Photoredox-Catalyzed Decarboxylative Cross-Coupling Reaction to Synthesis Unsymmetrical Diarylmethanes.

The photoredox-catalyzed decarboxylative cross-coupling reaction of aryl acetic acids and aryl nitriles has been achieved under an argon atmosphere in high yields. This method provides a fast way to obtain prevalent aryl acetic acids from an abundant natural source. A tentative radical mechanism has been proposed.

Selective plasmonic trapping of nano-particles by Archimedes metalens.

Optical tweezer is a non-invasive method for optical force tool applied in various fields like biology, physics, and lab on chip manipulation. The Archimedean helix shape is ideal for creating chiral nanostructures, and being able to generate plasmonic focused hotspot field for optical trapping. Here we design a metal disk with the Archimedean shape to own the ability of selective trapping nanoparticles based on the spin-orbit interactions with circularly polarized light. The plasmonic near field on the metalens can be designed by adjusting the geometric parameter flexibly. We numerically analyze the optimal size and screw pitch of the metal disk to realize the switch modulation of hotspot generation, and then demonstrate the novel switchable optical trapping ability in the view of optical force and potential well analysis under the circularly polarized light excitation by a 532 nm laser. The work shows significant potential for on-chip optical trapping in various fields.

Transversal optical singularity induced precision measurement of step-nanostructures.

Optical singularities indicate zero-intensity points in space where parameters, such as phase, polarization, are undetermined. Vortex beams such as the Laguerre-Gaussian modes are characterized by a phase factor eilθ, and contain a phase singularity in the middle of its beam. In the case of a transversal optical singularity (TOS), it occurs perpendicular to the propagation, and its phase integral is 2π in nature. Since it emerges within a nano-size range, one expects that TOSs could be sensitive in the light-matter interaction process and could provide a great possibility for accurate determination of certain parameters of nanostructure. Here, we propose to use TOSs generated by a three-wave interference to illuminate a step nanostructure. After interaction with the nanostructure, the TOS is scattered into the far field. The scattering direction can have a relation with the physical parameters of the nanostructure. We show that by monitoring the spatial coordinates of the scattered TOS, its propagation direction can be determined, and as consequence, certain physical parameters of the step nanostructure can be retrieved with high precision.

Temporal effect of the spin-to-orbit conversion in tightly focused femtosecond optical fields.

Spin and orbital angular momenta are two of the most fundamental physical quantities that describe the complex dynamic behaviors of optical fields. A strong coupling between these two quantities leads to many intriguing spatial topological phenomena, where one remarkable example is the generation of a helicity-dependent optical vortex that converts spin to orbital degrees of freedom. The spin-to-orbit conversion occurs inherently in lots of optical processes and has attracted increasing attention due to its crucial applications in spin-orbit photonics. However, current researches in this area are mainly focused on the monochromatic optical fields whose temporal properties are naturally neglected. In this work, we demonstrate an intriguing temporal evolution of the spin-to-orbit conversion induced by tightly-focused femtosecond optical fields. The results indicate that the conversion in such a polychromatic focused field obviously depends on time. This temporal effect originates from the superposition of local fields at the focus with different frequencies and is sensitive to the settings of pulse width and central wavelength. This work can provide fundamental insights into the spin-orbit dynamics within ultrafast wave packets, and possesses the potential for applications in spin-controlled manipulations of light.

Effect of the focused gap-plasmon mode on tip-enhanced Raman excitation and scattering.

As a powerful molecular detection approach, tip-enhanced Raman scattering (TERS) spectroscopy has the advantages of nanoscale spatial resolution, label-free detection and high enhancement factor, therefore has been widely used in fields of chemistry, materials and life sciences. A TERS system enhanced by the focused gap-plasmon mode composed of Surface Plasmon Polariton (SPP) focus and the metal probe has been reported, however, its underlying enhancement mechanism for Raman excitation and scattering remains to be deeply explored. Here, we focus on the different performances of optical focus and SPP focus in the TERS system, and verify that the cooperation of these two focuses can produce maximum enhancement in a local electromagnetic field. Further, the Purcell effect on sample scattering in such a system is studied for the enhancement of Raman scattering collection in the far field. Finally, the local field enhancement and the sample far-field scattering enhancement are combined to show a full view of the whole process of TERS enhancement. This research can be applied to optimize the excitation and collection of Raman signals in TERS systems, which is of great value for the research and development of TERS technology.

