[Land Change Simulation and Grassland Carbon Storage in the Loess Plateau Based on SSP-RCP Scenarios].

Exploring the spatial distribution of land use/coverage (LUCC) and ecosystem carbon reserves in the future of climate change can provide a scientific basis for optimizing the distribution of land resources and formulating social economic sustainable development policies. In this study, we integrated the plaques generating land use simulation (PLUS) model and ecosystem services and weighing comprehensive evaluation (InVEST) model. Based on the CMIP6-based sharing socio-economic path and representative concentration path (SSP-RCP), we evaluated the Loess Plateau for time and space dynamic changes in LUCC and ecosystem carbon reserves, analyzed the impact of driving factors on different regions, and explored the correlation between carbon reserves in various regions. The results showed:① In the future, the three scenarios were similar to the LUCC changes. The area of cultivated land, grassland, and unused land would be reduced to varying degrees, and the construction land had expanded sharply. The increase in the three scenarios was 29.23%-53.56% (SSP126), 34.59%-63.28% (SSP245), and 42.80%-73.27% (SSP585). ② Compared with that in 2020, the carbon reserves of SSP126 sites in 2040 increased by 1.813 8×106 t, and in the remaining scenarios it would continue to decline. By 2060, the grassland carbon reserves in the three scenarios decreased by 13.391×106, 33.548×106, and 85.871×106 t, respectively. ③ From the perspective of space correlation, the carbon reserves of the Loess Plateau were correlated between cities. The difference in future scenarios was not significant. The hotspots were distributed in the middle and north of the research area. There was no obvious cold spot area. ④ The changes in land use were predicted to increase or lose carbon reserves. Forestry, cultivated land, and grassland had more carbon reserves those in than other land types. Increasing their area and restrictions on the conversion of other land types should increase the ecosystem carbon reserves.

Key Role of Asymmetric Photothermal Effect in Selectively Chiral Switching of Plasmonic Dimer Driven by Circularly Polarized Light.

Strong interaction between circularly polarized light and chiral plasmonic nanostructures can enable controllable asymmetric photophysical processes, such as selective chiral switching of a plasmonic nanorod-dimer. Here, we uncover the underlying physics that governs this chiral switching by theoretically investigating the interplay between asymmetric photothermal and optomechanical effects. We find that the photothermally induced local temperature rises could play a key role in activating the dynamic chiral configurations of a plasmonic dimer due to the temperature-sensitive molecular linkages located at the gap region. Importantly, different temperature rises caused by the opposite handedness of light could facilitate selective chiral switching of the plasmonic dimer driven by asymmetric optical torques. Our analyses on the wavelength-dependent selectively chiral switching behaviors are in good agreement with the experimental observations. This work contributes to a comprehensive understanding of the physical mechanism involved in the experimentally designed photoresponsive plasmonic nanosystems for practical applications.

Controllable synthesis of FeMn bimetallic ferrocene-based metal-organic frameworks to boost the catalytic efficiency for removal of organic pollutants.

A series of FeMn bimetallic ferrocene-based metal-organic frameworks (FeMn-Fc-MOFs) with various molar ratios of Fe and Mn (1:9, 2:8, 4:6, 6:4) were successfully synthesized using a simple hydrothermal synthesis method and employed as an efficient activator on persulfate (PS) activation for water decontamination. Characterizations demonstrated that Fe and Mn were smoothly introduced into ferrocene-based MOFs and various molar ratios of Fe:Mn had some influence on crystallinity and surface structure of FeMn-Fc-MOFs. Within 120 min, Fe4Mn6-Fc-MOFs demonstrated the best catalytic activity among the different molar ratios, and acid orange 7(AO7) degradation rate was up to 92.0%. In addition, electrochemical experiments revealed that Fe4Mn6-Fc-MOFs possessed superior electron transfer capability than other FeMn-Fc-MOFs, leading to better catalytic performance. Moreover, quenching tests and electron paramagnetic resonance (EPR) detection indicated that hydroxyl radicals and sulfate radicals were both responsible for AO7 decomposition. Notably, the redox cycle of Fe(II)/Fe(III) and Mn(II)/Mn(IV) was discovered in the Fe4Mn6-Fc-MOFs/PS system, which was considered as the limiting process for the cleavage of the O-O bond in PS to generate active radicals. Ultimately, the Fe4Mn6-Fc-MOFs exhibits an excellent universality and good cycling stability for 5 continuous runs. This paper broadens the application of ferrocene-based MOFs on heterogeneous PS activation in environmental catalysis.

