Cancer-associated fibroblasts and its derived exosomes: a new perspective for reshaping the tumor microenvironment.

Cancer-associated fibroblasts (CAFs) are the most abundant stromal cells within the tumor microenvironment (TME). They extensively communicate with the other cells. Exosome-packed bioactive molecules derived from CAFs can reshape the TME by interacting with other cells and the extracellular matrix, which adds a new perspective for their clinical application in tumor targeted therapy. An in-depth understanding of the biological characteristics of CAF-derived exosomes (CDEs) is critical for depicting the detailed landscape of the TME and developing tailored therapeutic strategies for cancer treatment. In this review, we have summarized the functional roles of CAFs in the TME, particularly focusing on the extensive communication mediated by CDEs that contain biological molecules such as miRNAs, proteins, metabolites, and other components. In addition, we have also highlighted the prospects for diagnostic and therapeutic applications based on CDEs, which could guide the future development of exosome-targeted anti-tumor drugs.

Interactions between MFAP5 + fibroblasts and tumor-infiltrating myeloid cells shape the malignant microenvironment of colorectal cancer.

BACKGROUND: The therapeutic targeting of the tumor microenvironment (TME) in colorectal cancer (CRC) has not yet been fully developed and utilized because of the complexity of the cell-cell interactions within the TME. The further exploration of these interactions among tumor-specific clusters would provide more detailed information about these communication networks with potential curative value. METHODS: Single-cell RNA sequencing, spatial transcriptomics, and bulk RNA sequencing datasets were integrated in this study to explore the biological properties of MFAP5 + fibroblasts and their interactions with tumor-infiltrating myeloid cells in colorectal cancer. Immunohistochemistry and multiplex immunohistochemistry were performed to confirm the results of these analyses. RESULTS: We profiled heterogeneous single-cell landscapes across 27,414 cells obtained from tumors and adjacent tissues. We mainly focused on the pro-tumorigenic functions of the identified MFAP5 + fibroblasts. We demonstrated that tumor-resident MFAP5 + fibroblasts and myeloid cells (particularly C1QC + macrophages) were positively correlated in both spatial transcriptomics and bulk RNA-seq public cohorts. These cells and their interactions might shape the malignant behavior of CRC. Intercellular interaction analysis suggested that MFAP5 + fibroblasts could reciprocally communicate with C1QC + macrophages and other myeloid cells to remodel unfavorable conditions via MIF/CD74, IL34/CSF1R, and other tumor-promoting signaling pathways. CONCLUSION: Our study has elucidated the underlying pro-tumor mechanisms of tumor-resident MFAP5 + fibroblasts and provided valuable targets for the disruption of their properties.

Synthesis of a photo-responsive single-walled nanoscroll and its photo-reactivity in a nano-layered microenvironment.

A photo-responsive nanoscroll composed of niobate nanosheets and a polyfluoroalkyl azobenzene derivative (C3F-Azo-C6H) is one of the most interesting layered materials because the reversible winding and unwinding motion could be efficiently induced by photo-irradiations. Previously, we have studied a double-walled nanoscroll (DWNS) of niobate that could be synthesized by the intercalation of a cationic polyfluorinated surfactant only into the interlayer I of the layered niobate among the two interlayers, I and II. In this study, we have successfully synthesized another novel photo-responsive single-walled nanoscroll (SWNS) of niobate by a stepwise guest-guest ion-exchange method. All niobate nanosheets that were exfoliated at both interlayers I and II were efficiently converted to nanoscrolls by the intercalation of C3F-Azo-C6H. The synthetic yield has been quantitatively estimated. Though the photo-isomerization reaction of C3F-Azo-C6H was induced in the SWNS, its photo-reactivity was the lowest when compared with those of the nanosheet-stacked film and the DWNS. The photo-reactivity of C3F-Azo-C6H decreased in the order of DWNS > nanosheet-stacked film > SWNS. The different flexibility of the layered miroenvironment might influence the photo-reactivity of C3F-Azo-C6H in the niobate hybrid. The SWNS exhibited a reversible expansion and shrinkage of its interlayer spaces upon photo-irradiation, while the winding and unwinding motion was not observed, contrary to the DWNS. The direction of the expansion and shrinkage of the interlayer of the SWNS was opposite to those of the nanosheet-stacked film and the DWNS. Based on the experimental results, the tilt angle of C3F-Azo-C6H against the nanosheet surface and the matching structures of the top and bottom surfaces of the nanosheet could be the probable key factors that control the photo-reactivity of C3F-Azo-C6H in the layered microenvironment; the morphological changes of the nano hybrids was also discussed.

