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1.
Nature ; 575(7782): 336-340, 2019 11.
Artículo en Inglés | MEDLINE | ID: mdl-31723273

RESUMEN

Organoboron reagents are important synthetic intermediates that have a key role in the construction of natural products, pharmaceuticals and organic materials1. The discovery of simpler, milder and more efficient approaches to organoborons can open additional routes to diverse substances2-5. Here we show a general method for the directed C-H borylation of arenes and heteroarenes without the use of metal catalysts. C7- and C4-borylated indoles are produced by a mild approach that is compatible with a broad range of functional groups. The mechanism, which is established by density functional theory calculations, involves BBr3 acting as both a reagent and a catalyst. The potential utility of this strategy is highlighted by the downstream transformation of the formed boron species into natural products and drug scaffolds.


Asunto(s)
Compuestos de Boro/química , Compuestos de Boro/síntesis química , Boro/química , Productos Biológicos/síntesis química , Productos Biológicos/química , Teoría Funcional de la Densidad , Descubrimiento de Drogas , Indoles/química , Compuestos Organometálicos/química , Preparaciones Farmacéuticas/síntesis química , Preparaciones Farmacéuticas/química
2.
Opt Express ; 32(4): 6684-6699, 2024 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-38439366

RESUMEN

Topographic measurements of micro- or nanostructures are essential in cutting-edge scientific disciplines such as optical communications, metrology, and structural biology. Despite the advances in surface metrology, measuring micron-scale steps with wide field of view (FOV) and high-resolution remains difficult. This study demonstrates a dual-wavelength Fourier ptychographic microscopy for high-resolution topographic measurement across a wide FOV using an aperture scanning structure. This structure enables the capture of a three-dimensional (3D) sample's scattered field with two different wavelength lasers, thus allowing the axial measurement range growing from nano- to micro-scale with enhanced lateral resolution. To suppress the unavoidable noises and artifacts caused by temporal coherence, system vibration, etc., a total variation (TV) regularization algorithm is introduced for phase retrieval. A blazed grating with micron-scale steps is used as the sample to validate the performance of our method. The agreement between the high-resolution reconstructed topography with our method and that with atomic force microscopy verified the effectiveness. Meanwhile, numerical simulations suggest that the method has the potential to characterize samples with high aspect-ratio steps.

3.
J Opt Soc Am A Opt Image Sci Vis ; 41(4): 739-748, 2024 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-38568675

RESUMEN

With the development of autonomous driving, there has been considerable attention on 3D object detection using LiDAR. Pillar-based LiDAR point cloud detection algorithms are extensively employed in the industry due to their simple structure and high real-time performance. Nevertheless, the pillar-based detection network suffers from significant loss of 3D coordinate information during the feature degradation and extraction process. In the paper, we introduce a novel framework with high performance, termed EFNet. The EFNet uses the Enhancing Pillar Feature Module (EPFM) to provide more accurate representations of features from two directions: pillar internal space and pillar external space. Additionally, the Head Up Module (HUM) is utilized in the detection head to integrate multi-scale information and enhance the network's information perception ability. The EFNet achieves impressive results on the nuScenes datasets, namely, 53.3% NDS and 42.4% mAP. Compared to the baseline PointPillars, EFNet improves 8% NDS and 11.9% mAP. The results demonstrate that the proposed framework can effectively improve the network's accuracy while ensuring deployability.

4.
Sensors (Basel) ; 23(15)2023 Aug 03.
Artículo en Inglés | MEDLINE | ID: mdl-37571690

RESUMEN

In a data-driven context, bionic polarization navigation requires a mass of skylight polarization pattern data with diversity, complete ground truth, and scene information. However, acquiring such data in urban environments, where bionic polarization navigation is widely utilized, remains challenging. In this paper, we proposed a virtual-real-fusion framework of the skylight polarization pattern simulator and provided a data preparation method complementing the existing pure simulation or measurement method. The framework consists of a virtual part simulating the ground truth of skylight polarization pattern, a real part measuring scene information, and a fusion part fusing information of the first two parts according to the imaging projection relationship. To illustrate the framework, we constructed a simulator instance adapted to the urban environment and clear weather and verified it in 174 urban scenes. The results showed that the simulator can provide a mass of diverse urban skylight polarization pattern data with scene information and complete ground truth based on a few practical measurements. Moreover, we released a dataset based on the results and opened our code to facilitate researchers preparing and adapting their datasets to their research targets.

