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Chlorophyll (Chl) catabolism and anthocyanin synthesis play pivotal roles in determining the final skin color of fruits during maturation. However, in peach ( Prunus persica ) fruit, the regulatory mechanism governing skin color, especially the Chl catabolism, remains largely elusive. In this study, we identified ten Chl catabolic genes (CCGs), with PpSGR emerging as a key regulator in Chl degradation in peaches. Furthermore, a NAC-like, activated by AP3/P1 (NAP) transcription factor (TF), PpNAP4, was identified as a positive modulator of Chl breakdown. PpNAP4 induced the expression of PpSGR and other CCGs, including PpPPH , PpPAO , and PpTIC55-2 , by directly binding to their promoters. Overexpression of PpNAP4 resulted in a heightened expression of these genes and accelerated Chl degradation. Notably, PpNAP4 also positively regulated the expression of PpANS and PpMYB10.1 , one key structural gene and a core transcriptional regulator of anthocyanin synthesis, thereby contributing to fruit coloration. In summary, our findings elucidate that PpNAP4 serves as a pivotal regulator in determining the final skin color of peach by orchestrating Chl degradation and anthocyanin accumulation through direct activation of multiple CCGs and anthocyanin related genes.

As an emerging biomedical material, wound dressings play an important therapeutic function in the process of wound healing. It can provide an ideal healing environment while protecting the wound from a complex external environment. A hydrogel wound dressing composed of tilapia skin gelatin (Tsg) and fucoidan (Fuc) was designed in this article to enhance the microenvironment of wound treatment and stimulate wound healing. By mixing horseradish peroxidase (HRP), hydrogen peroxide (H 2 O 2 ), tilapia skin gelatin-tyramine (Tsg-Tyr), and carboxylated fucoidan-tyramine in agarose (Aga), using the catalytic cross-linking of HRP/H 2 O 2 and the sol-gel transformation of Aga, a novel gelatin-fucoidan (TF) double network hydrogel wound dressing was constructed. The TF hydrogels have a fast and adjustable gelation time, and the addition of Aga further enhances the stability of the hydrogels. Moreover, Tsg and Fuc are coordinated with each other in terms of biological efficacy, and the TF hydrogel demonstrated excellent antioxidant properties and biocompatibility in vitro . Also, in vivo wound healing experiments showed that the TF hydrogel could effectively accelerate wound healing, reduce wound microbial colonization, alleviate inflammation, and promote collagen deposition and angiogenesis. In conclusion, TF hydrogel wound dressings have the potential to replace traditional dressings in wound healing.

Förster resonance energy transfer (FRET)-based homogeneous immunoassay obviates tedious washing steps and thus is a promising approach for immunoassays. However, a conventional FRET-based homogeneous immunoassay operating in the visible region is not able to overcome the interference of complex biological samples, thus resulting in insufficient detection sensitivity and poor accuracy. Here, we develop a near-infrared (NIR)-to-NIR FRET platform (Ex = 808 nm, Em = 980 nm) that enables background-free high-throughput homogeneous quantification of various biomarkers in complex biological samples. This NIR-to-NIR FRET platform is portable and easy to operate and is mainly composed of a high-performance NIR-to-NIR FRET pair based on lanthanide-doped nanoparticles (LnNPs) and a custom-made microplate reader for readout of NIR luminescence signals. We demonstrate that this NIR-to-NIR FRET platform is versatile and robust, capable of realizing highly sensitive and accurate detection of various critical biomarkers, including small molecules (morphine and 1,25-dihydroxyvitamin D), proteins (human chorionic gonadotropin), and viral particles (adenovirus) in unprocessed complex biological samples (urine, whole blood, and feces) within 5-10 min. We expect this NIR-to-NIR FRET platform to provide low-cost healthcare for populations living in resource-limited areas and be widely used in many other fields, such as food safety and environmental monitoring.

The technology of liquid organic hydrogen carriers presents great promise for large-scale hydrogen storage. Nevertheless, the activation of inert C(sp 3 )-H bonds in hydrocarbon carriers poses formidable challenges, resulting in a sluggish dehydrogenation process and necessitating high operating temperatures. Here, we break the shackles of C-H bond activation under visible light irradiation by fabricating subnanometer Pt clusters on defective Ce-Zr solid solutions. We achieved an unprecedented hydrogen production rate of 2601 mmol g cat. -1 h -1 (turnover frequency >50,000 mol H2 mol Pt -1 h -1 ) from cyclohexane, surpassing the most advanced thermo- and photocatalysts. By optimizing the temperature-dominated hydrogen transfer process, achievable by harnessing hitherto wasted infrared light in sunlight, an astonishing 56% apparent quantum efficiency and a 5.2% solar-to-hydrogen efficiency are attained at 353 K. Our research stands as one of the most effective photocatalytic processes to date, holding profound practical significance in the utilization of solar energy and the exploitation of alkanes.

