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1.
J Am Chem Soc ; 145(21): 11789-11797, 2023 May 31.
Article in English | MEDLINE | ID: mdl-37198745

ABSTRACT

Asymmetric intermolecular C-H functionalization of pyridines at C3 is unprecedented. Herein, we report the first examples of such transformations: specifically, C3-allylation of pyridines via tandem borane and iridium catalysis. First, borane-catalyzed pyridine hydroboration generates nucleophilic dihydropyridines; then, the dihydropyridine undergoes enantioselective iridium-catalyzed allylation; and finally, oxidative aromatization with air as the oxidant gives the C3-allylated pyridine. This protocol provides direct access to C3-allylated pyridines with excellent enantioselectivity (up to >99% ee) and is suitable for late-stage functionalization of pyridine-containing drugs.

2.
Phys Rev Lett ; 129(16): 167403, 2022 Oct 14.
Article in English | MEDLINE | ID: mdl-36306749

ABSTRACT

In this Letter, we investigate a new class of polarization wave front transformations which exhibit nonconventional far field interference behavior. We show that these can be realized by double-layer metasurfaces, which overcome the intrinsic limitations of single-layer metasurfaces. Holograms that encode four or more distinct patterns in nonorthogonal polarization states are theoretically demonstrated. This Letter clarifies and expands the possibilities enabled by a broad range of technologies which can spatially modulate light's polarization state and, for metasurfaces specifically, rigorously establishes when double-layer metasurfaces are-and are not-required.

3.
J Am Chem Soc ; 144(11): 4810-4818, 2022 03 23.
Article in English | MEDLINE | ID: mdl-35258282

ABSTRACT

Achieving C3-selective pyridine functionalization is a longstanding challenge in organic chemistry. The existing methods, including electrophilic aromatic substitution and C-H activation, often require harsh reaction conditions and excess pyridine and generate multiple regioisomers. Herein, we report a method for borane-catalyzed tandem reactions that result in exclusively C3-selective alkylation of pyridines. These tandem reactions consist of pyridine hydroboration, nucleophilic addition of the resulting dihydropyridine to an imine, an aldehyde, or a ketone, and subsequent oxidative aromatization. Because the pyridine is the limiting reactant and the reaction conditions are mild, this method constitutes a practical tool for late-stage functionalization of structurally complex pharmaceuticals bearing a pyridine moiety.


Subject(s)
Aldehydes , Boranes , Alkylation , Catalysis , Imines , Ketones , Molecular Structure , Pyridines
4.
Sci Adv ; 7(33)2021 Aug.
Article in English | MEDLINE | ID: mdl-34389537

ABSTRACT

We propose a new class of computer-generated holograms whose far-fields have designer-specified polarization response. We dub these Jones matrix holograms. We provide a simple procedure for their implementation using form-birefringent metasurfaces. Jones matrix holography generalizes a wide body of past work with a consistent mathematical framework, particularly in the field of metasurfaces, and suggests previously unrealized devices, examples of which are demonstrated here. In particular, we demonstrate holograms whose far-fields implement parallel polarization analysis and custom waveplate-like behavior.

5.
Sci Adv ; 7(5)2021 Jan.
Article in English | MEDLINE | ID: mdl-33571130

ABSTRACT

Virtual and augmented realities are rapidly developing technologies, but their large-scale penetration will require lightweight optical components with small aberrations. We demonstrate millimeter-scale diameter, high-NA, submicron-thin, metasurface-based lenses that achieve diffraction-limited achromatic focusing of the primary colors by exploiting constructive interference of light from multiple zones and dispersion engineering. To illustrate the potential of this approach, we demonstrate a virtual reality system based on a home-built fiber scanning near-eye display.

6.
Sci Adv ; 6(23): eaba3367, 2020 Jun.
Article in English | MEDLINE | ID: mdl-32537506

ABSTRACT

Birefringence occurs when light with different polarizations sees different refractive indices during propagation. It plays an important role in optics and has enabled essential polarization elements such as wave plates. In bulk crystals, it is typically constrained to linear birefringence. In metamaterials with freeform meta-atoms, however, one can engineer the optical anisotropy such that light sees different indices for arbitrary-linear, circular, or elliptical-orthogonal eigen-polarization states. Using topology-optimized metasurfaces, we demonstrate this arbitrary birefringence. It has the unique feature that it can be continuously tuned from linear to elliptical birefringence, by changing the angle of incidence. In this way, a single metasurface can operate as many wave plates in parallel, implementing different polarization transformations. Angle-tunable arbitrary birefringence expands the scope of polarization optics, enables compact and versatile polarization operations that would otherwise require cascading multiple elements, and may find applications in polarization imaging, quantum optics, and other areas.

