ABSTRACT
The role of neutrophils in tumor initiation stage is rarely reported because of the lack of suitable models. We found that neutrophils recruited in early tumor nodules induced by subcutaneous inoculation of B16 melanoma cells were able to attack tumor cells by trogocytosis. The anti-tumor immunotherapy like peritoneal injection with TLR9 agonist CpG oligodeoxynucleotide combined with transforming growth factor ß2 inhibitor TIO3 could increase the trogocytic neutrophils in the nodules, as well as CD8+ T cells, natural killer (NK) cells, and their interferon-γ production. Local use of Cxcl2 small interfering RNA significantly reduced the number of neutrophils and trogocytic neutrophils in tumor nodules, as well as CD8+ T and NK cells, and also enlarged the nodules. These results suggest that neutrophils recruited early to the inoculation site of tumor cells are conducive to the establishment of anti-tumor immune microenvironment. Our findings provide a useful model system for studying the effect of neutrophils on tumors and anti-tumor immunotherapy.
ABSTRACT
Flexible full-textile pressure sensor is able to integrate with clothing directly, which has drawn extensive attention from scholars recently. But the realization of flexible full-textile pressure sensor with high sensitivity, wide detection range, and long working life remains challenge. Complex recognition tasks necessitate intricate sensor arrays that require extensive data processing and are susceptible to damage. The human skin is capable of interpreting tactile signals, such as sliding, by encoding pressure changes and performing complex perceptual tasks. Inspired by the skin, we have developed a simple dip-and-dry approach to fabricate a full-textile pressure sensor with signal transmission layers, protective layers, and sensing layers. The sensor achieves high sensitivity (2.16 kPa-1), ultrawide detection range (0 to 155.485 kPa), impressive mechanical stability of 1 million loading/unloading cycles without fatigue, and low material cost. The signal transmission layers that collect local signals enable real-world complicated task recognition through one single sensor. We developed an artificial Internet of Things system utilizing a single sensor, which successfully achieved high accuracy in 4 tasks, including handwriting digit recognition and human activity recognition. The results demonstrate that skin-inspired full-textile sensor paves a promising route toward the development of electronic textiles with important potential in real-world applications, including human-machine interaction and human activity detection.
ABSTRACT
Layered hybrid perovskites possess exceptional semiconductor features and structural versality, making them viable candidates for developing multifunctional dielectric phase-transition materials (PTMS). However, most PTMs based on layered hybrid perovskites still suffer from Pb toxicity and low operating temperature. The recently developed hybrid double perovskites provide a new routine to designed PTMs with desired working performance and environment-friendly chemical compositions. Herein, using rigid aromatic cations as templates, we have successfully synthesized a novel double perovskite (benzylammonium)4 AgBiBr8 (1), which consists of corner-sharing AgBr6 and BiBr6 layers and benzylammonium cations. Notably, 1 exhibits a high-temperature first-order reversible solid-state phase transition at 383/387â K (cooling/heating) and switchable dielectric performance around the temperature. Compared with the soft organic chain version of the compound, the phase transition temperature of 1 shows a large enhancement of 99â K, validating the correctness of the designing strategy. In addition, 1 also exhibits semiconductor characteristics with a calculated bandgap of 2.34â eV and an optical bandgap of 2.29â eV. Remarkably, the single crystal photodetector of 1 shows a low dark current (2.12×10-13 â A), a high on/off ratio (1.77×103 ), and a fast response (τrise =125â µs and τdecay =419â µs). Such a lead-free phase transition material combined with semiconductor properties provides a new strategy to develop environmentally friendly multifunctional materials.