Ultraviolet metalens for photoacoustic microscopy with an elongated depth of focus.

Ultraviolet photoacoustic microscopy (UV-PAM) can achieve in vivo imaging without exogenous markers and play an important role in pathological diagnosis. However, traditional UV-PAM is unable to detect enough photoacoustic signals due to the very limited depth of focus (DOF) of excited light and the sharp decrease in energy with increasing sample depth. Here, we design a millimeter-scale UV metalens based on the extended Nijboer-Zernike wavefront-shaping theory which can effectively extend the DOF of a UV-PAM system to about 220 µm while maintaining a good lateral resolution of 1.063 µm. To experimentally verify the performance of the UV metalens, a UV-PAM system is built to achieve the volume imaging of a series of tungsten filaments at different depths. This work demonstrates the great potential of the proposed metalens-based UV-PAM in the detection of accurate diagnostic information for clinicopathologic imaging.

Switchable rotation of metal nanostructures in an intensity chirality-invariant focus field.

Light-induced rotation is a fundamental motion form that is of great significance for flexible and multifunctional manipulation modes. However, current optical rotation by a single optical field is mostly unidirectional, where switchable rotation manipulation is still challenging. To address this issue, we demonstrate a switchable rotation of non-spherical nanostructures within a single optical focus field. Interestingly, the intensity of the focus field is chiral invariant. The rotation switch is a result of the energy flux reversal in front and behind the focal plane. We quantitatively analyze the optical force exerted on a metal nanorod at different planes, as well as the surrounding energy flux. Our experimental results indicate that the direct switchover of rotational motion is achievable by adjusting the relative position of the nanostructure to the focal plane. This result enriches the basic motion mode of micro-manipulation and is expected to create potential opportunities in many application fields, such as biological cytology and optical micromachining.

All-optically controlled holographic plasmonic vortex array for multiple metallic particles manipulation.

Due to the sub-diffraction-limited size and giant field enhancement, plasmonic tweezers have a natural advantage in trapping metallic particles. However, the strict excitation condition makes it difficult to generate an arbitrary plasmonic field in a controllable manner, thus narrowing its practical applications. Here, we propose an all-optical plasmonic field shaping method based on a digital holographic algorithm and generate plasmonic vortex arrays with controllable spot numbers, spatial location, and topological charge. Our experimental results demonstrate that multiple gold particles can be stably trapped and synchronously rotated in the vortex arrays, and the particles' kinestate can be dynamically switched. The proposed holographic plasmonic vortex tweezers are suitable for a broadband particle trapping, and this method can be generalized to other surface electromagnetic waves like Bloch surface wave.

A selective CB2R agonist (JWH133) protects against pulmonary fibrosis through inhibiting FAK/ERK/S100A4 signaling pathways.

BACKGROUND: The combination of the endocannabinoid system (ECS) and the type 2 cannabinoid receptor (CB2R) can activate various signal pathways, leading to distinct pathophysiological roles. This interaction has gained significant attention in recent research on fibrosis diseases. Focal adhesion kinase (FAK) plays a crucial role in regulating signals from growth factor receptors and Integrins. It is also involved in the transformation of fibroblasts into myofibroblasts. This study aims to investigate the impact of the CB2R agonist JWH133 on lung fibrosis and its potential to alleviate pulmonary fibrosis in mice through the FAK pathway. METHODS: The C57 mice were categorized into five groups: control, BLM, BLM + JWH133, BLM + JWH133 + NC, and BLM + JWH133 + FAK groups.JWH133 was administered to mice individually or in conjunction with the FAK vector. After 21 days, pathological changes in mouse lung tissues, inflammatory factor levels, hydroxyproline levels, and collagen contents were evaluated. Moreover, the levels of the FAK/ERK/S100A4 pathway-related proteins were measured. RESULTS: JWH133 treatment decreased inflammatory factor levels, attenuated pathological changes, and reduced extracellular matrix accumulation in the mouse model of bleomycin-induced pulmonary fibrosis; however, these effects were reversed by FAK. JWH133 attenuated fibrosis by regulating the FAK/ERK/S100A4 pathway. CONCLUSIONS: The results presented in this study show that JWH133 exerts a protective effect against pulmonary fibrosis by inhibiting the FAK/ERK/S100A4 pathway.Therefore, JWH133 holds promise as a potential therapeutic target for pulmonary fibrosis.