7.
Proc Natl Acad Sci U S A ; 116(46): 22959-22965, 2019 11 12.
Article in English | MEDLINE | ID: mdl-31659026

ABSTRACT

Jumping spiders (Salticidae) rely on accurate depth perception for predation and navigation. They accomplish depth perception, despite their tiny brains, by using specialized optics. Each principal eye includes a multitiered retina that simultaneously receives multiple images with different amounts of defocus, and from these images, distance is decoded with relatively little computation. We introduce a compact depth sensor that is inspired by the jumping spider. It combines metalens optics, which modifies the phase of incident light at a subwavelength scale, with efficient computations to measure depth from image defocus. Instead of using a multitiered retina to transduce multiple simultaneous images, the sensor uses a metalens to split the light that passes through an aperture and concurrently form 2 differently defocused images at distinct regions of a single planar photosensor. We demonstrate a system that deploys a 3-mm-diameter metalens to measure depth over a 10-cm distance range, using fewer than 700 floating point operations per output pixel. Compared with previous passive depth sensors, our metalens depth sensor is compact, single-shot, and requires a small amount of computation. This integration of nanophotonics and efficient computation brings artificial depth sensing closer to being feasible on millimeter-scale, microwatts platforms such as microrobots and microsensor networks.


Subject(s)
Lens, Crystalline/chemistry , Optics and Photonics/instrumentation , Spiders/physiology , Animals , Depth Perception , Equipment Design , Eye/chemistry , Metals/chemistry , Vision, Ocular
8.
Cancer Med ; 8(12): 5425-5430, 2019 Sep.
Article in English | MEDLINE | ID: mdl-31385452

ABSTRACT

In recent years, the incidence of gynecological malignant tumors during pregnancy has increased, mainly due to the increased number of old age pregnancy. The most common gynecological malignant tumors in pregnancy are cervical cancer, accounting for 71.6%, followed by ovarian malignant tumors, accounting for 7.0%. The incidence of cervical cancer in pregnancy is itself not very high, and the symptoms are easily confused with other diseases in pregnancy. During pregnancy, gynecological examination is limited, and therefore, the rate of misdiagnosis is higher. The treatment of cervical cancer during pregnancy is related to many factors, such as tumor size, pathological type, period of gestation, lymph node involvement, and patients' willingness to maintain pregnancy. As a reason of these factors, it is difficult to determine the optimal treatment. This article reviews the research progress on the diagnosis and treatment principles of cervical cancer in pregnancy, in order to strike a balance between effective treatment of tumors and protection of fetal health, and avoid delays in treatment and preterm delivery.


Subject(s)
Pregnancy Complications, Neoplastic/diagnosis , Pregnancy Complications, Neoplastic/therapy , Uterine Cervical Neoplasms/diagnosis , Uterine Cervical Neoplasms/therapy , Clinical Decision-Making , Disease Management , Female , Humans , Obstetric Labor, Premature/prevention & control , Practice Guidelines as Topic , Pregnancy , Risk Assessment
9.
Science ; 365(6448)2019 07 05.
Article in English | MEDLINE | ID: mdl-31273096

ABSTRACT

Recent developments have enabled the practical realization of optical elements in which the polarization of light may vary spatially. We present an extension of Fourier optics-matrix Fourier optics-for understanding these devices and apply it to the design and realization of metasurface gratings implementing arbitrary, parallel polarization analysis. We show how these gratings enable a compact, full-Stokes polarization camera without standard polarization optics. Our single-shot polarization camera requires no moving parts, specially patterned pixels, or conventional polarization optics and may enable the widespread adoption of polarization imaging in machine vision, remote sensing, and other areas.

10.
Org Biomol Chem ; 17(26): 6351-6354, 2019 07 14.
Article in English | MEDLINE | ID: mdl-31215946

ABSTRACT

A range of 3,3-disubstituted oxindoles accessed using para-quinone methides derived from isatins with thiols were used for the formation of unsymmetrical disulfides, and 3,3-disubstituted oxindoles with a chiral quaternary carbon center and unsymmetric disulfides could also be directly obtained with high selectivities catalyzed by chiral phosphines in one step.

