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1.
Food Chem ; 462: 141024, 2025 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-39217751

RESUMEN

With the aim of expanding the potential application scope of mulberries, eleven pH-switchable deep eutectic solvents were screened for the ultrasonic-assisted extraction of mulberry polysaccharides, and a salt/salt aqueous two-phase system was constructed for the efficient separation of mulberry polysaccharides by regulating the system pH. DES-9 (tetraethylammonium chloride: octanoic acid molar ratio = 1: 2) with a critical response pH value of approximately 6.1 was concluded to be the best extraction solvent for extracting mulberry polysaccharides. A maximum polysaccharide extraction yield of 270.71 mg/g was obtained under the optimal conditions. The maximum polysaccharide extraction efficiency was 78.09 % for the pH-driven tetraethylammonium chloride/K2HPO4 aqueous two-phase system. An acidic ß-pyran mulberry polysaccharide with a low-molecular weight of 9.26 kDa and a confirmed monosaccharide composition were obtained. This efficient and environmentally friendly polysaccharide separation method offers a new approach for the efficient extraction and utilization of other plant polysaccharides.


Asunto(s)
Disolventes Eutécticos Profundos , Morus , Extractos Vegetales , Polisacáridos , Morus/química , Polisacáridos/química , Polisacáridos/aislamiento & purificación , Concentración de Iones de Hidrógeno , Extractos Vegetales/química , Extractos Vegetales/aislamiento & purificación , Disolventes Eutécticos Profundos/química , Fraccionamiento Químico/métodos , Peso Molecular , Frutas/química , Cloruro de Sodio/química
2.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124993, 2025 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-39159512

RESUMEN

BODIPY-based chemosensors are widely used owing to merits like good selectivity, high fluorescence quantum yield, and excellent optical stability. As such, a pH-switchable hydrophilic fluorescent probe, BODIPY-PY-(SO3Na)2, was developed for detection of Fe3+ ion in aqueous solutions. BODIPY-PY-(SO3Na)2 revealed strong fluorescence intensity and was responsive to pH value in the range of 6.59-1.96. Additionally, BODIPY-PY-(SO3Na)2 showed good selectivity and sensitivity towards Fe3+. A good linear relationship for Fe3+ detection was obtained from 0.0 µM to 50.0 µM with low detecting limit of 6.34 nM at pH 6.59 and 2.36 nM at pH 4.32, respectively. The response to pH and detection of Fe3+ induced obvious multicolor changes. BODIPY-PY-(SO3Na)2 can also be utilized to quantitatively detect Fe3+ in real water sample. Different mechanisms of Fe3+ detection at investigated pH values were unraveled through relativistic density functional theory (DFT) calculations in BODIPY-PY-(SO3Na)2 and experiments of coexisting cations, anions and molecules. These results enabled us to gain a deeper understanding of the interactions between BODIPY-PY-(SO3Na)2 and Fe3+ and provide valuable fundamental information for design of efficient multicolor chemosensors for Fe3+ as well.

3.
Adv Sci (Weinh) ; : e2407588, 2024 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-39380495

RESUMEN

Adhesives that excel in wet or underwater environments are critical for applications ranging from healthcare and underwater robotics to infrastructure repair. However, achieving strong attachment and controlled release on difficult substrates, such as those that are curved, rough, or located in diverse fluid environments, remains a major challenge. Here, an octopus-inspired adhesive with strong attachment and rapid release in challenging underwater environments is presented. Inspired by the octopus's infundibulum structure, a compliant, curved stalk, and an active deformable membrane for multi-surface adhesion are utilized. The stalk's curved shape enhances conformal contact on large-scale curvatures and increases contact stress for adaptability to small-scale roughness. These synergistic mechanisms improve contact across multiple length scales, resulting in switching ratios of over 1000 within ≈30 ms with consistent attachment strength of over 60 kPa on diverse surfaces and conditions. These adhesives are demonstrated through the robust attachment and precise manipulation of rough underwater objects.

4.
Food Chem ; 463(Pt 2): 141170, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39288456

RESUMEN

When conventional solvents such as water, methanol, ethanol, hexane, petroleum ether, etc., are used to extract active ingredients from natural resources, an evaporation process is required to remove solvent from active ingredients, which not only consumes huge amounts of energy, but also causes harm to human health and the environment. The CO2-responsive switchable hydrophilic solvent (SHS) based on amines and water is an emerging, green and recyclable solvent, which not only has high extraction efficiency of active ingredients, but also can remove solvent from active ingredients without evaporation process. This paper reviews the research progress of amine-based SHS in the extraction of bioactive ingredients from natural resources. The process flow, extraction mechanism, critical influencing factors, recovery of amines and latest applications have been summarized. On this basis, some shortcomings of amine-based SHS are also pointed out. Finally, the improvement directions of amine-based SHS extraction in the future is prospected.