Polymer waveguide devices have attracted increasing interest in several rapidly developing areas of broadband communications since they are easily adaptable to on-chip integration and promise low propagation losses. As a key member of the waveguide gain medium, lanthanide doped nanoparticles have been intensively studied to improve the downconversion luminescence. However, current research efforts are almost confined to erbium-doped nanoparticles and amplifiers operating at the C-band; boosting the downconversion luminescence of Tm 3+ for S-band optical amplification still remains a challenge. Here we report a Tb 3+ -induced deactivation control to enhance Tm 3+ downconversion luminescence in a stoichiometric Yb lattice without suffering from concentration quenching. We also demonstrate their potential application in an S-band waveguide amplifier and record a maximum optical gain of 18 dB at 1464 nm. Our findings provide valuable insights into the fundamental understanding of deactivation-controlled luminescence enhancement and open up a new avenue toward the development of an S-band polymer waveguide amplifier with high gain.

Polymer-stabilized liquid crystals (PSLCs) are important electrically switchable materials due to their superior electro-optical properties. Nevertheless, it remains a formidable challenge to balance PSLCs' instant electro-optical performance and long-term durability due to their relatively low polymer content and the related sensitivity to external force. Herein, we demonstrate the possibility of regulating the polymer network structure in PSLCs via reversible addition-fragmentation chain transfer (RAFT) polymerization reactions of acrylate monomers with a chain transfer agent (CTA). By controlling the concentration of CTA and conditions of photopolymerization, the kinetics of the polymerization reaction can be modified. Compared to conventional free-radical (FR) polymerization, the reduced chain growth rate leads to sufficient chain relaxation, reorientation of liquid crystal (LC) directors, and alleviation of shrinkage stresses in the RAFT polymerization process. This in turn produces an ordered polymer network structure in the vertical direction and a uniform distribution in the horizontal plane. As a result, the PSLC network presents increased elasticity with a lower hysteresis effect and greatly improved durability. Our research offers insightful guidance for the fine-tuning of polymer network structures to prepare advanced LC/polymer composite structures with outstanding performances.

Wastewater-based epidemiology (WBE) has been utilized to track community infections of Coronavirus Disease 2019 (COVID-19) by detecting RNA of the severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), within samples collected from wastewater. The correlations between community infections and wastewater measurements of the RNA can potentially change as SARS-CoV-2 evolves into new variations by mutating. This study analyzed SARS-CoV-2 RNA, and indicators of human waste in wastewater from two sewersheds of different scales (University of Miami (UM) campus and Miami-Dade County Central District wastewater treatment plant (CDWWTP)) during five internally defined COVID-19 variant dominant periods (Initial, Pre-Delta, Delta, Omicron and Post-Omicron wave). SARS-CoV-2 RNA quantities were compared against COVID-19 clinical cases and hospitalizations to evaluate correlations with wastewater SARS-CoV-2 RNA. Although correlations between documented clinical cases and hospitalizations were high, prevalence for a given wastewater SARS-CoV-2 level varied depending upon the variant analyzed. The correlative relationship was significantly steeper (more cases per level found in wastewater) for the Omicron-dominated period. For hospitalization, the relationships were steepest for the Initial wave, followed by the Delta wave with flatter slopes during all other waves. Overall results were interpreted in the context of SARS-CoV-2 virulence and vaccination rates among the community.

Lanthanide upconversion nanoparticles (UCNPs) have been extensively explored as biomarkers, energy transducers, and information carriers in wide-ranging applications in areas from healthcare and energy to information technology. In promoting the brightness and enriching the functionalities of UCNPs, core-shell structural engineering has been well-established as an important approach. Despite its importance, a strong limiting issue has been identified, namely, cation intermixing in the interfacial region of the synthesized core-shell nanoparticles. Currently, there still exists confusion regarding this destructive phenomenon and there is a lack of facile means to reach a delicate control of it. By means of a new set of experiments, we identify and provide in this work a comprehensive picture for the major physical mechanism of cation intermixing occurring in synthesis of core-shell UCNPs, i.e., partial or substantial core nanoparticle dissolution followed by epitaxial growth of the outer layer and ripening of the entire particle. Based on this picture, we provide an easy but effective approach to tackle this issue that enables us to produce UCNPs with highly boosted optical properties.

Stable organic radicals, which possess half-filled orbitals in the vicinity of the Fermi energy, are promising candidates for electronic devices. In this Letter, using a combination of scanning-tunneling-microscopy-based break junction (STM-BJ) experiments and quantum transport theory, a stable fluorene-based radical is investigated. We demonstrate that the transport properties of a series of fluorene derivatives can be tuned by controlling the degree of localization of certain orbitals. More specifically, radical 36-FR has a delocalized half-filled orbital resulting in Breit-Wigner resonances, leading to an unprecedented conductance enhancement of 2 orders of magnitude larger than the neutral nonradical counterpart ( 36-FOH ). In other words, conversion from a closed-shell fluorene derivative to the free radical in 36-FR opens an electron transport path which massively enhances the conductance. This new understanding of the role of radicals in single-molecule junctions opens up a novel design strategy for single-molecule-based spintronic devices.