Elucidating the origin mechanism of a morphology-dependent layered double hydroxide catalyst toward organic contaminant oxidation via persulfate activation.

Understanding how the morphology of a layered double hydroxide (LDH)-based catalyst alters its catalytic activity provides an available strategy for the rational design and fabrication of high-efficiency catalysts at a micro-scale. Herein, three nickel-iron layered double hydroxide (NiFe-LDH) catalysts including 2D-plate-like hexagon (P-NiFe-LDH), 2D/3D-flower-like solid sphere (FS-NiFe-LDH), and 2D/3D-flower-like hollow sphere (FH-NiFe-LDH) with regulable oxygen vacancies (OVs) were fabricated via a morphological regulation method of Ostwald ripening. The experimental results demonstrated that the three types of NiFe-LDH exhibited different abilities to activate persulfate (PS) for the abatement of acid orange 7 (AO7) with a sequence of FH-NiFe-LDH > FS-NiFe-LDH > P-NiFe-LDH. Particularly, the FH-NiFe-LDH with a hollow structure exhibited the most considerable activity with the first-order rate constant up to k = 0.02639 min-1, benefiting from the highly accessible surface areas, higher intrinsic activity of the exposed crystal planes, and abundant OVs. Characterizations further confirmed that these properties could profoundly allow for more exposure of active sites and enhance the reactivity of OV-connected Ni or Fe to facilitate electron transfer and generate more reactive radicals, therefore elucidating the morphologic origin of catalytic performance. Based on the quenching experiments, sulfate radicals (SO4·-), hydroxyl radicals (·OH), and oxygen radicals (O2·-) were identified to be involved in the decomposition process. Furthermore, the continuous redox cycle of Ni(II)/Ni(III)/Ni(II) and Fe(II)/Fe(III)/Fe(II) was responsible for the generation of active radicals via activating PS.

Peroxydisulfate activation by LaNiO3 nanoparticles with different morphologies for the degradation of organic pollutants.

A series of LaNiO3 perovskite nanoparticles with different morphologies, such as spheres, rods and cubes, were prepared through co-precipitation and hydrothermal methods, and used as the catalysts for peroxydisulfate (PDS) activation. The physical and chemical characterization of LaNiO3 perovskites was performed, including X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen isotherm absorption (BET), electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). The LaNiO3 with different shapes showed different activities in Acid Orange 7 (AO7) degradation. Sphere-like LaNiO3 exhibited the highest catalytic activity, which is probably due to the largest specific surface area, higher proportion of reductive Ni2+ and the higher electron transfer ability. The radical scavenging experiments and electron paramagnetic resonance (EPR) revealed the production of massive sulfate radicals (SO4•-) and hydroxyl radicals (•OH) during the oxidation. Finally, the possible mechanisms of PDS activation and AO7 degradation were proposed. The prepared LaNiO3 perovskites also showed excellent reusability and stability.

Persulfate activation by ferrocene-based metal-organic framework microspheres for efficient oxidation of orange acid 7.