Construction of cationic polyfluorinated azobenzene/reduced graphene oxide for simultaneous determination of dopamine, uric acid and ascorbic acid.

A highly sensitive cationic polyfluorinated azobenzene/reduced graphene oxide (C3F7-azo+/RGO) nanocomposite electrochemical sensor for simultaneous detection of dopamine (DA), ascorbic acid (AA) and uric acid (UA) was successfully synthesized using a facile exfoliation/restacking method. The nanocomposite is self-assembled from oppositely charged graphene oxide nanosheets (GO) and polyfluorinated azobenzene cations (C3F7-azo+), and then obtained by electrochemical reduction. The structure and electrochemical properties were characterized by X-ray diffraction (XRD), energy dispersive spectrometer analysis (EDS), transmission electron microscope (TEM) and scanning electron microscope (SEM). The electrochemical property of C3F7-azo+/RGO was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). It can be clearly seen from experimental results that C3F7-azo+/RGO-modified electrode (C3F7-azo+/RGO/GCE) can detect DA, AA and UA simultaneously, and has good stability and anti-interference performance. The detection limits are 65 nM, 8 nM and 11 nM for DA, AA and UA in the ranges 57.28-134.28 µM, 0.04-6.01 µM, 9.23-23.45 µM, respectively.

A photoactivated artificial muscle model unit: reversible, photoinduced sliding of nanosheets.

A novel photoactivated artificial muscle model unit is reported. Here we show that organic/inorganic hybrid nanosheets reversibly slide horizontally on a giant scale and the interlayer spaces in the layered hybrid structure shrink and expand vertically by photoirradiation. The sliding movement of the system on a giant scale is the first example of an artificial muscle model unit having much similarity with that in natural muscle fibrils. In particular, our layered hybrid molecular system exhibits a macroscopic morphological change on a giant scale (~1500 nm) relative to the molecular size of ~1 nm by means of a reversible sliding mechanism.

In situ Preparation of HNbMoO6/C Nanocomposite for Sensitive Detection of Clenbuterol.

In this paper, we synthesized HNbMoO6/C composite through the calcination of octylamine-intercalated HNbMoO6 precursor. The resulting HNbMoO6/C composite showed some new phases of MoO2, MoO3, NbO2, Nb2O5, and carbon, which was fully confirmed via powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS) technologies. Besides, the HNbMoO6/C hybrid was coated on glass carbon electrode to construct an electrochemical sensor for sensitive determination of clenbuterol. The electrochemical behaviors of clenbuterol on the prepared electrode were tested by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The results showed that the intercalated carbon can act as active sites to accelerate electron transfer. In addition, more exposed surface areas of the HNbMoO6/C composite will facilitate the electrolyte to permeate. The oxidation peak current of clenbuterol was linearly related to its concentration in the range of 1.04 × 10-5 to 7.51 × 10-4 mol L-1, and the determination limit was calculated to be 3.03 × 10-6 mol L-1 (S/N = 3). This sensor exhibits excellent stability, reproducibility, specificity, and good recoveries when applied to monitor clenbuterol in real samples.

Fabrication of a New Self-assembly Compound of CsTi2NbO7 with Cationic Cobalt Porphyrin Utilized as an Ascorbic Acid Sensor.

A novel sandwich-structured nanocomposite based on Ti2NbO7- nanosheets and cobalt porphyrin (CoTMPyP) was fabricated through electrostatic interaction, in which CoTMPyP has been successfully inserted into the lamellar spacing of layered titanoniobate. The resultant Ti2NbO7/CoTMPyP nanocomposite was characterized by XRD, SEM, TEM, EDS, FT-IR, and UV-vis. It is demonstrated that the intercalated CoTMPyP molecules were found to be tilted approximately 63° against Ti2NbO7- layers. The glass carbon electrode (GCE) modified by Ti2NbO7/CoTMPyP film showed a fine diffusion-controlled electrochemical redox process. Furthermore, the Ti2NbO7/CoTMPyP-modified electrode exhibited excellent electrocatalytic oxidation activity of ascorbic acid (AA). Differential pulse voltammetric studies demonstrated that the intercalated nanocomposite detects AA linearly over a concentration range of 4.99 × 10-5 to 9.95 × 10-4 mol L-1 with a detection limit of 3.1 × 10-5 mol L-1 at a signal-to-noise ratio of 3.0.