ABSTRACT
Introduction: Transforming growth factor ß2 (TGF-ß2), also known as glioma-derived T-cell suppressor factor, is associated with the impairment of tumor immune surveillance. Therefore, blocking TGF-ß2 signaling probably be a feasible strategy to develop a novel type of adjuvant for glioma vaccines to enhance antitumor immunity. Methods: A TGF-ß2 inhibitory oligodeoxynucleotide, TIO3, was designed with sequences complementary to the 3' untranslated region of TGF-ß2 mRNA. The expression of TGF-ß2 and MHC-I was detected by qPCR, western and flow cytometry in vitro. All the percentage and activation of immune cells were detected by flow cytometry. Subsequently, TIO3 was formulated with Glioma cell lysate (TCL) and investigated for its antitumor effects in GL261 murine glioma prophylactic and therapeutic models. Results: TIO3 could efficiently downregulate the expression of TGF-ß2 while increase the MHC-I's expression in GL261 and U251 glioma cells in vitro. Meanwhile, TIO3 was detected in mice CD4+ T, CD8+ T, B and Ly6G+ cells from lymph nodes after 24 hours incubation. Moreover, TCL+TIO3 vaccination significantly prolonged the survival of primary glioma-bearing mice and protected these mice from glioma re-challenge in vivo. Mechanistically, TCL+TIO3 formulation strongly evoke the antitumor immune responses. 1) TCL+TIO3 significantly increased the composition of CD4+ and CD8+ T cells from draining lymph nodes while promoted their IFN-γ production and reduced the expression of TGF-ß2 and PD1. 2) TCL+TIO3 activated the NK cells with the elevation of CD69 or NKG2D expression and PD1 reduction. 3) TCL+TIO3 increased the glioma-specific lysis CTLs from spleen. 4) TCL+TIO3 downregulated PD-L1 expression in glioma tissues and in Ly6G+ cells among glioma-infiltrating immune cells. Conclusion: TIO3 is a promising adjuvant for enhancing TCL-based vaccines to produce a more vigorous and long-lasting antitumor response by interfering with TGF-ß2 expression.
Subject(s)
Glioma , Transforming Growth Factor beta2 , Animals , Mice , Transforming Growth Factor beta2/genetics , Oligodeoxyribonucleotides , Glioma/pathology , T-Lymphocytes, Cytotoxic , CD8-Positive T-Lymphocytes , Adjuvants, Immunologic , Adjuvants, PharmaceuticABSTRACT
Organic-inorganic hybrid perovskites carry unique semiconducting properties and advanced flexible crystal structures. These characteristics of organic-inorganic hybrid perovskites create a promising candidacy for circularly polarized light (CPL) detection. However, CPL detections based on chiral perovskites are limited to UV and visible wavelengths. The natural quantum well structures of layered hybrid perovskites generate strong light-matter interactions. This makes it possible to achieve near-infrared (NIR) CPL detection via two-photon absorption in the sub-wavelength region. In this study, cooperative strategies of dimension increase and mixed spacer cations are used to obtain a pair of chiral multilayered perovskites (R-ß-MPA)EA2 Pb2 Br7 and (S-ß-MPA)EA2 Pb2 Br7 (MPA = methylphenethylammonium and EA = ethylammonium). The distinctive bi-cations interlayer and multilayered inorganic skeletons provide enhanced photoconduction. Moreover, superior photoconduction leads to the prominent NIR CPL response with a responsivity up to 8.1 × 10-5 A W-1 . It is anticipated that this work can serve as a benchmark for the fabrication and optimization of efficient NIR CPL detection by simple chemical design.
ABSTRACT
Tumor immunotherapies have shown promising antitumor effects, especially immune checkpoint inhibitors (ICIs). However, only 12.46% of the patients benefit from the ICIs, the rest of them shows limited effects on ICIs or even accelerates the tumor progression due to the lack of the immune cell infiltration and activation in the tumor microenvironment (TME). In this study, we administrated a combination of Toll-like receptor 9 (TLR9) agonist CpG ODN and Transforming growth factor-ß2 (TGF-ß2) antisense oligodeoxynucleotide TIO3 to mice intraperitoneally once every other day for a total of four injections, and the first injection was 24 h after LLC cell inoculation. We found that the combination induced the formation of TME toward the enrichment and activation of CD8+ T cells and NK cells, accompanied with a marked decrease of TGF-ß2. The combined therapy also effectively inhibited the tumor growth and prolonged the survival of the mice, even protected the tumor-free mice from the tumor re-challenge. Both of CpG ODN and TIO3 are indispensable, because replacing CpG ODN with TLR9 inhibitor CCT ODN showed no antitumor effect, CpG ODN or TIO3 alone did not lead to ideal antitumor results. This effect was possibly initiated by the activation of dendritic cells at the tumor site. This systemic antitumor immunotherapy with a combination of the two oligonucleotides (an immune stimulant and an immunosuppressive cytokine inhibitor) before the tumor formation may provide a novel strategy for clinical prevention of the postoperative tumor recurrence.