11.
Opt Express ; 27(5): 7469-7484, 2019 Mar 04.
Article in English | MEDLINE | ID: mdl-30876310

ABSTRACT

Optical elements coupling the spin and orbital angular momentum (SAM/OAM) of light have found a range of applications in classical and quantum optics. The J-plate, with J referring to the photon's total angular momentum (TAM), is a metasurface device that imparts two arbitrary OAM states on an arbitrary orthogonal basis of spin states. We demonstrate that when these J-plates are cascaded in series, they can generate several single quantum number beams and versatile superpositions thereof. Moreover, in contrast to previous spin-orbit-converters, the output polarization states of cascaded J-plates are not constrained to be the conjugate of the input states. Cascaded J-plates are also demonstrated to produce vector vortex beams and complex structured light, providing new ways to control TAM states of light.

12.
Nano Lett ; 18(4): 2420-2427, 2018 04 11.
Article in English | MEDLINE | ID: mdl-29461838

ABSTRACT

In this paper, we report dispersion-engineered metasurfaces with distinct functionalities controlled by wavelength. Unlike previous approaches based on spatial multiplexing or vertical stacking of metasurfaces, we utilize a single phase profile with wavelength dependence encoded in the phase shifters' dispersion. We designed and fabricated a multiwavelength achromatic metalens (MAM) with achromatic focusing for blue (B), green (G), yellow (Y), and red (R) light and two wavelength-controlled beam generators (WCBG): one focuses light with orbital angular momentum (OAM) states ( l = 0,1,2) corresponding to three primary colors; the other produces ordinary focal spots ( l = 0) for red and green light, while generating a vortex beam ( l = 1) in the blue. A full color (RGB) hologram is also demonstrated in simulation. Our approach opens a path to applications ranging from near-eye displays and holography to compact multiwavelength beam generation.

13.
Nat Nanotechnol ; 13(3): 220-226, 2018 03.
Article in English | MEDLINE | ID: mdl-29292382

ABSTRACT

A key goal of metalens research is to achieve wavefront shaping of light using optical elements with thicknesses on the order of the wavelength. Such miniaturization is expected to lead to compact, nanoscale optical devices with applications in cameras, lighting, displays and wearable optics. However, retaining functionality while reducing device size has proven particularly challenging. For example, so far there has been no demonstration of broadband achromatic metalenses covering the entire visible spectrum. Here, we show that by judicious design of nanofins on a surface, it is possible to simultaneously control the phase, group delay and group delay dispersion of light, thereby achieving a transmissive achromatic metalens with large bandwidth. We demonstrate diffraction-limited achromatic focusing and achromatic imaging from 470 to 670 nm. Our metalens comprises only a single layer of nanostructures whose thickness is on the order of the wavelength, and does not involve spatial multiplexing or cascading. While this initial design (numerical aperture of 0.2) has an efficiency of about 20% at 500 nm, we discuss ways in which our approach may be further optimized to meet the demand of future applications.

14.
Nat Photonics ; 12(9): 540-547, 2018 Sep.
Article in English | MEDLINE | ID: mdl-30713581

ABSTRACT

Acquisition of high-resolution images from within internal organs using endoscopic optical imaging has numerous clinical applications. However, difficulties associated with optical aberrations and the trade-off between transverse resolution and depth-of-focus significantly limit the scope of applications. Here, we integrate a metalens, with the ability to modify the phase of incident light at sub-wavelength level, into the design of an endoscopic optical coherence tomography catheter (termed nano-optic endoscope) to achieve near diffraction-limited imaging through negating non-chromatic aberrations. Remarkably, the tailored chromatic dispersion of the metalens in the context of spectral interferometry is utilized to maintain high-resolution imaging beyond the input field Rayleigh range, easing the trade-off between transverse resolution and depth-of-focus. We demonstrate endoscopic imaging both in resected human lung specimens and in sheep airways in vivo. The combination of the superior resolution and higher imaging depth-of-focus of the nano-optic endoscope will likely increase the clinical utility of endoscopic optical imaging.

