Dual Enzyme-Locked Activation Reporter for Accurate Liver Cancer Surveillance.

Activatable probes with a higher signal-to-background ratio and accuracy are essential for monitoring liver cancer as well as intraoperative fluorescence navigation. However, the presence of only one biomarker is usually not sufficient to meet the high requirement of a signal-to-background ratio in cancer surveillance, leading to the risk of misdiagnosis. In this work, a dual-locked activation response probe, Si-NTR-LAP, for nitroreductase and leucine aminopeptidase was reported. This dual-locked probe provides better tumor recognition and a higher signal-to-noise ratio than that of single-locked probes (Si-LAP and Si-NTR). In both the subcutaneous tumor model and the more complex orthotopic hepatocellular carcinoma model, the probe was able to identify tumor tissue with high specificity and accurately differentiate the boundaries between tumor tissue and normal tissue. Therefore, the dual-locked probe may provide a new and practical strategy for applying to real patient tumor tissue samples.

Machine-Learning-Assisted Rational Design of Si─Rhodamine as Cathepsin-pH-Activated Probe for Accurate Fluorescence Navigation.

High-performance fluorescent probes stand as indispensable tools in fluorescence-guided imaging, and are crucial for precise delineation of focal tissue while minimizing unnecessary removal of healthy tissue. Herein, machine-learning-assisted strategy to investigate the current available xanthene dyes is first proposed, and a quantitative prediction model to guide the rational synthesis of novel fluorescent molecules with the desired pH responsivity is constructed. Two novel Si─rhodamine derivatives are successfully achieved and the cathepsin/pH sequentially activated probe Si─rhodamine─cathepsin-pH (SiR─CTS-pH) is constructed. The results reveal that SiR─CTS-pH exhibits higher signal-to-noise ratio of fluorescence imaging, compared to single pH or cathepsin-activated probe. Moreover, SiR─CTS-pH shows strong differentiation abilities for tumor cells and tissues and accurately discriminates the complex hepatocellular carcinoma tissues from normal ones, indicating its significant application potential in clinical practice. Therefore, the continuous development of xanthene dyes and the rational design of superior fluorescent molecules through machine-learning-assisted model broaden the path and provide more advanced methods to researchers.

Construction of a novel aminofluorene-based ratiometric near-infrared fluorescence probe for detecting carboxylesterase activity in living cells.

Herein, we constructed a novel aminofluorene-based fluorescence probe (FEN-CE) for the detection of carboxylesterase (CE) in living cells by a ratiometric near-infrared (NIR) fluorescence signal. FEN-CE with NIR emission (650 nm) could be hydrolyzed specifically by CE and transformed to FENH with the release of the self-immolative group, which exhibited a red-shifted emission peak of 680 nm. In addition, FEN-CE showed high selectivity for CE and was successfully used in the detection of CE activity in living cells through its ratiometric NIR fluorescence signals.

Molecular Engineering of Sulfone-Xanthone Chromophore for Enhanced Fluorescence Navigation.

Enriching the palette of high-performance fluorescent dyes is vital to support the frontier of biomedical imaging. Although various rhodamine skeletons remain the premier type of small-molecule fluorophores due to the apparent high brightness and flexible modifiability, they still suffer from the inherent defect of small Stokes shift due to the nonideal fluorescence imaging signal-to-background ratio. Especially, the rising class of fluorescent dyes, sulfone-substituted xanthone, exhibits great potential, but low chemical stability is also pointed out as the problem. Molecular engineering of sulfone-xanthone to obtain a large Stokes shift and high stability is highly desired, but it is still scarce. Herein, we present the combination modification method for optimizing the performance of sulfone-xanthone. These redesigned fluorescent skeletons owned greatly improved stability and Stokes shift compared with the parent sulfone-rhodamine. To the proof of bioimaging capacity, annexin protein-targeted peptide LS301 was introduced to the most promising dyes, J-S-ARh, to form the tumor-targeted fluorescent probe, J-S-LS301. The resulting probe, J-S-LS301, can be an outstanding fluorescence tool for the orthotopic transplantation tumor model of hepatocellular carcinoma imaging and on-site pathological analysis. In summary, the combination method could serve as a basis for rational optimization of sulfone-xanthone. Overall, the chemistry reported here broadens the scope of accessible sulfone-xanthone functionality and, in turn, enables to facilitate the translation of biomedical research toward the clinical domain.