Subject(s)
Lung Neoplasms , Toll-Like Receptor 9 , Animals , Mice , Toll-Like Receptor 9/agonists , Transforming Growth Factor beta2 , CD8-Positive T-Lymphocytes , Neoplasm Recurrence, Local/drug therapy , Adjuvants, Immunologic/therapeutic use , Oligodeoxyribonucleotides/pharmacology , Oligodeoxyribonucleotides/therapeutic use , Immunotherapy/methods , Tumor MicroenvironmentABSTRACT
Chiral hybrid perovskites (CHPs), aggregating chirality and favorable semiconducting properties in one, have taken a prominent position in direct circularly polarized light detection (CPL). However, passive high circular polarization sensitivity (gres) photodetection in CHPs is still elusive and challenging. Benefitting from efficient control and turning of carrier transport of CHPs by dimensional engineering, here, we unprecedentedly proposed a chain-to-layer dimensionality engineering to realize high-gres passive photodetection. Two novel 2D layered CHPs (R/S-PPA)EAPbBr4 (2R/2S) (PPA = 1-phenylpropylamine, EA = ethylammonium) are successfully synthesized by alloying an EA cation with small steric hindrance into the chained CHPs (R/S-PPA)PbBr3 (1R/1S). Particularly, compared with the neglectable photoresponse in 1R, the obtained 2R by chain-to-layer dimensionality engineering gives rise to an excellent photoconductivity and robust polar photovoltage effect (PPE) with a giant open-circuit voltage of 2.5 V. Furthermore, such PPE promotes realizing an impressive gres in 2R up to 0.42 at zero bias because of the independent separation of photoexcited carriers, which is the highest value among the reported layered chiral perovskites. This work paves the way for the vigorous development of higher dimensional CHPs and will reveal their applications in the field of passive high-gres CPL detection.
ABSTRACT
Circularly polarized light (CPL) detection has sparked overwhelming research interest for its widespread chiroptoelectronic and spintronic applications. Ferroelectric materials, especially emerging layered hybrid perovskite ferroelectrics, exhibiting striking bulk photovoltaic effect (BPVE) present significant possibilities for CPL detection by a distinctive working concept. Herein, for the first time, we demonstrate the realization of robust angular anisotropy of CPL detection in a new layered hybrid perovskite ferroelectric crystal (CPA)2FAPb2Br7 (1, CPA is chloropropylammonium, FA is formamidinium), which crystallized in an optically active achiral polar point group. Benefiting from the notable spontaneous polarization (5.1 µC/cm2) and excellent semiconducting characteristics, single crystals of 1 exhibit remarkable BPVE under light illumination, with a high current on/off switching ratio (ca. 103). More intriguingly, driven by the angular carrier drift originating from spin-dependent BPVE in optically active ferroelectrics, 1 displays highly sensitive self-powered CPL detection performance, showing a robust angular anisotropy factor up to 0.98, which is far more than those achieved by material intrinsic chirality. This work provides an unprecedented approach for realizing highly sensitive CPL detection, which sheds light on the further design of optically active ferroelectrics for chiral photonic applications.
ABSTRACT
We report the self-assembly of 2D double perovskite (BLA)2 CsAgBiBr7 (BLA=benzylammonium) on 3D Cs2 AgBiBr6 crystals, providing the first demonstration of polarization-sensitive photodetection using lead-free double perovskite heterocrystals (HCs). The (BLA)2 CsAgBiBr7 /Cs2 AgBiBr6 HC successfully combines the anisotropy of 2D double perovskites with the well-defined interface provided by heterogeneous integration. Driven by the built-in electric field in junction, photodetectors of HCs exhibit unique polarization dependence of zero-bias photocurrent with a large anisotropy ratio up to 9, which is 6â times amplified as compared to the pristine 2D (BLA)2 CsAgBiBr7 . More importantly, the present devices can remain polarization-sensitive with incident light intensity down to the nW cm-2 level. Our study on lead-free hybrid perovskite HCs marks a step toward establishing robust material foundations for fundamental scientific investigations and the development of optoelectronic devices.