The intrinsic nonstretchable feature of magnetic films has significantly limited its applications on wearable high-frequency devices. Recent studies have proved that the wrinkling surface structure based on the growth on polydimethylsiloxane (PDMS) is an effective route to obtain stretchable magnetic films. However, it is still a great challenge to simultaneously achieve a desired stretchability and stretching-insensitive high-frequency properties of magnetic films. Herein, we reported a convenient method to stabilize the high-frequency properties of stretchable magnetic films by depositing magnetic ribbon-patterned films on prestrain PDMS membranes. The ribbon-patterned wrinkling CoFeB films have far fewer cracks than the continuous film, which indicates a nice strain-relief effect and thus confers the stability of high-frequency properties for the films under stretching. However, the wrinkle bifurcation and the uneven thickness at the ribbon edge could adversely affect the stability of its high-frequency properties. The 200 μm wide ribbon-patterned film shows the best stretching-insensitive behaviors and maintains a constant resonance frequency of 3.17 GHz at strain from 10% to 25%. Moreover, a good repeatability has been demonstrated by performing thousands of stretch-release cycles, which did not significantly deteriorate its performances. The ribbon-patterned wrinkling CoFeB films with excellent stretching-insensitive high-frequency properties are promising for application in flexible microwave devices.

Nanotechnology is considered as an emerging effective means to augment plant photosynthesis. However, there is still a lot of work to be done in this field. Here, we applied the upconversion nanoparticles (UCNPs) on lettuce leaves and found that the UCNPs were able to transport into the lettuce body and colocalize with the chloroplasts. It was proved that UCNPs could harvest the near-infrared light of sunlight and increase the electron transfer rate in the photosynthesis process, thus increasing the photosynthesis rate. The gene expression analysis showed that more than 90% of gene expression in photosynthesis was upregulated. After spraying the UCNP solution on the leaves of lettuce and placing the lettuce under sunlight for 1 week, the wet/dry weight of the leaves increased by 53.33% and 45.71%, respectively. This nanoengineering of light-harvesting UCNPs may have great potential for applications in agriculture.

Severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) in wastewater has been used to track community infections of coronavirus disease-2019 (COVID-19), providing critical information for public health interventions. Since levels in wastewater are dependent upon human inputs, we hypothesize that tracking infections can be improved by normalizing wastewater concentrations against indicators of human waste [Pepper Mild Mottle Virus (PMMoV), β-2 Microglobulin (B2M), and fecal coliform]. In this study, we analyzed SARS-CoV-2 and indicators of human waste in wastewater from two sewersheds of different scales: a University campus and a wastewater treatment plant. Wastewater data were combined with complementary COVID-19 case tracking to evaluate the efficiency of wastewater surveillance for forecasting new COVID-19 cases and, for the larger scale, hospitalizations. Results show that the normalization of SARS-CoV-2 levels by PMMoV and B2M resulted in improved correlations with COVID-19 cases for campus data using volcano second generation (V2G)-qPCR chemistry ( r s = 0.69 without normalization, r s = 0.73 with normalization). Mixed results were obtained for normalization by PMMoV for samples collected at the community scale. Overall benefits from normalizing with measures of human waste depend upon qPCR chemistry and improves with smaller sewershed scale. We recommend further studies that evaluate the efficacy of additional normalization targets., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The understanding and control of the spin-orbit torque (SOT) are central to antiferromagnetic spintronics. Despite the fact that a giant SOT efficiency has been achieved in numerous materials, its efficient tuning in a given material has not been established. Materials with magnetic phase transitions (MPTs) offer a new perspective, as the SOT efficiency may vary significantly for the different magnetic orderings across the transition, and the transition itself can be readily tuned by various control parameters. This work reports that the SOT efficiency of a FeRh-based perpendicular magnetized heterostructure can be significantly tuned by varying the temperature across the MPT. The SOT efficiency exhibits a temperature hysteresis associated with the first-order nature of the MPT, and its value in the ferromagnetic phase is seen to be enhanced by ∼450%, simply by a lowering of temperature to drive FeRh into the antiferromagnetic phase. Furthermore, current-induced magnetization switching can be achieved without an assistant magnetic field for both ferromagnetic and antiferromagnetic FeRh, with a low critical switching current density for the latter. These results not only directly establish FeRh as an efficient spin generator but also present a strategy to dynamically tune SOT via varying the temperature across MPTs.

The early-stage repair of bone injuries dominated by the inflammatory phase is significant for successful bone healing, and the phenotypic transition of macrophages in the inflammatory phase plays indispensable roles during the bone healing process. The goal of this paper is to design a microRNA delivery nanocarrier for strictly temporal guidance of the polarization of macrophages by the sequential delivery of different microRNAs. The results showed that microRNA nanocarriers, synthesized through free radical polymerization, could be internalized by macrophages with about a cellular uptake efficiency of 80%, and the sequential delivery of microRNA-155 nanocarriers and microRNA-21 nanocarriers proved, for the first time, that it could promote an efficient and timely switch from the M1 to the M2 phenotype along the time point of bone tissue repair. The strategy proposed in this paper holds potential for controlling sequential M1-to-M2 polarization of macrophages, which provides another perspective for the treatment of bone tissue regeneration., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

We demonstrated a convenient method via applying uniaxial tensile strains to continuously tune the high-frequency properties of flexible magnetic films. CoFeB films were magnetron sputtered onto prestretched polydimethylsiloxane (PDMS) membranes. They exhibit a self-assembled periodic wrinkling surface structure because of the large mismatch of Young's moduli between the elastomeric PDMS substrates and the metal layers. The wrinkling morphology and the residual tensile stress caused by the Poisson effect can be continuously tuned by a uniaxial stretching strain less than the growth prestrain, which consequently results in changes in high-frequency performance. The initial permeability and the ferromagnetic resonance frequency of flexible CoFeB thin films can be monotonously tuned in wide ranges of about hundreds and 1 GHz, respectively. A good repeatability over thousands of stretching-relaxing cycles has been demonstrated without any obvious reduced high-frequency properties. This flexible CoFeB films with excellent stretching-tunable high-frequency performances are promising for application in flexible and tunable microwave devices.