Rational Design of pH-Independent and High-Fidelity Near-Infrared Tunable Fluorescent Probes for Tracking Leucine Aminopeptidase In Vivo.

Accurate detection of target analytes and generation of high-fidelity fluorescence signals are particularly critical in life sciences and clinical diagnostics. However, the majority of current NIR-I fluorescent probes are vulnerable to pH effects resulting in signal distortion. In this work, a series of fluorescence-tunable and pH-independent probes are reported by combining optically tunable groups of unsymmetric Si-rhodamines and introducing the methoxy instead of the spiro ring on the benzene ring at position 9. To validate the concept, the leucine aminopeptidase response site was introduced into Si-2,6OMe-NH2 with the best optical properties to synthesize Si-LAP for monitoring the intrahepatic LAP in vivo. Therefore, the design approach may provide a new and practical strategy for designing innovative functional fluorescent probes and generating high-stability and high-fidelity fluorescent signals.

Migration from Lysosome to Nucleus: Monitoring Lysosomal Alkalization-Related Biological Processes with an Aminofluorene-Based Probe.

Aberrant lysosomal alkalization is associated with various biological processes, such as oxidative stress, cell apoptosis, ferroptosis, etc. Herein, we developed a novel aminofluorene-based fluorescence probe named FAN to monitor the lysosomal alkalization-related biological processes by its migration from lysosome to nucleus. FAN possessed NIR emission, large Stokes shift, high pH stability, and high photostability, making it suitable for real-time and long-term bioimaging. As a lysosomotropic molecule, FAN can accumulate in lysosomes first and then migrate to the nucleus by right of its binding capability to DNA after lysosomal alkalization. In this manner, FAN was successfully used to monitor these physiological processes which triggered lysosomal alkalization in living cells, including oxidative stress, cell apoptosis, and ferroptosis. More importantly, at higher concentrations, FAN could also serve as a stable nucleus dye for the fluorescence imaging of the nucleus in living cells and tissues. This novel multifunctional fluorescence probe shows great promise for application in lysosomal alkalization-related visual research and nucleus imaging.

Magnetization reversal driven by low dimensional chaos in a nanoscale ferromagnet.

Energy-efficient switching of magnetization is a central problem in nonvolatile magnetic storage and magnetic neuromorphic computing. In the past two decades, several efficient methods of magnetic switching were demonstrated including spin torque, magneto-electric, and microwave-assisted switching mechanisms. Here we experimentally show that low-dimensional magnetic chaos induced by alternating spin torque can strongly increase the rate of thermally-activated magnetic switching in a nanoscale ferromagnet. This mechanism exhibits a well-pronounced threshold character in spin torque amplitude and its efficiency increases with decreasing spin torque frequency. We present analytical and numerical calculations that quantitatively explain these experimental findings and reveal the key role played by low-dimensional magnetic chaos near saddle equilibria in enhancement of the switching rate. Our work unveils an important interplay between chaos and stochasticity in the energy assisted switching of magnetic nanosystems and paves the way towards improved energy efficiency of spin torque memory and logic.

Parametric Resonance of Magnetization Excited by Electric Field.

Manipulation of magnetization by electric field is a central goal of spintronics because it enables energy-efficient operation of spin-based devices. Spin wave devices are promising candidates for low-power information processing, but a method for energy-efficient excitation of short-wavelength spin waves has been lacking. Here we show that spin waves in nanoscale magnetic tunnel junctions can be generated via parametric resonance induced by electric field. Parametric excitation of magnetization is a versatile method of short-wavelength spin wave generation, and thus, our results pave the way toward energy-efficient nanomagnonic devices.