Ferrocene-based metal-organic framework with different transition metals (M-Fc-MOFs, M = Fe, Mn, Co) was synthesized by a simple hydrothermal method and used as a heterogeneous catalyst for persulfate activation. The samples were characterized by X-ray diffraction, transmission electron microscopy, X-ray electron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Meanwhile, the influences of factors such as catalyst dosage, persulfate concentration, and pH on the degradation of acid orange 7 (AO7) were studied in detail. The results showed that hollow cobalt-based ferrocenyl metal-organic framework microspheres (Co-Fc-MOFs) exhibited the best catalytic performance, which is closely related to the synergy of Fc/Fc+ and Co(II)/Co(III) cycles in persulfate activation. Free radical quenching studies indicated that both sulfate and hydroxyl appeared to contribute to the degradation of AO7.

Plasmonic Nanosensors with Extraordinary Sensitivity to Molecularly Enantioselective Recognition at Nanoscale Interfaces.

Molecular chirality recognition plays a pivotal role in chiral generation and transfer in living systems and makes important contribution to the development of diverse applications spanning from chiral separation to soft nanorobots. To detect chirality recognition, most of the molecular sensors described to date are based on the design and preparation of the host-guest complexation with chromophore or fluorophore at the reporter unit. Nevertheless, the involved tedious procedures and complicated chemical syntheses hamper their practical applications. Here, we report the plasmonically chiroptical detection of molecular chirality recognition without the need for a chromophore or fluorophore unit. This facile methodology is based on plasmonic nanotransducers that can convert molecular chirality recognitions occurring at nanoscale interfaces into asymmetrically amplified plasmonic circular dichroism readouts, enabling enantiospecific recognition and quantitative determination of the enantiomeric excess of small amino acids. Importantly, such a plasmon-based chirality sensing shows 102-103 amplification in the plasmonic circular dichroism signals from the detections of racemate and near-racemate of molecular analysts, demonstrating an extraordinary sensitivity to the host-guest enantioselective interactions. Furthermore, with advantages of easy-processing, cost-effective, and specific to interfacial molecular chirality, our chiroptical sensing scheme could hold considerable promise toward applications of enantioselective high-throughput screening in biology, stereochemistry, and pharmaceutics.

Nonlinear Amplification of Chirality in Self-Assembled Plasmonic Nanostructures.

Molecular chirality transfer and amplification is at the heart of the fundamental understanding of chiral origin and fabrication of artificial chiral materials. We investigate here the nonlinear amplification effect in the chiral transfer from small molecules to assembled plasmonic nanoparticles. Our results show clearly a recognizable nonlinear behavior of the electronic and plasmonic circular dichroism activities, demonstrating the validity of the "majority-rules" principle operating in both the three-dimensional interface-confined molecularly chiral environment and the assembled plasmonic nanoparticles. Such twin "majority-rules" effects from the self-assembled organic-inorganic nanocomposite system have not been reported previously. By establishing a direct correlation between the dynamic template of the molecularly chiral environment and the nonlinear chiral amplification in the nanoparticle assemblies, this study may provide an insightful understanding of the hierarchical and cooperative chiral information transfer from molecular levels to nanoscales.

Vector Exceptional Points with Strong Superchiral Fields.

Exceptional points (EPs), branch points of complex energy surfaces at which eigenvalues and eigenvectors coalesce, are ubiquitous in non-Hermitian systems. Many novel properties and applications have been proposed around the EPs. One of the important applications is to enhance the detection sensitivity. However, due to the lack of single-handed superchiral fields, all of the proposed EP-based sensing mechanisms are only useful for the nonchiral discrimination. Here, we propose theoretically and demonstrate experimentally a new type of EP, which is called a radiation vector EP, to fulfill the homogeneous superchiral fields for chiral sensing. This type of EP is realized by suitably tuning the coupling strength and radiation losses for a pair of orthogonal polarization modes in the photonic crystal slab. Based on the unique modal-coupling property at the vector EP, we demonstrate that the uniform superchiral fields can be generated with two beams of lights illuminating the photonic crystal slab from opposite directions. Thus, the designed photonic crystal slab, which supports the vector EP, can be used to perform surface-enhanced chiral detection. Our findings provide a new strategy for ultrasensitive characterization and quantification of molecular chirality, a key aspect for various bioscience and biomedicine applications.