A radical-based asymmetric olefin difunctionalization strategy for rapidly forging all-carbon quaternary stereocenters α to diverse azaarenes is reported. Under cooperative photoredox and chiral Brønsted acid catalysis, cyclopropylamines with α-branched 2-vinylazaarenes can undergo a sequential two-step radical process, furnishing various valuable chiral azaarene-substituted cyclopentanes. The use of the rigid and confined C 2 -symmetric imidodiphosphoric acid catalysts achieves high enantio- and diastereo-selectivities for these asymmetric [3 + 2] cycloadditions.

We demonstrate an opto-thermomechanical (OTM) nanoprinting method that allows us not only to additively print nanostructures with sub-100 nm accuracy but also to correct printing errors for nanorepairing under ambient conditions. Different from other existing nanoprinting methods, this method works when a nanoparticle on the surface of a soft substrate is illuminated by a continuous-wave (cw) laser beam in a gaseous environment. The laser heats the nanoparticle and induces a rapid thermal expansion of the soft substrate. This thermal expansion can either release a nanoparticle from the soft surface for nanorepairing or transfer it additively to another surface in the presence of optical forces for nanoprinting with sub-100 nm accuracy. Details of the printing mechanism and parameters that affect the printing accuracy are investigated. This additive OTM nanoprinting technique paves the way for rapid and affordable additive manufacturing or 3D printing at the nanoscale under ambient conditions.

In view of the size and hydrophilicity of glycopeptides, materials having suitable channels (size-exclusion) and strong hydrophilic surface (hydrophilic interaction) are preferred to enrich the glycopeptides in biological samples. Metal-organic frameworks (MOFs) are good candidates. However, their smaller microporous channels and low chemical stability have limited the application. Herein, a facile strategy was established to construct hydrophilic mesoporous MOF via synergistic etching and surface functionalization by using phytic acid (PA). Besides, polyvinylpyrrolidone (PVP) was added during MOF synthesis to enhance the water stability of the MOF. Owing to the expanded hydrophilic mesoporous channels, the PA-modified Ce-MOF effectively and selectively captured 422 glycopeptides from 155 glycoproteins in tryptic digests of human serum (2 μL). The present work sheds light on the easy fabrication of hydrophilic mesoporous materials, and this established material holds unique advantages for glycopeptides analysis in biological samples.

Nitric oxide (NO) can play both prosurvival and prodeath roles in photodynamic therapy (PDT). The generation efficiency of peroxynitrite anions (ONOO - ), by NO and superoxide anions (O 2 •- ), significantly influenced the outcome. Reports indicated that such efficiency is closely related to the distance between NO and O 2 •- . Thus, in this manuscript, l-arginine (Arg) ethyl ester-modified zinc phthalocyanine (Arg-ZnPc) was designed and synthesized as a photosensitizer (PS) and NO donor. Post light irradiation, the guanido of Arg-ZnPc can be effectively oxidized by the generated reactive oxygen species (ROS) in the PDT process to release NO. Such a strategy could ensure O 2 •- and NO generation in the same place at the same time to guarantee effective ONOO - formation. In addition, NO has other multiple synergistic cancer treatment functions, including tumor tissue vasodilatation for drug extravasation promotion, P-glycoprotein (P-gp) downregulation for drug efflux inhibition, and glutathione depletion for cancer cell endogenous antioxidant defense destruction. In vitro and in vivo results indicated that the effective ONOO - formation and multiple functions of Arg-ZnPc could synergistically enhance its PDT activity and ensure satisfactory cancer treatment outcome.

The ability of band offsets at multiferroic/metal and multiferroic/electrolyte interfaces in controlling charge transfer and thus altering the photoactivity performance has sparked significant attention in solar energy conversion applications. Here, we demonstrate that the band offsets of the two interfaces play the key role in determining charge transport direction in a downward self-polarized BFO film. Electrons tend to move to BFO/electrolyte interface for water reduction. Our experimental and first-principle calculations reveal that the presence of neodymium (Nd) dopants in BFO enhances the photoelectrochemical performance by reduction of the local electron-hole pair recombination sites and modulation of the band gap to improve the visible light absorption. This opens a promising route to the heterostructure design by modulating the band gap to promote efficient charge transfer.

The perfect energy level overlap of 2 H 11/2 , 4 S 3/2 , and 4 F 9/2 in Er 3+ ions with those of 5 F 3 , 5 F 4 / 5 S 2 , and 5 F 5 in adjacently codoped Ho 3+ ions allows efficient interenergy transfer. Therefore, in addition to routine activators, Er 3+ or Ho 3+ can further act as sensitizers to transfer the upconverted energy to nearby Ho 3+ or Er 3+ , resulting in enhanced upconversion luminescence due to the emission overlap. Proper codoping of Er 3+ /Ho 3+ or Ho 3+ /Er 3+ obviously elevates the maximum doping concentration (thus producing additional upconverted photons) to a level higher than that causing luminescence quenching and significantly enhances upconversion emissions compared with those of singly Er 3+ or Ho 3+ -doped host materials. Indeed, the so-far strongest red upconversion emission under 1532 nm excitation was obtained in LiYF 4 :Er/Ho@LiYF 4 nanoparticles and Ho 3+ -sensitized Er 3+ upconversion emissions excited by 1150 nm laser was simultaneously discovered. With great enhancement compared with that of singly Ho 3+ doped counterparts, this work demonstrates the generality and rationality of our design strategy.