Porous iron molybdate nanorods: in situ diffusion synthesis and low-temperature H2S gas sensing.

In the paper, we developed an in situ diffusion growth method to fabricate porous Fe2(MoO4)3 nanorods. The average diameter and the length of the porous nanorods were 200 nm and 1.2-4 µm, respectively. Moreover, many micropores existed along axial direction of the Fe2(MoO4)3 nanorods. In terms of nitrogen adsorption-desorption isotherms, calculated pore size was in the range of 4-115 nm, agreeing well with the transmission electron microscope observations. Because of the uniquely porous characteristics and catalytic ability at low temperatures, the porous Fe2(MoO4)3 nanorods exhibited very good H2S sensing properties, including high sensitivity at a low working temperature (80 °C), relatively fast response and recovery times, good selectivity, and long-term stability. Thus, the porous Fe2(MoO4)3 nanorods are very promising for the fabrication of high-performance H2S gas sensors. Furthermore, the strategy presented here could be expended as a general method to synthesize other hollow/porous-type transition metal molybdate nanostructures by rational designation in nanoscale.

Quaternary nanocomposites consisting of graphene, Fe3O4@Fe core@shell, and ZnO nanoparticles: synthesis and excellent electromagnetic absorption properties.

This paper presents for the first time a successful synthesis of quaternary nanocomposites consisting of graphene, Fe(3)O(4)@Fe core/shell nanopariticles, and ZnO nanoparticles. Transmission electron microscopy measurements show that the diameter of the Fe(3)O(4)@Fe core/shell nanoparitcles is about 18 nm, the Fe(3)O(4) shell's thickness is about 5 nm, and the diameter of ZnO nanoparticles is in range of 2-10 nm. The measured electromagnetic parameters show that the absorption bandwidth with reflection loss less than -20 dB is up to 7.3 GHz, and in the band range more than 99% of electromagnetic wave energy is attenuated. Moreover, the addition amount of the nanocomposites in the matrix is only 20 wt %. Therefore, the excellent electromagnetic absorption properties with lightweight and wide absorption frequency band are realized by the nanocomposites.

Voltage-induced ferromagnetic resonance in magnetic tunnel junctions.

We demonstrate excitation of ferromagnetic resonance in CoFeB/MgO/CoFeB magnetic tunnel junctions (MTJs) by the combined action of voltage-controlled magnetic anisotropy (VCMA) and spin transfer torque (ST). Our measurements reveal that GHz-frequency VCMA torque and ST in low-resistance MTJs have similar magnitudes, and thus that both torques are equally important for understanding high-frequency voltage-driven magnetization dynamics in MTJs. As an example, we show that VCMA can increase the sensitivity of an MTJ-based microwave signal detector to the sensitivity level of semiconductor Schottky diodes.

Fe2O3/TiO2 tube-like nanostructures: synthesis, structural transformation and the enhanced sensing properties.

The paper describes for the first time the successful synthesis of Fe(2)O(3)/TiO(2) tube-like nanostructures, in which TiO(2) shell is of quasi-single crystalline characteristic and its thickness can be controlled through adjusting the added amount of aqueous Ti(SO(4))(2) solution. The characterization of samples obtained at different stages using transmission electron microscope indicates that the outer TiO(2) shell is changed gradually from amorphous and polycrystalline phase into quasi-single crystal under thermal actions through the Ostwald ripening process, accompanying the corrosion of the central parts of Fe(2)O(3) nanorods, and the formation of small particles separating each other, leading to the special core/shell nanorods. Furthermore, Fe(2)O(3)/TiO(2) tube-like nanostructures can be transformed into Fe(2)TiO(5) nanostructures after they are thermally treated at higher temperatures. Those nanostructures exhibit enhanced ethanol sensing properties with respect to the monocomponent. Our results imply that not only hollow nanostructures, but also a novel type of nanostructures can be fabricated by the present method for nanodevices.