5.
Angew Chem Int Ed Engl ; 62(44): e202313205, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37721200

RESUMEN

Enamides, functional derivatives of enamines, play a significant role as synthetic targets. However, the stereoselective synthesis of these molecules has posed a longstanding challenge in organic chemistry, particularly for acyclic enamides that are less thermodynamically stable. In this study, we present a general strategy for constructing ß-borylenamides by C-H borylation, which provides a versatile platform for generating the stereodefined enamides. Our approach involves the utilization of metalloid borenium cation, generated through the reaction of BBr3 and enamides in the presence of two different additives, avoiding any exogenous catalyst. Importantly, the stereoconvergent nature of this methodology allows for the use of starting materials with mixed E/Z configurations, thus highlighting the unique advantage of this chemistry. Mechanistic investigations have shed light on the pivotal roles played by the two additives, the reactive boron species, and the phenomenon of stereoconvergence.

6.
Opt Express ; 30(9): 15777-15795, 2022 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-35473291

RESUMEN

Large optical flats play a remarkable role in advanced large-aperture optical systems and the testing of the surface shape error is indispensable for the fabrication. The widely adopted Ritchey-Common test for large optical flats will fail without the rigorous test configurations including a large F/# prerequisition and a flat-to-interferometer distance invariance. A virtual-real combination Ritchey-Common interferometry is proposed to avoid the large F/# prerequisition by accurately modelling the optical path in a virtual interferometer. Furthermore, a virtual-real combination iterative algorithm is proposed in this method to break the flat-to-interferometer distance invariance. Measurement experiments for 100 mm and 422 mm aperture flats were performed to demonstrate the feasibility of this method. Compared with a direct testing in a standard Zygo interferometer, the peak to valley (PV) and root mean square (RMS) errors were less than 0.1 λ and 0.01 λ (λ=632.8 nm), respectively, in different Ritchey angles and flat-to-interferometer distances. Further numerical simulations demonstrate that RMS errors for various Zernike aberrations in arbitrary F/# are less than 0.01 λ. This method can break the distance invariance restriction and achieve high accuracy with an arbitrary F/#, thus providing substantial freedom in the design of test configurations to accommodate various test scenarios.

7.
Chemistry ; 28(9): e202104100, 2022 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-34878200

RESUMEN

Transition-metal-catalyzed C-H borylation has been widely used in the preparation of organoboron compounds. Here, we developed a general protocol on metal-free P(III)-directed C-H borylation of phosphines mediated by BBr3 , resulting in the formation of products bearing both phosphorus and boron. The development of the metal-free strategy to mimic previous metallic processes has shown low cost, superior practicality, and environmental friendliness. Density functional theory (DFT) calculations demonstrate the preferred pathway for this metal-free directed C-H borylation process.

8.
Opt Express ; 29(11): 16804-16819, 2021 May 24.
Artículo en Inglés | MEDLINE | ID: mdl-34154234

RESUMEN

The description of deformable mirror (DM) surface, which is usually a complex freeform surface, affects the measurement speed and accuracy in a real-time interferometric measurement system with a DM as the dynamic compensator. We propose an accurate and fast description method with automatically configurable Gaussian radial basis function. The distribution and shape factors of GRBFs are related to the complexity of the surface with sufficient flexibility to improve the accuracy, and the fitting results are automatically obtained using a traversal optimization algorithm, which can improve the fitting speed by reducing the number of time-consuming calculations. The feasibility is verified by numerical and practical experiment.

9.
Sensors (Basel) ; 21(7)2021 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-33915823

RESUMEN

The refractive index is one of the most important parameters of optical glasses and has a significant effect on optical properties. The measurement of optical glasses, especially for optical elements such as lenses, is urgently needed. However, several presented methods require the immersion of the sample in liquid and provide indirect measurements, while others require structural parameters as priori knowledge, which is complex and time-consuming. In this study, a Brewster-Law-based direct and simple measurement method for the refractive index of glasses with arbitrary shapes is proposed, and a laser beam is focused on the surface of the sample as a probe. The incident angle of the chief ray is close to the Brewster angle. The reflected light is collected by an array detector. The refractive index is calculated from the minimum intensity position obtained with image processing. Additionally, a symmetric measurement scheme is proposed to improve the accuracy. Using these methods, a prism and four spherical lens samples with different refractive indices or radii of curvature are tested and error analyses are carried out. Results indicate that the accuracy can reach 10-4.