Solar steam generation and photocatalytic degradation have been regarded as the most promising techniques to address clean water scarcity issues. Although enormous efforts have been devoted to exploring high-efficiency clean water generation, many challenges still remain in terms of single decontamination function, relatively low efficiency, and inability to practical application. Herein, we first report the bioinspired fabrication of black titania (BT) nanocomposites with moth-eye-like nanostructures on carbon cloth for solar-driven clean water generation through solar steam generation and photocatalytic degradation. The moth-eye-like BT nanoarrays can largely prolong the effective propagation path of absorbing light and enhance the scattering of light, thereby exhibiting outstanding light absorption of 96% in the full spectrum. Such hierarchical-nanostructured BT nanocomposites not only impressively achieve solar steam efficiency of 94% under a simulated light of 1 kW m -2 but also show the prominent performance of desalination and steam generation in real life condition. In addition, 96% of rhodamine B is degraded using BT nanocomposites as a photocatalyst in 100 min. The moth-eye-like bioinspired designing concept and bifunctional applications in this study may open up a new strategy for maximizing solar energy utilization and clean water generation.

Fluorescent carbon dots (FCDs) have received considerable attention because of the great potential for a wide range of applications, from bioimaging to optoelectronic devices. In this work, we reported the synthesis of nitrogen-doped FCDs with an average size of 2 nm in a subcritical water apparatus by using biomass waste (i.e., expired milk) as the precursor. The obtained FCDs were highly dispersed in aqueous solution because of the presence of O-containing functional groups on their surfaces. Under the excitation of ultraviolet and blue light, the FCDs exhibited excitation wavelength-dependent fluorescence in the emission range of 400-550 nm. The FCDs could be easily taken up by HeLa cells without additional surface functionalization, serving as fluorescent nanoprobes for bioimaging. The applications of FCDs as sensing agents for the detection of Fe 3+ , solid-state fluorescent patterning, and transparent hybrid films were also performed, demonstrating their potential for solid-state fluorescent sensing, security labeling, and wearable optoelectronics., Competing Interests: The authors declare no competing financial interest.

Superlattices are of great importance due to their potential as new materials genome to synthesize new functional materials. Thus, tuning of the ground state of superlattices is crucial to further control their physical properties. In this study, superlattices (SLs) consisting of alternating layers of SrRuO 3 (SRO) (5 nm) and La 0.5 Ca 0.5 MnO 3 (LCMO) (5 nm) are epitaxially grown on SrTiO 3 (STO) and LaAlO 3 (LAO) substrates with 10-unit-cell periods. A variation in the substrate-induced-strain for this choice of SLs triggers observation of remarkable properties, such as magnetic anisotropy and large magnetic hysteresis. The strain states experienced by LCMO and SRO in these SLs result in strong ferromagnetic interlayer coupling and weak antiferromagnetic interlayer coupling at low temperatures in SLs of LCMO-SRO/STO and a strong antiferromagnetic interlayer coupling in SLs of LCMO-SRO/LAO. Besides, a large magnetic hysteresis resulting from the predominant magnetic anisotropy of SRO together with the strength of magnetic coupling is observed in SLs of LCMO-SRO/LAO along the out-of-plane direction of the LAO substrate. These four different magnetic behaviors along four different directions of substrate orientations are interpreted in terms of preferential orbital occupation and competing magnetic exchange coupling together with magnetic anisotropy. This study demonstrates the subtleties in controlling the strength of magnetic coupling at the interface and stands as a model system to realize fascinating magnetic phenomena in layer-by-layer hetero-epitaxial oxide films., Competing Interests: The authors declare no competing financial interest.

In this work, multifunctional Ti 4+ -immobilized phytic acid-modified magnetic graphene (denoted as MagG@PEI@PA-Ti 4+ ) nanocomposites were fabricated through a facile route for simultaneous/respective enrichment of N-glyco- and phosphopeptides. Phytic acid (PA), with six phosphate groups, possesses excellent hydrophilicity and metal ion coordination ability, which endowed the MagG@PEI@PA-Ti 4+ with combined properties of immobilized metal ion affinity chromatography (IMAC)- and hydrophilic interaction liquid chromatography (HILIC)-based materials. On the basis of the different binding ability of N-glyco- and phosphopeptides on MagG@PEI@PA-Ti 4+ , the MagG@PEI@PA-Ti 4+ nanocomposites could enrich N-glyco- and phosphopeptides simultaneously or respectively by using different enrichment conditions, achieving controllable selective enrichment of N-glyco- and phosphopeptides. The proposed nanocomposites demonstrated an outstanding performance for selective enrichment of N-glycopeptides (selectivity, 1:1000 molar ratios of IgG/BSA; sensitivity, 0.5 fmol/μL IgG; loading capacity, 300 mg g -1 ; recovery, >90%) and phosphopeptides (selectivity, 1:5000 molar ratios of α-casein/BSA; sensitivity, 0.1 fmol/μL α-casein; loading capacity, 100 mg g -1 ; recovery, >90%). Taking advantage of these merits, a total of 393 N-glycopeptides derived from 259 glycoproteins and 574 phosphopeptides derived from 341 phosphoproteins were identified from 200 μg of HeLa cell extracts through a single-step enrichment using MagG@PEI@PA-Ti 4+ .