Recognition of chiral zwitterionic interactions at nanoscale interfaces by chiroplasmonic nanosensors.

The ability to detect chiral molecules renders plasmonic nanosensors as promising tools for the study of chirality phenomena in living systems. Using gold nanorod based plasmonic nanosensors, we investigated here typically chiral zwitterionic electrostatic (Zw-Es) and hydrogen-bonding (Hb) interactions occurring via amine and carboxylic groups at nanoscale interfaces in aqueous solutions. Our results reveal that the plasmonic circular dichroism responses of the nanosensors can have both conformational sensitivity and chiral selectivity to the interfacial molecular interactions. Such a dual function of the plasmonic nanosensors enables a new chiroptical way to differentiate between chiral Zw-Es and Hb interactions, to monitor the transformation between these two interaction forces, and particularly to recognize homochiral Zw-Es interactions in solution. Together with the surface enhanced Raman scattering (SERS) technique, this plasmonic CD based biosensing could have important values for the insightful understanding of chirality-dependent molecular recognition in biological and pharmaceutical systems.

Amplification of the molecular chiroptical effect by low-loss dielectric nanoantennas.

We report here the chiroptical amplification effect occurring in the hybrid systems consisting of chiral molecules and Si nanostructures. Under resonant excitation of circularly polarized light, the hybrid systems show strong CD induction signals at the optical frequency, which arise from both the electric and magnetic responses of the Si nanostructures. More interestingly, the induced CD signals from Si-based dielectric nanoantennas are always larger than that from Au-based plasmonic counterparts. The related physical origin was disclosed. Furthermore, compared to the Au-based high-loss plasmonic nanoantennas, Si-based low-loss structures would generate negligible photothermal effect, which makes Si nanoantennas an optimized candidate to amplify molecular CD signals with ultralow thermal damage. Our findings may provide a guideline for the design of novel chiral nanosensors, which are applicable in the fields of biomedicine and pharmaceutics.

A giant chiroptical effect caused by the electric quadrupole.

Recently, there has been great interest in studying ultrasensitive detection and characterization of biomolecules using plasmonic particles, because they are of considerable importance in biomedical science and pharmaceutics. So far, all the theories on plasmon-induced circular dichroism (CD) have been based on the dipole approximation; the electric quadrupolar contribution is generally considered to be relatively small and neglected. Here we demonstrate that the electric quadrupolar contribution not only cannot be ignored, but it also plays a key role in many cases. Particularly, for the chiral medium that possesses preferential molecular orientations and is located at the hotspot of plasmonic nanostructures, the plasmonic CD strength contributed by molecular electric quadrupoles (EQs) can be two orders of magnitude higher than that contributed by molecular electric/magnetic dipoles. Unlike the case of the dipole approximation, molecular EQ associated plasmonic CD activity appears mainly at the plasmonic resonance absorptions that facilitate the optically enhanced near-field with steep electric field gradients, and is correlated with the boosted emission rate of a molecular EQ. Based on such physical understandings, we can design nanostructures to realize a giant chiroptical effect using the EQ contribution according to the requirements, which provide a new strategy for ultrasensitive detection and quantification of molecular chirality.

Plasmon-induced strong interaction between chiral molecules and orbital angular momentum of light.

Whether or not chiral interaction exists between the optical orbital angular momentum (OAM) and a chiral molecule remains unanswered. So far, such an interaction has not been observed experimentally. Here we present a T-matrix method to study the interaction between optical OAM and the chiral molecule in a cluster of nanoparticles. We find that strong interaction between the chiral molecule and OAM can be induced by the excitation of plasmon resonances. An experimental scheme to observe such an interaction has been proposed. Furthermore, we have found that the signal of the OAM dichroism can be either positive or negative, depending on the spatial positions of nanocomposites in the cross-sections of OAM beams. The cancellation between positive and negative signals in the spatial average can explain why the interaction has not been observed in former experiments.