Strategy for the Realization of Highly Efficient Solution-Processed All-Fluorescence White OLEDs-Encapsulated Thermally Activated Delayed Fluorescent Yellow Emitters.

Fabrication of highly efficient all thermally activated delayed fluorescence (TADF) white organic light-emitting diodes (WOLEDs) through solution-process still remains a big challenge. Here, two encapsulated TADF molecules with a small singlet-triplet energy gap (Δ EST) and high photoluminescence quantum yield (PLQY) were designed and synthesized as yellow emitters for solution-processed WOLEDs. The high current, power, and external quantum efficiencies of 41.6 cd A-1, 30.4 lm W-1, and 17.3% were achieved for the solution-processed all-fluorescence WOLEDs with a single-emission layer. In contrast, even with the same Δ EST and PLQY, the corresponding unencapsulated parent emitters will account for nearly 50% loss of the potential device efficiency. This is for the first time that the small molecular TADF blue host and TADF yellow guest are used to construct solution-processed all-fluorescence WOLEDs, which exhibit high efficiency comparable with most of the vacuum-deposited all-fluorescence white devices. These results not only demonstrate the great potential of TADF emitters in achieving highly efficient solution-processed WOLEDs, but also testify the key role of molecular encapsulation in reducing polar-exciton quenching and enhancing electroluminescence performance.

Efficient Photocatalytic Degradation of Malachite Green in Seawater by the Hybrid of Zinc-Oxide Nanorods Grown on Three-Dimensional (3D) Reduced Graphene Oxide(RGO)/Ni Foam.

A hybrid of ZnO nanorods grown onto three-dimensional (3D) reduced graphene oxide (RGO)@Ni foam (ZnO/RGO@NF) is synthesized by a facile hydrothermal method. The as-prepared hybrid material is physically characterized by SEM, XRD, Raman, and X-ray photoelectron spectroscopy (XPS). When the as-prepared 3D hybrid is investigated as a photocatalyst, it demonstrates significant high photocatalytic activity for the degradation of methylene blue (MB), rhodamine (RhB), and mixed MB/RhB as organic dye pollutants. In addition, the practical application and the durability of the as-prepared catalyst to degradation of malachite green (MG) in seawater are firstly assessed in a continuous flow system. The catalyst shows a high degradation efficiency and stable photocatalytic activity for 5 h continuous operation, which should be a promising catalyst for the degradation of organic dyes in seawater.

Design of encapsulated hosts and guests for highly efficient blue and green thermally activated delayed fluorescence OLEDs based on a solution-process.

The molecular aggregation and exciton-polaron interaction of the host-guest system were successfully restricted by efficient molecular encapsulation. The solution-processed blue and green TADF OLEDs have been realized with external quantum efficiencies above 23% by employing the encapsulated TADF host and guest as emission layers.

Highly Efficient All-Solution-Processed Fluorescent Organic Light-Emitting Diodes Based on a Novel Self-Host Thermally Activated Delayed Fluorescence Emitter.

Here, we conveniently designed and synthesized a self-host thermally activated delayed fluorescence (TADF) emitter, which can not only form a uniform thin film through wet-process, but also allow the subsequently deposition of electron transporting layer (ETL) by orthogonal solvent. By using this self-host material as emitter, the all-solution-processed multilayer TADF organic light emitting diodes (OLEDs) was successfully fabricated. The maximum current, power and external quantum efficiencies of this nondoped device are 46.3 cd A-1, 39.3 lm W1- and 15.5%, respectively, which are much higher than the values of all-solution-processed OLEDs based on tranditional fluorescence and even comparable to the TADF devices with vacuum-deposited ETL. Moreover, the device maintains the high efficiency of 42.9 cd A-1 and 39.0 cd A-1 at the luminance of 100 cd m-2 for display and 1000 cd m-2 for practical lighting. The high efficiency and small efficiency roll-off of the all-solution-processed fluorescent OLEDs can be attributed to the superiority of the newly designed self-host TADF emitter, which possesses the perfect electroluminescent property and sufficient solvent resistance at the same time.

One-Pot Synthesis of Concave Platinum-Cobalt Nanocrystals and Their Superior Catalytic Performances for Methanol Electrochemical Oxidation and Oxygen Electrochemical Reduction.