A strain-relief structure by combining the strain-engineered periodic wrinkles and the parallel ribbons was employed to fabricate flexible dual spin valves onto PDMS substrates in a direct sputtering method. The strain-relief structure can accommodate the biaxial strain accompanying with stretching operation (the uniaxial applied tensile strain and the induced transverse compressive strain due to the Poisson effect), thus significantly reducing the influence of the residual strain on the giant magnetoresistance (GMR) performance. The fabricated GMR dual spin-valve sensor exhibits the nearly unchanged MR ratio of 9.9%, magnetic field sensitivity up to 0.69%/Oe, and zero-field resistance in a wide range of stretching strain, making it promising for applications on a conformal shape or a movement part.

In the current study, ovariectomized (OVX) rats and the senescence-accelerated mouse strain P6 (SAMP6) were employed to establish models of postmenopausal osteoporosis and senile osteoporosis, respectively. The effects of treatment with sialoglycoprotein isolated from the eggs of Carassius auratus (Ca-SGP) on these two types of osteoporosis were investigated in vivo. Results showed that Ca-SGP significantly increased bone mineral density, ameliorated trabecular bone microstructure, and improved bone biomechanical properties in both OVX rats and SAMP6. The osteogenesis related Wnt/β-catenin pathway was targeted to study the underlying mechanism of Ca-SGP activity. In postmenopausal osteoporosis, Ca-SGP suppressed the activation of Wnt/β-catenin signal via down-regulating the expression of key genes including LRP5, β-catenin, and Runx2, suggesting that overactive osteogenesis was controlled by Ca-SGP. The bone formation was sharply weakened in senile osteoporosis, whereas Ca-SGP treatment promoted osteoblast activity by stimulating the Wnt/β-catenin signal. In conclusion, Ca-SGP ameliorated these two types of osteoporosis by normalizing bone anabolism.

Benefiting from the advances made in well-controlled materials synthesis techniques, nanocomposites have drawn considerable attention due to their enthralling physics and functionalities. In this work, we report a new heteroepitaxial mesocrystal-perovskite nanocomposite, (NiFe2O4)0.33:(La0.67Ca0.33MnO3)0.67. Elaborate structural studies revealed that tiny NiFe2O4 nanocrystals aggregate into ordered octahedral mesocrystal arrays with {111} facets together with a concomitant structural phase transition of the La0.67Ca0.33MnO3 matrix upon postannealing process. Combined magnetic and X-ray absorption spectroscopic measurements show significant enhancement in the magnetic properties at room temperature due to the structural evolution of magnetic NiFe2O4 and the consequent magnetic coupling at the heterointerfaces mediating via well connected octahedrons of Mn-O6 in La0.67Ca0.33MnO3 and (Ni,Fe)-O6 in NiFe2O4. This work demonstrates an approach to manipulate the exciting physical properties of material systems by integrating desired functionalities of the constituents via synthesis of a self-assembled mesocrystal embedded nanocomposite system.

Magnetic refrigeration, resulting from the magnetocaloric effect of a material around the magnetic phase-transition temperature, is a topic of great interest as it is considered to be an alternate energy solution to conventional vapor-compression refrigeration. The viability of a magnetic refrigeration system for magnetic cooling can be tested by exploiting materials in various forms, from bulk to nanostrucutres. In this study, magnetocaloric properties of self-assembled Mn3O4-La(0.7)Sr(0.3)MnO3 nanocomposites, with varying doping concentrations of Mn3O4 in the form of nanocrystals embedded in the La(0.7)Sr(0.3)MnO3 matrix, are investigated. The temperatures corresponding to the paramagnetic-to-ferromagnetic transitions are higher, and the values of change in magnetic entropy under a magnetic field of 2 T show an enhancement (highest being ∼130%) for the nanocomposites with low doping concentrations of Mn3O4, compared to that of pure La(0.7)Sr(0.3)MnO3 thin films. Relative cooling power remain close to those of La(0.7)Sr(0.3)MnO3. The enhanced magnetic phase-transition temperature and magnetocaloric effect are interpreted and evidenced in the framework of interfacial coupling between Mn3O4 and La(0.7)Sr(0.3)MnO3. This work demonstrates the potentiality of self-assembled nanostructures for magnetic cooling near room temperature under low magnetic fields.

Mesocrystal, a new class of crystals as compared to conventional and well-known single crystals and polycrystalline systems, has captured significant attention in the past decade. Recent studies have been focused on the advance of synthesis mechanisms as well as the potential on device applications. In order to create further opportunities upon functional mesocrystals, we fabricated a self-assembled nanocomposite composed of magnetic CoFe2O4 mesocrystal in Sr-doped manganites. This combination exhibits intriguing structural and magnetic tunabilities. Furthermore, the antiferromagnetic coupling of the mesocrystal and matrix has induced an additional magnetic perturbation to spin-polarized electrons, resulting in a significantly enhanced magnetoresistance in the nanocomposite. Our work demonstrates a new thought toward the enhancement of intrinsic functionalities assisted by mesocrystals and advanced design of novel mesocrystal-embedded nanocomposites.