High gas sensing performance of one-step-synthesized Pd-ZnO nanoflowers due to surface reactions and modifications.

Pd-ZnO nanoflowers with high uniformity were prepared via a novel one-step hydrothermal route. High sensitivity, fast response, high selectivity and low work temperature are obtained from Pd-ZnO nanoflower sensors. The sensitivity upon exposure to 300 ppm ethanol is up to 168 at 300 °C and maintains 2.6 at 120 °C. Such behaviors can be attributed to Schottky contact at the Pd/ZnO interface and catalytic activity of Pd nanoparticles. The present results open a way for uniform surface modification of one-dimensional nanostructures with Pd nanoparticles and further enhancing their gas sensing performance.

Enhanced gas sensing performance of SnO2/α-MoO3 heterostructure nanobelts.

Extremely high sensitivity and low working temperature of gas sensors are realized from SnO(2)/α-MoO(3) heterostructure nanobelts. Their sensitivity against 500 ppm ethanol is up to 67.76 at the working temperature of 300 °C, which is higher than that of bare α-MoO(3) and SnO(2) nanostructures. Also the working temperature can be lowered down to 120 °C. Such behaviors are attributed to the variation of the junction barrier at the SnO(2)/α-MoO(3) interface. The present results imply that heterostructured 1D nanomaterials may yield gas sensors with improved characteristics, and can be applied to a wide range of gas sensors.

SnO2/α-MoO3 core-shell nanobelts and their extraordinarily high reversible capacity as lithium-ion battery anodes.

Extraordinarily high reversible capacity of lithium-ion battery anodes is realized from SnO(2)/α-MoO(3) core-shell nanobelts. The reversible capacity is much higher than traditional theoretical results. Such behavior is attributed to α-MoO(3) that makes extra Li(2)O reversibly convert to Li(+).

Porous Co3O4 nanoneedle arrays growing directly on copper foils and their ultrafast charging/discharging as lithium-ion battery anodes.

Ultrafast charging/discharging of lithium-ion battery anodes is realized from porous Co(3)O(4) nanoneedle arrays growing on copper foils. Their charge time can be shortened to ∼6 s, their reversible capacity at 0.5C rate is 1167 mAh/g. This implies that nano-arrays growing directly on copper foils are good candidates for anodes.

Abnormal gas sensing characteristics arising from catalyzed morphological changes of ionsorbed oxygen.

Abnormal gas sensing characteristics are observed at low temperature in uniformly loaded Pt@SnO(2) nanorod gas sensors. The sensors operated at 200 degrees C exhibit opposite variations of resistances, and the change of resistance decreases with increasing ethanol concentration. In contrast, the sensors operated at 300 degrees C show regular behavior and the sensitivity is extremely high. Such behaviors are ascribed to Pt-catalyzed morphological changes of ionsorbed oxygen at low temperature. The present results are the bases for further investigating the effect of ionsorbed oxygen morphologies on gas sensing.

Synthesis and enhanced ethanol sensing characteristics of alpha-Fe2O3/SnO2 core-shell nanorods.

Alpha-Fe(2)O(3)/SnO(2) core-shell nanorods are synthesized via a three-step process. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses reveal that their diameters and lengths are respectively in the ranges 35-120 nm and 0.35-1.2 microm, and the thickness of the shell composed of 3.5 nm SnO(2) nanoparticles is about 10 nm. The core-shell nanostructures exhibit a dramatic improvement in ethanol sensing characteristics compared to pure alpha-Fe(2)O(3) nanorods. The sensor response is up to 19.6 under 10 ppm ethanol exposure at 220 degrees C. Both the response time and the recovery time of the core-shell structures are less than 30 s. Based on the space-charge layer model and semiconductor heterojunction theory, the small thickness of the SnO(2) shell and the formation of heterojunctions contribute to the enhanced ethanol sensing characteristics. Our results demonstrate that one-dimensional metal oxide core-shell nanostructures whose shell thickness is smaller than the Debye length are very promising materials for fabricating gas sensors with good performances.