Exploring highly efficient electro-catalysts is of significant urgency for the widespread uptake of the direct methanol fuel cells (DMFCs). Pt-Co nanocrystals have attracted considerable attentions because of their superior catalytic performance toward both methanol oxidation and oxygen reduction in the preliminary assessments. This Research Article presents a Pt-Co bimetal catalyst that is synthesized through a facile coreduction strategy. The Pt-Co nanocrystals have concave cubic shape with a high uniform size of 7-9 nm and Pt-rich surfaces. The catalysis of the concave cubic Pt-Co nanoparticles toward both methanol electrochemical oxidation reaction (MOR) and oxygen electrochemical reduction reaction (ORR) is evaluated. In comparison with the commercial Pt/C catalyst (Johnson Matthey), the present concave cubic Pt-Co catalyst displays superior performances in not only catalytic activity but also durability. The concave Pt-Co catalyst also shows higher activities than spherical and cubic Pt-Co nanoparticles. The dramatic enhancement is mainly attributed to its alloyed composition, Pt-rich surface and the concave nanostructure. The results of our research indicate that the concave Pt-Co nanocrystal could be a promising catalyst for both MOR and ORR. The present work might also raise more concerns on exploiting morphology and composition of nanocrystal catalysts, which are expected to provide high catalytic performance in electrochemical reactions.

Photo-induced morphological winding and unwinding motion of nanoscrolls composed of niobate nanosheets with a polyfluoroalkyl azobenzene derivative.

Photo-responsive nanoscrolls can be successfully fabricated by mixing a polyfluoroalkyl azobenzene derivative and a niobate nanosheet, which is exfoliated from potassium hexaniobate. In this study, we have found that the photo-responsive nanoscroll shows a morphological motion of winding and unwinding, which is basically due to the nanosheet sliding within the nanoscroll, by efficient photo-isomerization reactions of the intercalated azobenzene in addition to the interlayer distance change of the nanoscrolls. The relative nanosheet sliding of the nanoscroll is estimated to be ca. 280 nm from the AFM morphology analysis. The distance of the sliding motion is over 20 times that of the averaged nanosheet sliding in the azobenzene/niobate hybrid film reported previously. Photo-responsive nanoscrolls can be expected to be novel photo-activated actuators and artificial muscle model materials.

High Durable Ternary Nanodendrites as Effective Catalysts for Oxygen Reduction Reaction.

Exploiting high catalytic activities and superior durability is significant for the lifetime and the cost of electro-catalysts for oxygen reduction reaction (ORR). Pt-Ni nanocrystals have attracted considerable attention owing to their exceptionally catalytic performance. However, the durability of Pt-Ni nanoparticles in acid media is still far below satisfaction. Consequently, improving the durability is extremely urgent for the application of Pt-Ni catalysts. To this end, we herein develop Pt-Ni-Ir ternary nanocrystals with dendritic shape, which are synthesized through a facile one-pot strategy. Such nanostructures featured with multibranches show an area specific activity of 1.58 mA cm(-2), seven times more than that of the commercial Pt/C catalyst (0.21 mA cm(-2)). More importantly, the dendritic Pt-Ni-Ir catalyst displays extraordinarily high durability. In contrast to the commercial Pt/C counterparts, which exhibit losses of 53.2% in EASA and 41% in area specific activity after 12 000 cycles of sweeping in the potential range of 0.6-1.1 V, only respective losses of 5.5% and 6% are detected for our dendritic Pt-Ni-Ir catalyst. The high activity and remarkable durability are mainly attributed to the dendritic morphology and the introduction of Ir. This work demonstrates that the Pt-Ni-Ir dendritic nanostructures are promising electro-catalysts for ORR.

Novel soft chemical method for optically transparent Ru(bpy)3-K4Nb6O17 thin film.

A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17).3H(2)O that possesses both (1) optical transparency and (2) ion-exchangeability under ambient conditions without calcination at high temperature. An optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film, a photoresponsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV(2+)-K(4)Nb(6)O(17) as a precursor. The optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin films have been characterized by X-ray diffraction, SEM, AFM, IR, and UV spectroscopies, as well as elemental analysis. The electrochemical behavior of the ITO/Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film electrode was studied; it also exhibits swift photoresponse in the visible region.

Characterization of a layered methylene blue/vanadium oxide nanocomposite and its application in a reagentless H2O2 biosensor.