ABSTRACT
Development of new mechanochromic luminescent (MCL) materials from aggregation-induced emission luminogens (AIEgens) has attracted wide attention due to their potential application in multiple areas. However, rational design and crafting of new MCL materials from the simple AIEgens skeleton is still a big challenge because of the undesirable concentration quenching effect. In this study, we have constructed a new class of MCL materials by adding one phenyl as a new rotator and incorporating one pair of electron donor (D) and acceptor (A) into the system of rofecoxib skeleton. This strategy endowed the compounds (Y1-Y8) with tunable emission behavior and some of them with the AIE effect and reversible MCL behavior. These properties may be caused by the highly twisted conformation and loosely molecular packing modes, which were elucidated clearly by analyzing the data of single-crystal X-ray diffraction, powder X-ray diffraction, and differential scanning calorimetry. Further investigation revealed that Y7 displayed acidochromic property due to the protonation of the nitrogen atom. Moreover, Y7, as a typical compound, showed its potential applications in the area of anticounterfeiting, pH sensor, and LD-specific bioimaging.
Subject(s)
Fluorescent Dyes , Luminescence , Fluorescent Dyes/chemistry , Lactones , SulfonesABSTRACT
2D van der Waals materials are widely explored for in-plane polarized light detection owing to their distinctive in-plane anisotropic feature. However, most of these polarized light-sensitive devices root in their low symmetry of in-plane structure and work depending on external power sources, which greatly impedes the simplification of integrated devices and sustainable development. Bulk photovoltaic effect (BPVE), which separates photoexcited carriers via built-in electric field without an external power source and shows an angle-dependence on light polarization, is promising for self-powered polarized light detection to break through the restriction of in-plane anisotropy. Herein, a 2D lead-free van der Waals perovskite (Cl-PMA)2 CsAgBiBr7 (1, Cl-PMA = 4-Chlorobenzylamine) is successfully designed through the dimension reduction strategy. 1 exhibits BPVE with an open-circuited photovoltage up to ≈0.5 V. Driven by the BPVE, self-powered in-plane polarized light detection with a large polarization ratio of 1.3 is obtained for 1. As far as it is known, the first in-plane polarized light detection in hybrid perovskites based on BPVE is realized here. This work highlights the strategy of designing lead-free hybrid perovskite with BPVE and opens an avenue for exploiting in-plane highly sensitive polarized light detection in 2D van der Waals materials.
ABSTRACT
Halide perovskite heterocrystals, composed of distinct perovskite single crystals, have generated great interest for both fundamental research and applied device designs. One of the key advantages of using such a heterocrystal is its built-in electric potential, which enhances charge transport and suppresses the noise in the solid-state devices. On the basis of this strategy, high-performance optoelectronic devices (e.g., X-ray detectors) have been successfully demonstrated. However, the toxicity of metal cations (Pb) in those reported heterocrystals hinders their wider applications. Thus, developing lead-free halide perovskite heterocrystals is significant but remains highly challenging. Here, we report a solution-processed in situ heteroepitaxial approach that enables us to create the first lead-free halide perovskite heterocrystal, (BA)2CsAgBiBr7/Cs2AgBiBr6(BA = n-butylammonium), with dimensions of up to 10 × 7 × 6 mm3. The as-grown heterocrystals have high crystalline quality and present near atomically sharp interfaces. More excitingly, the (BA)2CsAgBiBr7/Cs2AgBiBr6 heterogeneous integration allows the formation of a built-in electric potential in the junction, which triggers spontaneous charge separation/transport. Consequently, X-ray detectors using the heterocrystals can operate in a self-driven mode and exhibit an impressive sensitivity (206 µC Gy-1 cm-2) superior to that of the pristine Cs2AgBiBr6 crystal detectors, an ultralow dark current, and operational stability. Our findings provide the first demonstration of lead-free halide perovskite heterocrystals and may open up opportunities for a host of sustainable and miniaturized perovskite optoelectronic devices.
