's face in one stage. LAD-RCNN also includes a series of image enhancement methods to improve its performance. LAD-RCNN has been evaluated on multiple datasets, including a goat dataset and infrared images of goats. Evaluation results show that the average precision of face detection was more than 97%, and the deviations between the detected rotation angle and the ground-truth rotation angle were less than 6.42° on all the test datasets. LAD-RCNN runs very fast and only takes 13.7 ms to process a picture on a single RTX 2080Ti GPU. This shows that LAD-RCNN has an excellent performance in livestock face recognition and direction detection, and therefore it is very suitable for livestock face detection and normalization.

6.
Angew Chem Int Ed Engl ; 61(50): e202213910, 2022 Dec 12.
Article in English | MEDLINE | ID: mdl-36261322

ABSTRACT

Here we report the formation of giant {Mo126 W30 } polyoxometalate cages templated by π-conjugated planar ligands. Their inorganic shells incorporate arrays of 18 stacked aromatic carboxylates, such as 1,3,5-benzenetricarboxylate or 5-nitroisophthalate, and the assembly is stabilized by multiple π-π interactions. NMR data confirmed that the cages are stable in solution and the inner aromatic templates can be postsynthetically replaced by selected aliphatic dicarboxylates, paving the way for endo-functionalization and exploration of the reactivities within the cage cavities.

7.
ACS Omega ; 7(36): 31767-31777, 2022 Sep 13.
Article in English | MEDLINE | ID: mdl-36120046

ABSTRACT

Excessive phosphorus (P) in water is the main reason for eutrophication, which has been a global problem for many years. For the adsorption treatment of phosphorus-containing wastewater, adsorbents are key research topics. In this study, we develop the synthesis of a series of Ce/Fe adsorbents by modifying the commercial cerium carbonate with Fe2(SO4)3. By conducting comprehensive analysis with XRD, FTIR, and SEM, we find that the amorphous granular structure and large chunky structure created by the high and low Fe content, respectively, both had a negative effect on the adsorption capacity of phosphate. Among different adsorbents, Ce/Fe-15/3, with Ce loading of 28.33 wt % and Fe loading of 5.66 wt %, exhibits high P adsorption capacity of 58 mg P/g (in pH = 7, 30 mg P/L solution). It also demonstrates excellent selectivity toward phosphate adsorption in Cl-, SO4 2-, and NO3 - solution (up to 20 times of the phosphate molarity) and good adsorption stability in acidic environments (pH = 3-6). The adsorption behavior of Ce/Fe-15/3 can be modeled well by the Langmuir model and pseudo-second-order (PSO) model. By conducting the XPS analysis, we conclude that the adsorption mechanism is a combination effect of Ce/PO4 3- and Fe/PO4 3- chemical interactions.

8.
Chem Sci ; 13(19): 5718-5725, 2022 May 18.
Article in English | MEDLINE | ID: mdl-35694331

ABSTRACT

The pre-assembly and post-assembly approaches in the functionalization of a polyoxovanadate-organic cuboid, [{V6S}8(QPTC)8{V3}2]10-, are discussed. We have shown that the two pathways have led to distinctly different systems, with either an expanded or contracted interior void space, when phenylphosphonate is introduced at different stages of the self-assembly. One leaves the cuboid framework largely intact, whereas the other results in a compact, twisted cuboid. Kinetic factors will have to be considered in the equilibrium of these complex processes. Furthermore, the exceptional stability of these polyoxometalate-organic systems facilitates mass spectrometric characterization, which confirms the composition of the complexes and also indicates that the methoxide groups on the vanadium cluster nodes are labile. The results will help deepen the mechanistic understanding of the formation mechanisms of polyoxovanadate-based metal-organic cages and other functionalized polyoxovanadate clusters in general.

9.
ACS Omega ; 7(23): 19743-19753, 2022 Jun 14.
Article in English | MEDLINE | ID: mdl-35721969

ABSTRACT

Sevelamer hydrochloride (SH), originally developed as an oral pharmaceutical for controlling blood phosphate levels, is a polyallylamine resin that could be used in water treatments. Although it binds phosphates effectively, its adsorption capacity suffers from a significant loss at high pH. Here, we modify SH with lanthanum oxalate to improve its phosphate adsorption in alkaline environments. With less than 6.00 wt% in La content, the composite adsorbent (SH-1C-1La) exhibits an adsorption capacity of 109.3 mg P g-1 at pH 8.0 and 100.2 mg P g-1 at pH 10.0, demonstrating significant enhancement from the original SH (86.3 mg P g-1 at pH 8.0 and 69.4 mg P g-1 at pH 10.0). Besides its high adsorption capacity and rapid adsorption kinetics, SH-1C-1La is capable of maintaining more than 78% of its capacity after four regeneration cycles, showing good durability in long-term applications. Zeta-potential measurements and XPS analysis reveal that the lanthanum oxalate species increase the surface potential to enhance the electrostatic adsorption while introducing chemical binding sites for phosphate ions. Both factors lead to the improved adsorption properties. The modification by lanthanum oxalate species might provide a new alternative for improving the phosphate adsorption properties of anion-exchange resins.

10.
ACS Appl Mater Interfaces ; 6(10): 7275-85, 2014 May 28.
Article in English | MEDLINE | ID: mdl-24731240

ABSTRACT

High-specific-surface-area magnetic porous carbon microspheres (MPCMSs) were fabricated by annealing Fe(2+)-treated porous polystyrene (PS) microspheres, which were prepared using a two-step seed emulsion polymerization process. The resulting porous microspheres were then sulfonated, and Fe(2+) was loaded by ion exchange, followed by annealing at 250 °C for 1 h under an ambient atmosphere to obtain the PS-250 composite. The MPCMS-500 and MPCMS-800 composites were obtained by annealing PS-250 at 500 and 800 °C for 1 h, respectively. The iron oxide in MPCMS-500 mainly existed in the form of Fe3O4, which was concluded by characterization. The MPCMS-500 carbon microspheres were used as catalysts in heterogeneous Fenton reactions to remove methylene blue (MB) from wastewater with the help of H2O2 and NH2OH. The results indicated that this catalytic system has a good performance in terms of removal of MB; it could remove 40 mg L(-1) of MB within 40 min. After the reaction, the catalyst was conveniently separated from the media within several seconds using an external magnetic field, and the catalytic activity was still viable even after 10 removal cycles. The good catalytic performance of the composites could be attributed to synergy between the functions of the porous carbon support and the Fe3O4 nanoparticles embedded in the carrier. This work indicates that porous carbon spheres provide good support for the development of a highly efficient heterogeneous Fenton catalyst useful for environmental pollution cleanup.

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