Plasmonic polymers with strong chiroptical response for sensing molecular chirality.

We report on the chiroptical transfer and amplification effect observed in plasmonic polymers consisting of achiral gold nanorod monomers linked by cysteine chiral molecules in an end-to-end fashion. A new strategy for controlling the hot spots based circular dichroism (CD)-active sites in plasmonic polymers was developed to realize tailored and reproducible chiroptical activity in a controlled way. We showed that by regulating the bond angles between adjacent nanorods and the degree of polymerization in the linear plasmonic polymer, weak molecular chirality in the ultraviolet spectral region can be amplified by more than two orders of magnitude via the induced CD response in the visible/near infrared region. We demonstrate that this plasmonic polymer can be used to provide not only the Raman "fingerprint" information for identifying the molecular identity but also the CD signatures for (i) resolving the enantiomeric pairs of cysteine molecules at a small quantity level, and (ii) quantifying the enantiomeric purity of the chiral analytes. Chiral analyses by chiroptically responsive plasmonic polymers may find important applications in bioscience and biomedicine.

Distinct kinetics of molecular gelation in a confined space and its relation to the structure and property of thin gel films.

Thin films of molecular gels formed in a confined space have potential applications in transdermal delivery, artificial skin, molecular electronics, etc. The microstructures and properties of thin gel films can be significantly different from those of their bulk counterparts. However, so far a comprehensive understanding of the effects of spatial confinement on the molecular gelation kinetics, fiber network structure and related mechanical properties is still lacking. In this work, using rheological techniques, we investigated the effect of one-dimensional confinement on the formation kinetics of fiber networks in the molecular gelation process. Fractal analyses of the kinetic information in terms of an extended Dickinson model enabled us to describe quantitatively the distinct kinetic signature of molecular gelation. The structural features derived from gelation kinetics support well the fractal patterns of the fiber networks acquired by optical and electron microscopy. With the kinetics-structure correlation, we can gain an in-depth understanding of the confinement-induced differences in the structure and consequently the mechanical properties of a model molecular gelling system. Particularly, the confinement induced structural transition, from a three-dimensional, dense and compact spherulitic network composed of highly branched fibers to a quasi-two-dimensional sparse spherulitic network composed of less branched fibers and entangled fibrils at the boundary areas, renders a gel film to become less stiff but more ductile. Our study suggests here a new strategy of engineering the fiber network microstructure to achieve functional gel films with unusual but useful properties.

Giant circular dichroism enhancement and chiroptical illusion in hybrid molecule-plasmonic nanostructures.

Recently, there are great interest in studying the interaction between chiral molecules and plasmonic particles, because a weak circular dichroism (CD) signal in the ultraviolet (UV) region from chiral molecules can be both enhanced and transferred to the visible wavelength range by using plasmonic particles. Thus, ultrasensitive probe of tiny amounts of chiral substance by CD are worth waiting for. Here we present another way to strongly enhance CD of chiral molecules by using plasmonic particle cluster, which need not transfer to the visible wavelength. The method to calculate CD of chiral molecules in nanosphere clusters has been developed by means of multiple scattering of electromagnetic multipole fields. Our calculated results show that 2 orders of magnitude CD enhancement in the UV region for chiral molecules can be realized. Such a CD enhancement is very sensitive to the cluster structure. The cluster structure can cause chiroptical illusion in which a mirror symmetry in the CD spectra of opposite enantiomeric molecules is broken. The correction of quantum size effect on the phenomenon has also been considered. Our findings open up an alternative avenue for the ultrasensitive detection and illusion of chiral information.

Giant optical activity from the radiative electromagnetic interactions in plasmonic nanoantennas.