Layered nanocomposite of methylene blue (MB)-intercalated vanadium oxide was obtained through a simple hydrothermal synthesis method using MB, V2O5, and NaI as starting materials. The intercalation reaction was proven to be successful using X-ray diffraction pattern. The MB-V2O5 nanocomposite was characterized using a scanning electron micrograph, infrared spectra, thermogravimetric analysis, UV spectra, and electrochemical measurements. The intercalated MB cations showed a fine diffusion-controlled electrochemical redox process and facilitated the immobilized horseradish peroxidase's (HRP) good catalytic reduction upon H2O2. The as-prepared MB-V2O5/HRP biosensor showed a linear response to H2O2 over a range from 2.0 × 10(-6) to 9.5 × 10(-5) M with a detection limit of 9.7 × 10(-7) M (S/N ratio = 3).

Facile assembly for fast construction of intercalation hybrids of layered double hydroxides with anionic metalloporphyrin.

Anionic manganese tetrasulfonatophenyl porphyrin (MnTSPP) has been intercalated into the interlamellar space of Mg-Al and Ni-Al layered double hydroxides (LDHs) through the exfoliation/restacking approach by using exfoliated LDH nanosheets and guest molecules as building blocks. The obtained hybrids were characterized by a variety of analytical techniques such as CHN analysis, XRD, FTIR, SEM, HRTEM, UV-vis spectroscopy and thermal analysis. Interlayer spacings determined from XRD patterns reveal a perpendicular orientation of the MnTSPP anions between the hyroxylated layers of both LDHs. The results of zeta potential measurements give information about the surface charge change of LDH nanoparticles associated with the spontaneous coassembly process. The catalytic performance of the heterogeneous catalysts MnTSPP/Mg-Al LDH2.0 and MnTSPP/Ni-Al LDH1.0 for the epoxidation of cyclohexene was investigated using molecular oxygen as an oxidant and isobutylaldehyde as a co-reductant. The intercalated hybrids appear to be promising catalysts owing to their good catalytic activity and selectivity.

Comparison of chitosan/starch composite film properties before and after cross-linking.

Unmodified and cross-linked chitosan/starch composite films were prepared using the solvent evaporation method. The properties of the films were studied to obtain useful information about the possible applications of composite films. FT-IR, SEM, and swelling property investigations show that the cross-linking agent glutaraldehyde reacts in the chitosan and starch blend. The compatibility of chitosan and starch blends before and after cross-linking was studied by UV-vis spectroscopy. The compatibility of the blends deteriorated after cross-linking. This finding was confirmed by the results of mechanical properties. The films show improved water barrier performance after cross-linking. The use of trace concentrations of glutaraldehyde in chitosan/starch films allows for possible application in the biomedical field.

A facile method for synthesis of N-doped ZnO mesoporous nanospheres and enhanced photocatalytic activity.

A facile synthesis route is reported for preparation of N-doped mesoporous ZnO nanospheres by a solvothermal treatment of Zn(NO3)2·6H2O which provides a source of both zinc and nitrogen. A variety of different spectroscopic and analytical techniques, such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis and X-ray photoelectron (XPS) spectroscopies were used to characterize the physicochemical properties of catalysts. The photocatalytic activities of the composites were evaluated by the degree of degradation of rhodamine B in aqueous solutions at room temperature with near-UV light irradiation. These nanocomposites exhibit higher photocatalytic activity compared with pure ZnO nanoparticles. The enhancement of photocatalytic activity of N-doped ZnO nanoparticles is mainly attributed to their absorption of more photons and reduced electron-hole pair recombination. Our one-step, environmentally friendly synthetic method may provide a new means of designing and synthesizing series of N-doped metal oxide semiconductors for use in photo-assisted catalytic reactions.

An artificial muscle model unit based on inorganic nanosheet sliding by photochemical reaction.

From the viewpoint of developing photoresponsive supramolecular systems in microenvironments to exhibit more sophisticated photo-functions even at the macroscopic level, inorganic/organic hybrid compounds based on clay or niobate nanosheets as the microenvironments were prepared, characterized, and examined for their photoreactions. We show here a novel type of artificial muscle model unit having much similarity with that in natural muscle fibrils. Upon photoirradiation, the organic/inorganic hybrid nanosheets reversibly slide horizontally on a giant scale, and the interlayer spaces in the layered hybrid structure shrink and expand vertically. In particular, our layered hybrid molecular system exhibits a macroscopic morphological change on a giant scale (~1500 nm) compared with the molecular size of ~1 nm, based on a reversible sliding mechanism.