Human Wharton's jelly-derived mesenchymal stem cells prevent pregnancy loss in a rat by JAK/STAT-mediated immunomodulation.

AIM: Spontaneous abortion (SA) is a multiple-original syndrome with immune imbalance as one of its major risk factors. As Wharton's jelly-mesenchymal stem cells (WJ-MSCs) are considered to be able to prevent abortion, this study aims to explore the currently poorly understood underlining molecular signaling pathways and regulatory mechanisms of WJ-MSCs in pregnancy maintenance. METHODS: Abortion mode is established by subcutaneous injection of bromocriptine in rat on day 9 and abortion prevention is achieved by WJ-MSCs injection via tail vein. WJ-MSCs were cultured with/without the inhibitors of JAK/STAT or NF-κB. The uterus was collected on the 14th day of gestation and the rate of embryo absorption was calculated. The expression of Th1/Th2/Th3 cytokines in decidual, placental tissue, and peripheral blood was analyzed. RESULTS: WJ-MSCs treatment significantly reduced the abortion rate in bromocriptine-treated pregnancy such that it was not significantly different from a normal pregnancy. JAK/STAT inhibition abolished pregnancy preserving effects of WJ-MSCs but NF-κB inhibition did not. The levels of Th1-related cytokines and mRNA levels in the bromocriptine abortion model were significantly higher than the normal pregnancy group and ethanol control group, while levels of the Th2-related cytokines and mRNA levels significantly decreased. WJ-MSCs transfusion into the abortion model restored cytokine profiles such that they were not significantly different from the normal pregnancy group and ethanol control group. JAK/STAT inhibition of WJ-MSCs prevented their effect on cytokine and mRNA levels, but NF-κB inhibition did not. CONCLUSIONS: WJ-MSCs significantly lower the rate of embryo resorption of spontaneous abortion by reducing Th1-related cytokines while increasing Th2 and Th3-related cytokines in JAK/STAT-dependent manner.

Effect evaluation and influencing factor analysis of vaginal carbon dioxide laser in the treatment of stress urinary incontinence.

To evaluate the clinical efficacy of carbon dioxide laser in the treatment of female stress urinary incontinence and analyze the influencing factors. A total of 46 patients with stress urinary incontinence treated in the Affiliated Hospital of Nantong University from March 2021 to August 2022 were included through strict inclusion criteria and exclusion criteria. All patients were treated with transvaginal carbon dioxide laser therapy, and Patient Global Impression of Change (PGI-C) was used to evaluate patients' subjective satisfaction after treatment. The efficacy was evaluated by patient's subjective assessment of leakage, IngelmanSundberg scale, 1-h urine pad test, and international consultation on incontinence questionnaire short form (ICI-Q-SF) before and after treatment, and the adverse reactions after treatment were recorded. The treatment effect was divided into "significant effect group" and "no significant effect group" by subjective satisfaction and post-treatment-related scale evaluation. After laser treatment, patients' subjective symptom improved, the volume of 1-h urine pad test was reduced, and the ICI-Q-SF score was decreased, and the differences were statistically significant (P < 0.05). There was no significant difference in IngelmanSundberg scale before and after treatment (P = 1.00). Multivariate logistic regression analysis showed that pad test volume was significantly correlated with treatment effect (P = 0.007). Transvaginal carbon dioxide laser is a safe and effective method for the treatment of mild to moderate stress urinary incontinence in females. The less severe the urinary leakage, the better the treatment effect.

Development and Validation of a Stable Isotope Dilution Headspace-SPME-GC/MS Method for the Determination of Vanillin in Fragrant Vegetable Oils.