ABSTRACT
Chiral hybrid organic-inorganic perovskites (HOIPs) have been well developed for circularly polarized light (CPL) detection, while new members that target at solar-blind ultraviolet (UV) region remain completely unexplored. Here, an effective design strategy to demonstrate circular polarization-sensitive solar-blind UV photodetection by growing wide-bandgap chiral HOIP [(R)-MPA]2 PbCl4 ((R)-MPA = methylphenethylammonium) single crystals onto silicon wafers, with well-defined heterostructures, is reported. The solid mechanical and electrical connection between the chiral HOIP and silicon wafer results in strong built-in electric field at heterojunction, providing a desirable driving force for separating/transporting carriers generated under CPL excitation at 266 nm. Unexpectedly, during such a transport process, not only the chirality of HOIP crystal is transferred to the heterostructure, but also the circular polarization sensitivity is significantly amplified. Consequently, anisotropy factor of the resultant detectors can reach up to 0.4 at zero bias, which is much higher than that of the pristine single-phase chiral HOIP (≈0.1), reaching the highest among the reported CPL-UV photodetectors. As far as we know, the integration of chiral HOIP crystals with silicon technology is unprecedent, which paves a way for designing boosted-performance CPL detectors in solar-blind UV region as well as for other advanced optoelectronic devices.
ABSTRACT
Due to the breakthrough development of layered hybrid perovskites, the multilayered hybrid double perovskites have emerged as outstanding semiconducting materials owing to their environmental friendliness and superior stability. Despite recent booming advances, the realization of above-room temperature ferroelectricity in this fascinating family remains a huge challenge. Herein, when the molecular design strategy of aromatic cation alloying is applied, an above-room temperature "green" bilayered hybrid double perovskite photoferroelectric, (C6H5CH2NH3)2CsAgBiBr7 (BCAB), is successfully developed with a notable saturation polarization of 10.5 µC·cm-2 and high-Curie temperature (Tc â¼ 483 K). Strikingly, such a Tc achieves a new record in multilayered hybrid perovskite ferroelectrics, which extends the ferroelectric working temperature to a high level. Further computational investigation reveals that the high-Tc originated from the high phase-transition energy barrier switched by the rotation of the aromatic cation in the confined environment of the inorganic layers. In addition, benefiting from the attractive polarization and remarkable photoelectric properties, a bulk photovoltaic effect (BPVE) with a prominent zero-bias photocurrent (2.5 µA·cm-2) is achieved. As far as we know, such a high-Tc multilayered hybrid double perovskite ferroelectric is unprecedented, which sheds light on the rational design of an environmental photoferroelectric for high performance photoelectric devices.
ABSTRACT
Circularly polarized light (CPL)-sensitive direct detection is attracting increasing attention owing to its various optical technology applications and ultracompact device structures. However, current CPL-sensitive direct detection mainly focuses on a single mode, whereas the visible-near-infrared (vis-NIR) dual-modal detection, which is important for improving device sensitivity and night-vision performance, still remains to be explored. Here, for the first time, the vis-NIR dual-modal CPL-sensitive direct detection is presented in bulk single crystals of two-dimensional chiral perovskite (R-BPEA)2PbI4 (R-BPEA = (R)-1-(4-bromophenyl)ethylammonium). Benefiting from the strong light-matter interaction of the layered structure, (R-BPEA)2PbI4 shows a two-photon absorption (TPA) coefficient of up to 55 cm/MW, which almost falls around the highest value of 2D hybrid perovskites. Notably, (R-BPEA)2PbI4 exhibits a high vis-NIR dual-modal CPL-sensitive direct detecting performance under both visible light (520 nm) and NIR light (800 nm), with the on/off ratios of current higher than 103, and the anisotropy factors for photocurrent higher than 0.1. This work will shed light on the design of new chiral semiconductors with a large TPA coefficient and promote their applications in vis-NIR dual-modal CPL-sensitive direct detection.
