Fresnel lens three-dimensionally printed on the facet of a single mode fiber for trapping, manipulation, and spectrum.

Fiber optical tweezers (FOTs) provide a functionality for micro-/nanoparticle manipulation with a slim and flexible optical fiber setup. An added in situ spectroscopic functionality can achieve characterization of the trapped particle, potentially useful for endoscopic, in-vivo studies in an inherently heterogeneous environment if the applicator end is all-fiber-built. Here, we demonstrate all-fiber optical tweezers (a-FOTs) for the trapping and in situ spectral measurement of a single, cell-sized microparticle. The key to ensure the simultaneous bifunctionality is a high numerical aperture (NA) Fresnel lens fabricated by two-photon direct laser writing (DLW) corrected by grid-correction methods. We demonstrate trapping and time-resolved, in situ spectroscopy of a single upconversion particle (UCP), a common fluorescent biomarker in biophotonics. The system achieves a 0.5-s time resolution in the in situ spectral measurement of a trapped UCP. The all-fiber designed system preserves the advantages of flexibility and robustness of the fiber, potentially useful for in-vivo biomedical studies such as cell-to-cell interactions, pH and temperature detection, and nucleic acids detection.

Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction.

The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture1,2. Copper (Cu) is relied on today for carbon-carbon coupling, in which it produces mixtures of more than ten C2+ chemicals3-6: a long-standing challenge lies in achieving selectivity to a single principal C2+ product7-9. Acetate is one such C2 compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes10-chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10 atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C2+ product11.

Raman spectroscopy of optical-trapped single particle using bull's eye nanostructure.

Surface-enhanced Raman spectroscopy (SERS) has enabled single nanoparticle Raman sensing with abundant applications in analytical chemistry, biomaterials, and environmental monitoring. Genuine single particle Raman sensing requires a cumbersome technique, such as atomic force microscopy (AFM) based tip-enhanced Raman spectroscopy; SERS-based single particle Raman sensing still collects an ensemble signal that samples, in principle, a number of particles. Here, we develop in situ Raman-coupled optical tweezers, based on a hybrid nanostructure consisting of a single bowtie aperture surrounded by bull's eye rings, to trap and excite a rhodamine-6G-dye-doped polystyrene sphere. We simulated a platform to ensure sufficient enhancement capability for both optical trapping and SERS of a single nanoparticle. Experiments with well-designed controls clearly attribute the Raman signal origin to a single 15-nm particle trapped at the center of a nanohole, and they also clarified the trapping and Raman enhancement role of the bull's eye rings. We claim Raman sensing of a smallest optically trapped particle.

Directivity-Enhanced Detection of a Single Nanoparticle Using a Plasmonic Slot Antenna.

In situ refractive index sensors integrated with nanoaperture-based optical tweezers possess stable and sensitive responsivity to single nanoparticles. In most existing works, detection events are only identified using the total light intensity with directivity information ignored, leading to a low signal-to-noise ratio. Here, we propose to detect an optically trapped 20 nm silica particle by monitoring directivity of a plasmonic antenna. The main and secondary radiation lobes of the antenna reverse upon trapping because the particle-induced perturbation negates the relative phase between two antenna elements, leading to a significant change of the antenna front-to-back ratio. As a result, we obtain a signal-to-noise ratio of 20, with an order-of-magnitude improvement as compared to the intensity-only detection scheme.

Plant tissue imaging with bipyramidal upconversion nanocrystals by introducing Tm3+ ions as energy trapping centers.

Plant cell imaging is critical for agricultural production and plant pathology study. Advanced upconversion nanoparticles (UCNPs) are being developed as fluorescent probes for imaging cells and tissues in vivo and in vitro. Unfortunately, the thick cellulosic walls as barriers together with hemicelluloses and pectin hinder the entrance of macromolecules into the epidermal plant cell. Hence, realizing satisfactory temporal and spatial resolution with UCNPs remains an arduous task. Here, bipyramidal LiErF4:1%Tm3+@LiYF4 core-shell UCNPs with a super-bright red emission upon 980 nm laser excitation are explored, where the introduction of Tm3+ ions permits alleviation of the energy loss at defective sites and a significant improvement of the upconversion output. The as-obtained bipyramidal UCNPs could readily puncture plant cell walls and further penetrate into cell membranes, facilitating improved tissue imaging of cellular internalization, as demonstrated with the luminescence images obtained by multiphoton laser-scanning microscopy. Hence our work opens up a new avenue for exploring effective upconversion nanoparticles for achieving high resolution imaging of plant tissues.

Ultrahigh photo-stable all-inorganic perovskite nanocrystals and their robust random lasing.

Photo-instability has prevented further commercialization of all-inorganic perovskite nanocrystals (NCs) in the field of high-power optoelectronics. Here, an accelerated transformation process from non-luminescent Cs4PbBr6 to CsPbBr3 NCs with bright green emission is explored with irradiation at 365 nm during water-triggered structural transformation. The photoelectric field provided by the photon energy of 365 nm promotes the rapid stripping of CsBr and atomic reconstruction, contributing to the production of ultrahigh photo-stable defect-free CsPbBr3 NCs. The robust emission output of the as-obtained CsPbBr3 NCs is well preserved even when recorded after 160 min. Moreover, a long-term stable random lasing could be achieved when excited using an ∼800 nm femtosecond laser for at least 8.6 × 107 laser shots. Our results not only elucidate the photo-induced accelerated phase transformation process of the all-inorganic perovskites, but also open up opportunities to synthesize highly stable CsPbBr3 NCs for their practical application in photovoltaics and optoelectronics.

Modified surface states of NaGdF4:Yb3+/Tm3+ up-conversion nanoparticles via a post-chemical annealing process.

An amorphous layer acting as a quenching center at the surface of oleic acid-capped NaGdF4:Yb3+/Tm3+ nanoparticles is observed directly, which can be reconstructed via a novel post-chemical annealing process. The amorphous phase of the surface layer of NaGdF4:Yb3+/Tm3+ nanoparticles gradually crystallizes as the post-chemical annealing temperature increases; meanwhile, the good dispersibility of the as-obtained nanoparticles is maintained. The reduction of surface defects and higher local symmetry of the crystal field environment around the doped rare-earth ions contribute to drastically increased up-conversion (UC) emission intensity of the NaGdF4:Yb3+/Tm3+ nanoparticles. In particular, the blue emission of Tm3+ at 450 nm enhances 10-fold after the post-chemical annealing process at 250 °C compared with the counterpart without further surface-state treatments. The color gamut of well-crystallized NaGdF4:Yb3+/Tm3+ with a modified surface covers the blue to yellow region in CIE chromaticity coordinates via a non-steady-state UC process. The results indicate that the surface states of these UC nanoparticles can be feasibly improved via the post-chemical annealing process without encouraging agglomeration, which further optimizes their UC properties for practical applications.