Self-assembled nanocomposites with a high interface-to-volume ratio offer an opportunity to overcome limitations in current technology, where intriguing transport behaviors can be tailored by the choice of proper interactions of constituents. Here we integrated metallic perovskite oxide SrRuO3-wurzite semiconductor ZnO nanocomposites to investigate the room-temperature metal-insulator transition and its effect on photoresponse. We demonstrate that the band structure at the interface can be tuned by controlling the interface-to-volume ratio of the nanocomposites. Photoinduced carrier injection driven by visible light was detected across the nanocomposites. This work shows the charge interaction of the vertically integrated multiheterostructures by incorporating a controllable interface-to-volume ratio, which is essential for optimization of the design and functionality of electronic devices.

Metabolomics is developing as an important functional genomics tool for understanding plant systems' response to genetic and environmental changes. Here, we characterized the metabolic changes of cultivated soybean C08 (Glycine max L. Merr) and wild soybean W05 (Glycine soja Sieb.et Zucc.) under salt stress using MS-based metabolomics, in order to reveal the phenotypes of their eight hybrid offspring (9H0086, 9H0124, 9H0391, 9H0736, 9H0380, 9H0400, 9H0434, and 9H0590). Total small molecule extracts of soybean seedling leaves were profiled by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-Fourier transform mass spectrometry (LC-FT/MS). We found that wild soybean contained higher amounts of disaccharides, sugar alcohols, and acetylated amino acids than cultivated soybean, but with lower amounts of monosaccharides, carboxylic acids, and unsaturated fatty acids. Further investigations demonstrated that the ability of soybean to tolerate salt was mainly based on synthesis of compatible solutes, induction of reactive oxygen species (ROS) scavengers, cell membrane modifications, and induction of plant hormones. On the basis of metabolic phenotype, the salt-tolerance abilities of 9H0086, 9H0124, 9H0391, 9H0736, 9H0380, 9H0400, 9H0434, and 9H0590 were discriminated. Our results demonstrated that MS-based metabolomics provides a fast and powerful approach to discriminate the salt-tolerance characteristics of soybeans.

Metabonomics is an important platform for investigating the metabolites of integrated living systems and their dynamic responses to changes caused by both endogenous and exogenous factors. A metabonomics strategy based on liquid chromatography-mass spectrometry/mass spectrometry in both positive and negative ion modes was applied to investigate the short-term and long-term stability of metabolites in plasma. Principal components analysis and ten types of identified metabolites were used to summarize the time-dependent change rules in metabolites systematically at different temperatures. The long-term stability of metabolites in plasma specimens stored at -80 °C for five years was also studied. Analysis of these subjects identified 36 metabolites with statistically significant changes in expression (p < 0.05) and found a kind of metabolite with a hundred-fold change. The stability of metabolites in blood at 4 °C for 24 h was also investigated. These studies show that a thorough understanding of the effects of metabolite stability are necessary for improving the reliability of potential biomarkers.

Successful further development of superhigh-constrast upconversion (UC) bioimaging requires addressing the existing paradox: 980 nm laser light is used to excite upconversion nanoparticles (UCNPs), while 980 nm light has strong optical absorption of water and biological specimens. The overheating caused by 980 nm excitation laser light in UC bioimaging is computationally and experimentally investigated for the first time. A new promising excitation approach for better near-infrared to near-infrared (NIR-to-NIR) UC photoluminescence in vitro or in vivo imaging is proposed employing a cost-effective 915 nm laser. This novel laser excitation method provides drastically less heating of the biological specimen and larger imaging depth in the animals or tissues due to quite low water absorption. Experimentally obtained thermal-graphic maps of the mouse in response to the laser heating are investigated to demonstrate the less heating advantage of the 915 nm laser. Our tissue phantom experiments and simulations verified that the 915 nm laser is superior to the 980 nm laser for deep tissue imaging. A novel and facile strategy for surface functionalization is utilized to render UCNPs hydrophilic, stable, and cell targeting. These as-prepared UCNPs were characterized by TEM, emission spectroscopy, XRD, FTIR, and zeta potential. Specifically targeting UCNPs excited with a 915 nm laser have shown very high contrast UC bioimaging. Highly stable DSPE-mPEG-5000-encapsulated UCNPs were injected into mice to perform in vivo imaging. Imaging and spectroscopy analysis of UC photoluminescence demonstrated that a 915 nm laser can serve as a new promising excitation light for UC animal imaging.