It has been reported that vanillin has been intentionally added to enhance the taste and flavor of low-quality vegetable oils. Therefore, it is crucial to investigate the accurate concentrations of vanillin in three types of fragrant vegetable oils commonly consumed in China. In this study, a method has been developed for the quantification of vanillin in commercial fragrant vegetable oils using the stable isotope dilution assay (SIDA) and headspace-solid-phase microextraction (HS-SPME) coupled with gas chromatography/mass spectrometry (GC/MS). The limit of detection (LOD) and limit of quantification (LOQ) of the analyte were determined to be 20 µg kg-1 and 50 µg kg-1, respectively. The validation study demonstrated that the recoveries ranged from 89% to 101%, with intra-day and inter-day precision being less than 7.46%. A survey of 80 commercially available fragrant vegetable oils was performed using the present method. Vanillin was found to be widely present in fragrant vegetable oils, with sesame oils showing the highest average content (842.6 µg kg-1), followed by rapeseed oils (262.1 µg kg-1) and peanut oils (115.0 µg kg-1). The results indicate that the proposed method is a simple, accurate, and eco-friendly approach for determining the presences of vanillin in fragrant vegetable oils.

Polarization singularities hidden in a deep subwavelength confined electromagnetic field with angular momentum.

Topologies associated with polarization point and line singularities can provide tools for controlling light propagation. By using the Stokes parameter, we demonstrate the emergence of polarization singularities hidden in deep subwavelength confined electromagnetic fields with angular momentum. We show that when the incoming orbital angular momentum is appropriately chosen, highly confined electromagnetic fields with super-diffraction-limited spatial dimensions can be obtained. At the same time, a conversion of orbital to spin angular momentum occurs, leading to a non-trivial topology. Our method provides a platform for developing topological photonics and studying the behavior of polarization singularities under strong focusing.

Controllable transportation of microparticles along structured waveguides by the plasmonic spin-hall effect.

With the nanoscale integration advantage of near field photonics, controllable manipulation and transportation of micro-objects have possessed plentiful applications in the fields of physics, biology and material sciences. However, multifunctional optical manipulation like controllable transportation and synchronous routing by nano-devices are limited and rarely reported. Here we propose a new type of Y-shaped waveguide optical conveyor belt, which can transport and route particles along the structured waveguide based on the plasmonic spin-hall effect. The routing of micro-particles in different branches is determined by the optical force components difference at the center of the Y junction along the two branches of the waveguide. The influence of light source and structural parameters on the optical forces and transportation capability are numerically studied. The results illustrate that the proposed structured waveguide optical conveyor belt can transport the microparticles controllably in different branches of the waveguide. Due to the selective transportation ability of microparticles by the 2D waveguide, our work shows great application potential in the region of on-chip optical manipulation.

Optical singularity assisted method for accurate parameter detection of step-shaped nanostructure in coherent Fourier scatterometry.

Accurate determination of the physical parameters of nanostructures from optical far-field scattering is an important and challenging topic in the semiconductor industry. Here, we propose a novel metrology method to determine simultaneously the height and side-wall angle of a step-shaped silicon nanostructure. By employing an optical singular beam into a typical coherent Fourier scatterometry system, both parameters can be retrieved through analyzing the intensity profile of the far-field scattering pattern. The use of singular beam is shown to be sensitive to slight changes of the parameters of the step. By changing the relative direction between the singularity and structure, the height and side-wall angle can both be retrieved with high precision. This new method is robust, simple, and can provide valuable means for micro-and-nano- metrologies.

Detecting cylindrical vector beams with an on-chip plasmonic spin-Hall metalens.

In recent years, singular optical beams, including optical vortex (OV) beams with phase singularities and cylindrical vector beams (CVBs) with polarization singularities, have brought new degrees of freedom for many applications. Although there have been various microscale devices for OV detection, the detection of CVBs with a microscale device is still a challenge. Here, we propose a new method for detection of CVBs with a designed on-chip plasmonic spin-Hall metalens structure. The focal position of the metalens and the splitting effect of at focus are studied in both an analytical model and numerical simulation. The results demonstrate that the metalens can not only detect different polarization orders of incident CVBs but also have an ability to distinguish radial, azimuthal and other vectorial polarization states under the same order of CVBs. This method has potential applications in compact integrated optical communication and processing systems.

Time-varying orbital angular momentum in tight focusing of ultrafast pulses.