We fabricate the linear chains of twisted gold nanorods by a facile chiral molecular templating method. In such a chiral plasmonic system, particle-particle separation distances are in the order of the light wavelength and are much larger than the sizes of individual particles. As a result, the inter-particle interactions in this chiral system are mediated mainly by a relatively weak far-field plasmonic coupling, rather than a strong near-field coupling. However, such a chiral system of twisted gold nanorods show a huge surface plasmon based circular dichroism response, with the highest anisotropy factor around 0.027. This is in contrast to the previous studies in which near-field plasmonic coupling is an indispensable prerequisite to obtain strong optical activity from a chiral plasmonic nanostructure. Our study demonstrates here an alternative strategy for achieving huge chiroptical response of a chiral plasmonic nanostructure based on far-field, radiative electromagnetic interactions of metallic nanoparticles. Theoretical simulations show a satisfactory agreement with the experimental results. This study may provide more flexible ways to design chiral plasmon nanostructures with strong CD responses for various applications.

From kinetic-structure analysis to engineering crystalline fiber networks in soft materials.

Understanding the role of kinetics in fiber network microstructure formation is of considerable importance in engineering gel materials to achieve their optimized performances/functionalities. In this work, we present a new approach for kinetic-structure analysis for fibrous gel materials. In this method, kinetic data is acquired using a rheology technique and is analyzed in terms of an extended Dickinson model in which the scaling behaviors of dynamic rheological properties in the gelation process are taken into account. It enables us to extract the structural parameter, i.e. the fractal dimension, of a fibrous gel from the dynamic rheological measurement of the gelation process, and to establish the kinetic-structure relationship suitable for both dilute and concentrated gelling systems. In comparison to the fractal analysis method reported in a previous study, our method is advantageous due to its general validity for a wide range of fractal structures of fibrous gels, from a highly compact network of the spherulitic domains to an open fibrous network structure. With such a kinetic-structure analysis, we can gain a quantitative understanding of the role of kinetic control in engineering the microstructure of the fiber network in gel materials.

Controlling nanoparticle formation via sizable cages of supramolecular soft materials.

We present a new generic strategy to fabricate nanoparticles in the "cages" within the fibrous networks of supramolecular soft materials. As the cages can be acquired by a design-and-production manner, the size of nanoparticles synthesized within the cages can be tuned accordingly. To implement this idea, both selenium and silver were chosen for the detailed investigation. It follows that the sizes of selenium and silver nanoparticles can be controlled by tuning the pore size of the fiber networks in the material. When the concentration of the gelator is high enough, monodisperse nanoparticles can be prepared. More interestingly, the morphology of the nanoparticles can be altered: silver disks can be formed when the concentrations of both the gelator and silver nitrate are sufficiently low. As the fiber network serves as a physical barrier and semisolid support for the nanoparticles, the stability in the aqueous media and the ease of application of these nanoparticles can be substantially enhanced. This robust surfactant-free approach will not only allow the controlled fabrication of nanoparticles, but also can be applied to the fabrication of composite materials for robust applications.

Nanoengineering of a biocompatible organogel by thermal processing.

The formation of most organogels requires the compatibility of both the gelator and solvent. It is very desirable if the rheological properties of a gel can be manipulated to achieve the desired performance. In this paper, a novel organogel was developed and its rheological properties and fiber network were engineered by controlling the thermal processing conditions. The gel was formed by the gelation of 12-hydroxystearic acid as a gelator in benzyl benzoate. It was observed that the degree of supercooling for gel formation has a significant effect on the rheological properties and fiber network structure. By increasing supercooling, the elasticity of the gel was enhanced, and the correlation length of the fibers was shortened, leading to the formation of denser fiber networks. The good biocompatibility of both the gelator and solvent makes this gel a promising vehicle for a variety of bioapplications such as controlled transdermal drug release and in vivo tissue repair.