An integrated ionization approach of electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) combining with rapid resolution liquid chromatography mass spectrometry (RRLC-MS) has been developed for performing global metabonomic analysis on complex biological samples. This approach was designed to overcome the low ionization efficiencies of endogenous metabolites due to diverse physicochemical properties as well as ion suppression, and obtain comprehensive metabolite profiles in LC-MS analysis. Ionization capability and applicability were manifested by improved ionization efficiency and enlarged metabolite coverage in analysis on typical urinary metabolite standards and urine samples from healthy volunteers. The method was validated by the limit of detection and precision. When applied to the global metabonomic studies of lung cancer, more comprehensive biomarker candidates were obtained to reflect metabolic traits between healthy volunteers and lung cancer patients, including 74 potential biomarkers in positive ion mode and 59 in negative ion mode. Taking identical potential biomarkers of any two or three ionization methods into account, analysis using ESI-MS in positive (+) and negative (-) ion mode contributed to 70 and 64% of the total potential biomarkers, respectively. The biomarker discovery capability of (+/-) APCI-MS accounted for 45 and 42% of the overall; meanwhile (+/-) APPI-MS amounted for 39 and 54%. These results indicated that potential biomarkers with vital biological information could be missed if only a single ionization method was used. Furthermore, 11 potential biomarkers were identified including amino acids, nucleosides, and a metabolite of indole. They revealed elevated amino acid and nucleoside metabolism as well as protein degradation in lung cancer patients. This proposed approach provided a more comprehensive picture of the metabolic changes and further verified identical biomarkers that were obtained simultaneously using different ionization methods.

A spiral plasmonic lens can focus circular polarization of a given handedness while simultaneously defocus the circular polarization of the opposite chirality, which may be used as a miniature circular polarization analyzer. In this letter, we experimentally investigated the plasmonic focusing properties of the spiral lens using a collection mode near-field scanning optical microscope. A single Archimedes' spiral slot with a single turn was etched through gold thin film as a spiral plasmonic lens. The plasmonic field at the focus of a spiral lens strongly depends on the spin of the incident photon. Circular polarization extinction ratio better than 50 is obtainable with a device size as small as only 4 times of surface plasmon wavelength.

Optimal plasmonic focusing can be achieved through matching the rotational symmetry of the plasmonic lens to the polarization symmetry of a radially polarized illumination. In this letter, we report the experimental confirmation of the focusing properties and field enhancement effect of plasmonic lens made of multiple concentric annular rings using a collection mode near field scanning optical microscope. Surface plasmons excited at all azimuthal directions propagate toward the geometric center and constructively interfere at the focus to create a strongly enhanced evanescent optical "needle" field that is substantially polarized vertically to the plasmonic lens surface. The field enhancement factor can be improved through adding more rings while maintaining the plasmonic focal spot size. Strategy for optimizing the field enhancement factor is studied with both analytical and numerical methods.

We report a discovery that self-assembled perovskite-spinel nanostructures can be controlled simply by selecting single-crystal substrates with different orientations. In a model BiFeO(3)-CoFe(2)O(4) system, a (001) substrate results in rectangular-shaped CoFe(2)O(4) nanopillars in a BiFeO(3) matrix; in contrast, a (111) substrate leads to triangular-shaped BiFeO(3) nanopillars in a CoFe(2)O(4) matrix, irrespective of the volume fraction of the two phases. This dramatic reversal is attributed to the surface energy anisotropy as an intrinsic property of a crystal.

The interactions of various polypeptides with individual carbon nanotubes (CNTs), both multiwall (MW) and single wall (SW), were investigated by atomic force microscopy (AFM). While adhesion forces arising from electrostatic attraction interactions between the protonated amine groups of polylysine and carboxylic groups on the acid-oxidized multi-wall carbon nanotubes (Ox-MWCNTs) dominate the interaction at a low pH, weaker adhesion forces via the hydrogen bonding between the neutral -NH2 groups of polylysine and -COO- groups of the Ox-MWCNTs were detected at a high pH. The adhesion force was further found to increase with the oxidation time for Ox-MWCNTs and to be negligible for oxidized single-wall carbon nanotubes (Ox-SWCNTs) because carboxylate groups were only attached onto the nanotube tips in the latter whereas onto both the nanotube tips and sidewall in the former. Furthermore, it was demonstrated that proteins containing aromatic moieties, such as polytryptophan, showed a stronger adhesion force with Ox-MWCNTs than that of polylysine because of the additional pi-pi stacking interaction between the polytryptophan chains and CNTs.

We present direct evidence for room-temperature magnetization reversal induced by an electric field in epitaxial ferroelectric BiFeO3-ferrimagnetic CoFe2O4 columnar nanostructures. Piezoelectric force microscopy and magnetic force microscopy were used to locally image the coupled piezoelectric-magnetic switching. Quantitative analyses give a perpendicular magnetoelectric susceptibility of approximately 1.0 x 10(-2) G cm/V. The observed effect is due to the strong elastic coupling between the two ferric constituents as the result of the three-dimensional heteroepitaxy.

We have applied two-step laser mass spectrometry (L2MS) to the qualitative chemical analysis of porphyrin-derived photosensitizer dyes used for detection and photodynamic therapy of cancer. The only ionization technique applied so far to these low-volatility compounds had been fast atom bombardment (FAB), which suffers from problems associated with cluster formation of the porphyrins upon FAB ionization. From FAB and chromatography data, the existence of porphyrin dimers, trimers, and oligomers in commercial photosensitizers was concluded to be crucial for tumor localization, but it is possible that clustering or preformed van der Waals aggregates gave rise to these results. L2MS indicates that commercially available hematoporphyrin derivative and Photofrin II contain no detectable amounts of covalently bound porphyrin oligomers. Synthetic porphyrin dimers and trimers could be unambiguously detected by L2MS.