The orbital angular momentum (OAM) of light has important applications in a variety of fields, including optical communication, quantum information, super-resolution microscopic imaging, particle trapping, and others. However, the temporal properties of OAM in ultrafast pulses and in the evolution process of spin-orbit coupling has yet to be revealed. In this work, we theoretically studied the spatiotemporal property of time-varying OAM in the tightly focused field of ultrafast light pulses. The focusing of an incident light pulse composed of two time-delayed femtosecond sub-pulses with the same OAM but orthogonal spin states is investigated, and the ultrafast dynamicsa time delay of OAM variation during the focusing process driven by the spin-orbit coupling is visualized. Temporal properties of three typical examples, including formation, increase, and transformation of topological charge are investigated to reveal the non-uniform evolutions of phase singularities, local topological charges, self-torques, and time-varying OAM per photon. This work could deepen the understanding of spin-orbit coupling in time domain and promote many promising applications such as ultrafast OAM modulation, laser micromachining, high harmonic generation, and manipulation of molecules and nanostructures.

Energy flow inversion in an intensity-invariant focusing field.

Dependence of light intensity on energy flow is the most intuitive presentation of an optical field. This dependence, however, also limits the applications to the interaction of the light field with matter. For further insight into this, we demonstrate a novel case of the optical field, named as the counterintuitive chiral intensity field (CCIF), in the highly focusing situation: the energy flow reverses during the propagation but the intensity distribution pattern is kept approximately invariant. Our results show that, in this process, the mode correlation decreases rapidly while the intensity correlation remains invariant in the focus area. Furthermore, this property is still valid even if the pattern helicity and number of spiral arms are changed. This work deepens the understanding of the relationship between energy flow and field intensity, and it will offer diversified operations in many applications, such as optical micromanipulation, optical fabrication, etc.

A "Double-Locked" and Enzyme/pH-Activated Theranostic Agent for Accurate Tumor Imaging and Therapy.

Theranostic agents for concurrent cancer therapy and diagnosis have begun attracting attention as a promising modality. However, accurate imaging and identification remains a great challenge for theranostic agents. Here, we designed and synthesized a novel theranostic agent H6M based on the "double-locked" strategy by introducing an electron-withdrawing nitro group into 1-position of a pH-responsive 3-amino-ß-carboline and further covalently linking the hydroxamic acid group, a zinc-binding group (ZBG), to the 3-position of ß-carboline to obtain histone deacetylase (HDAC) inhibitory effect for combined HDAC-targeted therapy. We found that H6M can be specifically reduced under overexpressed nitroreductase (NTR) to produce H6AQ, which emits bright fluorescence at low pH. Notably, H6M demonstrated a selective fluorescence imaging via successive reactions with NTR (first "key") and pH (second "key"), and precisely identified tumor margins with a high S/N ratio to guide tumor resection. Finally, H6M exerted robust HDAC1/cancer cell inhibitory activities compared with a known HDAC inhibitor SAHA. Therefore, the NTR/pH-activated theranostic agent provided a novel tool for precise diagnosis and efficient tumor therapy.

Examining industrial air pollution embodied in trade: implications of a hypothetical China-UK FTA.

Very few developed economies have a full free trade agreement (FTA) with China. This study employs one GTAP model and builds an extended environmental multi-region input-output model to investigate a hypothetical China-UK FTA, concerning embodied industrial emissions of SO2, PM2.5, NOX, and NH3. The economic sectors are also classified based on their embodied pollution intensity and trade advantage index under various FTA scenarios. Results show that the UK's GDP and welfare and China's welfare will increase, along with changes in their trade structures. Overall, this FTA brings about larger net impacts on embodied emissions of SO2 than on PM2.5, NOX and NH3, and both countries are net importers of the latter three pollutants. Key sectors such as non-metallic mineral products, chemical products, and agriculture are inclined to become less competitive and less polluting under the FTA. The inclusion of agri-food sectors exhibits slight counteracting effects in general. The findings are of policy importance as they provide insights into how best to target key sectors, seeking a balance between trade development and environmental protection. Supplementary Information: The online version contains supplementary material available at 10.1007/s10668-022-02612-z.