ABSTRACT
Chiral hybrid perovskites have brought an unprecedented opportunity for circularly polarized light (CPL) detection. However, the circular polarization sensitivity of such a detector remains extremely low because of the high exciton recombination rate in those single-phase hybrid perovskites. Here, a heterostructure construction strategy is proposed to reduce the electron-hole recombination rate in a chiral hybrid perovskite and achieve CPL detectors with greatly amplified circular polarization sensitivity. A heterostructure crystal, namely, [(R)-MPA]2MAPb2I7/MAPbI3 ((R)-MPA = (R)-methylphenethylamine, MA = methylammonium), has been successfully created by integrating a chiral two-dimensional (2D) perovskite with its three-dimensional counterpart via solution-processed heteroepitaxy. Strikingly, the sharp interface of the as-grown heterostructure crystal facilitates the formation of a built-in electric field, enabling the combined concepts of charge transfer and chirality transfer, which effectively reduces the recombination probability for photogenerated carriers while retaining chiroptical activity of chiral 2D perovskite. Thereby, the resultant CPL detector exhibits significantly amplified circular polarization sensitivity at zero bias with an impressive anisotropy factor up to 0.67, which is about six times higher than that of the single-phase [(R)-MPA]2MAPb2I7 (0.1). As a proof-of-concept, the strategy we presented here enables a novel path to modulate circular polarization sensitivity and will be helpful to design chiral hybrid perovskites for advanced chiroptical devices.
ABSTRACT
High-Curie-temperature (Tc) ferroelectrics have exhibited broad applications in optoelectronic devices. Recently, two-dimensional multilayered perovskite ferroelectrics with excellent photoelectric attributes are attracting increasing interest as new systems of photoferroelectrics. However, the effective tuning of the Tc value of a multilayered perovskite photoferroelectric system still remains a huge challenge. Here, by a halogen substitution strategy to introduce bromine atoms on n-propylamine cations, the hybrid perovskite photoferroelectric (3-bromopropylaminium)2(formamidinium)Pb2Br7 (BFPB) with a high Tc value (348.5 K) was obtained. It is notable that BFPB adopts a two-dimensional bilayered inorganic framework, with tight linking to the organic cation by C-Br···Br-Pb halogen···halogen interactions and N-H···Br hydrogen bonds. Intriguingly, in comparison with the prototypical compound (n-propylaminium)2(formamidinium)Pb2Br7, a remarkable augmentation of 85.2 K in the resulting Tc value of BFPB is clearly observed, which further broadens the temperature range of its application. In combination with the remarkable ferroelectric and semiconducting attributes, the reversible bulk photovoltaic effect was realized in single crystals of BFPB. This finding can not only enhance the hybrid perovskite ferroelectric family but also further promote the photoelectric application of ferroelectrics.
ABSTRACT
Through a functional unit-transmutation strategy, a fatigue-free layered hybrid perovskite ferroelectric (C6 H5 CH2 NH3 )2 CsPb2 Br7 (BCPB) has been developed, which demonstrates stable spontaneous polarization (Ps ) of 6.5â µC cm-2 and high Curie temperature up to 425â K. Meanwhile, BCPB shows splendid bulk photovoltaic effect (BPVE) properties with noticeable zero-bias photocurrent density (5 µA cm-2 ), and high on/off switching ratio of current (over 3×105 ); these merits even overmatch the most known ferroelectric semiconductor BiFeO3 . The unique structure with self-regulated net electrical charged layers gives rise to the fatigue-free feature of Ps and BPVE (no significant fatigue after 108 polarity switching cycles), promoting the potential applications of BCPB in photovoltaic non-volatile memories. This work offers an efficient approach for exploring fatigue-free semiconducting ferroelectrics as well as excavates their further applications in next-generation electronic devices.
ABSTRACT
Benefiting from their structural flexibility and solution processability, organic-inorganic metal halide hybrids with efficient white-light emission present a great promise for solid-state lighting and display applications. However, most of these reported high-performance single-component white-light materials contain lead. Herein, we report a "green" organic zinc halide, [(N-AEPz)ZnCl4]Cl (1; N-AEPz = N-aminoethylpiperazine), exhibiting prominent bluish-white-light emission with a photoluminescence quantum efficiency as high as 11.52%. Such a value is among the highest in the reported metal halide white-light emitters. Mechanism studies disclose that the broad-band emission is ascribed to the synergistic work of organic salts and inorganic clusters. This work would incent research on single-component white-light materials for next-generation display and lighting technologies.
ABSTRACT
A new iodide layered double perovskite (C3H9NI)4AgBiI8 (IPAB) has been developed based on a short-chain spacer cation, which is the first homologous compound in iodide double perovskites that adopt the Ruddlesden-Popper structure type. Importantly, IPAB is a promising environmentally friendly alternative to the recently rapidly progressing lead halide semiconductors owing to its narrow direct-bandgap of 1.87 eV and excellent stability.