15.
Nano Lett ; 17(5): 3188-3194, 2017 05 10.
Article in English | MEDLINE | ID: mdl-28388086

ABSTRACT

Immersion objectives can focus light into a spot smaller than what is achievable in free space, thereby enhancing the spatial resolution for various applications such as microscopy, spectroscopy, and lithography. Despite the availability of advanced lens polishing techniques, hand-polishing is still required to manufacture the front lens of a high-end immersion objective, which poses major constraints for lens design. This limits the shape of the front lens to spherical. Therefore, several other lenses need to be cascaded to correct for spherical aberration, resulting in significant challenges for miniaturization and adding design complexity for different immersion liquids. Here, by using metasurfaces, we demonstrate liquid immersion meta-lenses free of spherical aberration at various design wavelengths in the visible spectrum. We report water and oil immersion meta-lenses of various numerical apertures (NA) up to 1.1 and show that their measured focal spot sizes are diffraction-limited with Strehl ratios of approximately 0.9 at 532 nm. By integrating the oil immersion meta-lens (NA = 1.1) into a commercial scanning confocal microscope, we achieve an imaging spatial resolution of approximately 200 nm. These meta-lenses can be easily adapted to focus light through multilayers of different refractive indices and mass-produced using modern industrial manufacturing or nanoimprint techniques, leading to cost-effective high-end optics.

16.
Anim Nutr ; 3(2): 151-155, 2017 Jun.
Article in English | MEDLINE | ID: mdl-29767048

ABSTRACT

This study was conducted to investigate the effects of raw material extrusion and steam conditioning on feed pellet quality and nutrient digestibility of growing meat rabbits, in order to determine appropriate rabbit feed processing methods and processing parameters. In Exp. 1, an orthogonal design was adopted. Barrel temperature, material moisture content and feed rate were selected as test factors, and acid detergent fiber (ADF) content was selected as an evaluation index to research the optimum extrusion parameters. In Exp. 2, a two-factor design was adopted. Four kinds of rabbit feeds were processed and raw material extrusion adopted optimum extrusion parameters of Exp. 1. A total of 40 healthy and 42-day-old rabbits with similar weight were used in a randomized design, which consisted of 4 groups and 10 replicates in each group (1 rabbits in each replicate). The adaptation period lasted for 7 d, and the digestion trial lasted for 4 d. The results showed as follows: 1) ADF was significantly affected by barrel temperature (P < 0.05); the optimum extrusion parameters were barrel temperature 125 °C, moisture content 16% and feed rate 9 Hz. 2) Raw material extrusion and steam conditioning both significantly decreased powder percentage, pulverization ratio and protein solubility (P < 0.05), significantly improved hardness and starch gelatinization degree of rabbit feed (P < 0.05). They both had significant interaction effects on the processing quality of rabbit feed (P < 0.05). 3) Extrusion significantly improved the apparent digestibility of dry matter and total energy (P < 0.05). Extrusion and steam conditioning both significantly improved the apparent digestibility of crude fiber (CF), ADF and NDF (P < 0.05), but they had no interaction effects on the apparent digestibility of rabbit feed. Thus, using extrusion and steam conditioning technology at the same time in the weaning rabbits feed processing can improve the pellet quality and nutrient apparent digestibility of rabbit feed.

17.
Food Chem ; 163: 1-5, 2014 Nov 15.
Article in English | MEDLINE | ID: mdl-24912688

ABSTRACT

The hydrolysis kinetics and radical-scavenging activity of gelatin were investigated under simulated gastrointestinal digestion in this study. In the gastric phase, the degree of gelatin hydrolysis increased from 0.17% to 1.20%, while the DPPH radical-scavenging rate increased from 6.27% to 24.56%. Further digestion in the intestinal phase brought the degree of hydrolysis and radical-scavenging rate to 26.08% and 44.76%, respectively. After digestion, the gelatin hydrolysates were separated into two fractions by ultrafiltration. The fraction with an average molecular weight of 312.98 Da exhibited the higher yield (78.26%) and radical-scavenging activity (IC50=2.09 mg/ml), suggesting the high digestibility and bioactivity of gelatin after oral administration. The fraction was further purified with multi-step column chromatography and identified to be Gly-Pro-Met (303.38 Da) by UPLC-ESI-MS. These results may help us to better understand its physiological effects and to use it properly in foods and pharmaceuticals.


Subject(s)
Free Radical Scavengers/pharmacology , Gastrointestinal Tract/metabolism , Gelatin/metabolism , Amino Acid Sequence , Digestion , Gelatin/chemistry , Gelatin/pharmacology , Hydrolysis , Kinetics , Ultrafiltration
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