10.
Nat Commun ; 15(1): 7380, 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39191737

RESUMEN

Recent strides in C-H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C-C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies have been proposed for hydroboration of cyclopropanes by activating C-C bonds, conventionally relying on noble and hazardous metal catalysts to control reaction outcomes. Here, we present a strategy for crafting stereochemically precise γ-borylenamides through ring-opening of cyclopropanes avoiding any metallic entities. Boryl species, generated through a ternary reaction with BCl3, cyclopropanes, and a tertiary amine, selectively undergo C-C bond eliminative borylation under the directing of N-acyl group, thereby ensuring enhanced selectivity and efficiency along the reaction pathway. Such inherently stereoconvergent approach accommodates precursors of diverse geometries, including cis/trans isomeric blends.

11.
Quant Imaging Med Surg ; 13(3): 1426-1439, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36915357

RESUMEN

Background: Imaging and tracking are crucial for microrobots which navigate through complex 3D environments. Fluorescent imaging (FI) by microscope offers a high-resolution and high-sensitive imaging method to study the property of microrobots. However, conventional microscope suffers from shallow depth of field (DOF) and lacks 3D imaging capability. Methods: We proposed a high-resolution and high-speed 3D tracking method for microrobots based on a fluorescent light field microscope (FLFM). We designed the FLFM system according to the size of a representative helical microrobot (150 µm body length, 50 µm screw diameter), and studied the system's performance. We also proposed a 3D tracking algorithm for microrobots using digital refocusing. Results: We validated the method by simulations and built an FLFM system to perform the tracking experiments of microrobots with representative size. Our 3D tracking method achieves a 30 fps data acquisition rate, 10 µm lateral resolution and approximately 40 µm axial resolution over a volume of 1,200×1,200×326 µm3. Results indicate that the accuracy of the method can reach about 9 µm. Conclusions: Compared with the FI by a conventional microscope, the FLFM-based method gains wider DOF and 3D imaging capability with a single-shot image. The tracking method succeeds in providing the trajectory of the microrobot with a good lateral resolution.

12.
Biomaterials ; 291: 121873, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-36343610

RESUMEN

With multiple emissions ranging from NIR-IIb to visible lights, near-infrared light-excited lanthanide nanoparticle (LnNP) is an ideal in-vivo theranostic platform to achieve imaging guided phototherapy. However, current reported LnNPs typically demonstrate simultaneous up and downconversion emissions with fixed single excitation light, which impairs therapeutic efficiency and generates side effect during navigation. Here we develop a lanthanide-based conversion switching nanoparticle (CSNP) with independent activation of 1550 nm NIR-IIb downconversion emission under 808 nm excitation and 345/450 nm upconversion emission under 980 nm excitation. CSNP is modified with Cy-GSH to quench NIR-IIb emission and photosensitizer hypocrellin A. In vivo delivery of CSNP is traced via 808 nm irradiation, and Cy-GSH changes structure in response to glutathione to activate NIR-IIb imaging. This indicates the tumor position and timing to switch for 980 nm irradiation to activate hypocrellin A for photodynamic therapy. Orthogonal activation of CSNP up/down conversion emissions demonstrates high tumor-to-normal tissue ratio in vivo and good therapeutic result, would have promising potential as a theranostics platform.


Asunto(s)
Elementos de la Serie de los Lantanoides , Nanopartículas , Neoplasias , Humanos , Elementos de la Serie de los Lantanoides/química , Medicina de Precisión , Nanopartículas/química , Neoplasias/tratamiento farmacológico
13.
Nat Commun ; 11(1): 1316, 2020 03 12.
Artículo en Inglés | MEDLINE | ID: mdl-32165636

RESUMEN

Transition metal-catalysed C-H hydroxylation is one of the most notable advances in synthetic chemistry during the past few decades and it has been widely employed in the preparation of alcohols and phenols. The site-selective hydroxylation of aromatic C-H bonds under mild conditions, especially in the context of substituted (hetero)arenes with diverse functional groups, remains a challenge. Here, we report a general and mild chelation-assisted C-H hydroxylation of (hetero)arenes mediated by boron species without the use of any transition metals. Diverse (hetero)arenes bearing amide directing groups can be utilized for ortho C-H hydroxylation under mild reaction conditions and with broad functional group compatibility. Additionally, this transition metal-free strategy can be extended to synthesize C7 and C4-hydroxylated indoles. By utilizing the present method, the formal synthesis of several phenol intermediates to bioactive molecules is demonstrated.

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