5.
Acta Biomater ; 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39243836

RESUMEN

Photodynamic therapy (PDT) has attracted widespread attention from researchers as an emerging cancer treatment method. There have been many reports on various types of NIR-II photosensitizers for imaging and treatment of tumor sites. However, there are few reports on the development of NIR-II organic small molecule photosensitizers that have intelligent response to the tumor microenvironment, precise imaging, real-time treatment, and high biocompatibility. In this work, we developed a series of NIR-II photosensitizers (RBTs) with near-infrared excitation, good photostability, and large Stokes shift. Among them, RBT-Br exhibited higher reactive oxygen species (ROS) generation efficiency due to the introduction of halogen heavy atoms to enhance intersystem crossing (ISC). It is noteworthy that RBT-Br can generate singlet oxygen (1O2) and superoxide anion radicals (•O2-) simultaneously under 730 nm laser. Subsequently, we used molecular engineering technology to construct three pH-responsive NIR-II photosensitizers (RBT-pHs) by utilizing the closure of the lactam ring, among which RBT-pH-1 (pKa = 6.78) is able to be directionally activated under the stimulation of tumor micro-acid environment, with its fluorescence emission window reaching 933 nm. Subsequently, RBT-pH-1 NPs encapsulated in DSPE-mPEG5k were applied for PDT treatment of mouse tumors. The results showed that RBT-pH-1 NPs were activated by the acidic tumor microenvironment and generated ROS under laser excitation, exhibiting precise tumor imaging and significant tumor growth inhibition. We look forward to these multifunctional NIR-II organic small molecule photosensitizers providing a more efficient approach for clinical treatment of tumors. STATEMENT OF SIGNIFICANCE: A reversible pH-switchable NIR-II nano-photosensitizer RBT-pH-1 NPs (pKa = 6.76) is developed for precise imaging and PDT therapy of mouse tumors, which can be effectively used for targeted enrichment and activation of tumor micro-acid environments. The results show that this NIR-II photosensitizer generates ROS through tumor micro-acid environment stimulation and laser triggering, showing precise tumor imaging guidance and significant tumor growth inhibition.

6.
Biosens Bioelectron ; 266: 116736, 2024 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-39226751

RESUMEN

In photoelectrochemical (PEC) sensors, traditional detection modes such as "signal-on", "signal-off", and "polarity-switchable" limit target signals to a single polarity range, necessitating novel design strategies to enhance the operational scope. To overcome this limitation, we propose, for the first time, a "polarity-transcendent" design concept that enables a continuous response across the polarity spectrum, significantly broadening the sensor's concentration detection range. This concept is exemplified in our new "background-enhanced signal-off polarity-switchable" (BESOPS) mode, where the model analyte let-7a activates a cascade shearing reaction of a DNAzyme walker in conjunction with CRISPR/Cas12a, quantitatively peeling off Cu2O-H2 strands at the Cu2O/TiO2 electrode interface to expose the TiO2 surface. This exposure generates an anodic photocurrent at the expense of the cathodic photocurrent from Cu2O/TiO2, facilitating a seamless transition of the target signal from cathodic to anodic. Through systematic experiments and comparative analyses, the BESOPS sensor demonstrates highly sensitive and precise quantification of let-7a, with a detection limit of 2.5 aM and a broad operating range of 10 aM to 10 nM. Its performance exceeds most reported sensor platforms, highlighting the significant potential of our polarity-transcendent design in expanding the operational range of PEC sensors. This innovative approach paves the way for developing next-generation PEC sensors with enhanced applicability and heightened sensitivity in various critical fields.


Asunto(s)
Técnicas Biosensibles , Cobre , Técnicas Electroquímicas , Límite de Detección , Titanio , Técnicas Biosensibles/instrumentación , Técnicas Electroquímicas/métodos , Cobre/química , Titanio/química , MicroARNs/análisis , Humanos , Diseño de Equipo , Sistemas CRISPR-Cas , Electrodos
7.
J Colloid Interface Sci ; 678(Pt C): 690-703, 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39307058

RESUMEN

Photodynamic therapy (PDT) employs reactive oxygen species (ROS) from a photosensitizer (PS) under light, inhibiting multi-drug resistance in bacteria. However, hypoxic conditions in infection sites and biofilms challenge PDT efficiency. We developed fluorinated small molecular micelles (PF-CBMs) as PS carriers to address this, relieving hypoxia and enhancing PS penetration into biofilms. Perfluorocarbons in PF-CBMs transport more oxygen due to their excellent oxygen-dissolving capability. Fluorination enhances loading capacity and serum stability, reduces premature release, and improves cellular uptake, to improve PDT efficacy. PF-CBMs, with acid-induced surface charge transformation, exhibit superior biofilm penetration, resulting in increased antibiofilm activity of PDT. Compared to fluorine-free micelles (PC-CBMs), PF-CBMs demonstrate better serum stability, higher drug loading, and reduced premature release, leading to significantly improved antibacterial efficacy in vitro and in vivo. In conclusion, fluorinated micelles with surface charge reversal enhance PDT for antibacterial and antibiofilm applications.

8.
J Control Release ; 375: 478-494, 2024 Sep 20.
Artículo en Inglés | MEDLINE | ID: mdl-39293528

RESUMEN

Nanoparticles fabricated to deliver anticancer drugs are usually designed to present optimized tumor penetration and cell internalization. However, there are some barriers and difficulties with most current technologies. Herein, size and charge switchable polyamidoamine (PAMAM) megamers (SChPMs) were prepared for the delivery of doxorubicin (DOX). SChPMs were fabricated by connecting PAMAM dendrimers with pH-sensitive bonds and surface PEGylation. At pH 7.4, the size and surface charge of these nanocarriers were approximately 100 nm and + 0.75 mV, but at the acidic extracellular pH of tumor cells (pH 6.5), their size were reduced dramatically (15 nm) and their surface charge increased to +6.7 mV. Cell studies confirmed that alteration of the size and surface charge enhanced their penetration into multicellular spheroids and cell internalization. These megamers, in addition to delivering the drug to the deeper areas of the tumor, could powerfully overcome physiological resistance to anthracycline-based drugs. The nanocarrier revealed enhanced antitumoral activity in animal studies. Toxicology studies and histopathological assessments of vital tissues of 4 T1 tumor bearing mice indicated minimal tissue damage when DOX-loaded SChPMs (DSChPMs) were used. It can be concluded that the versatile and agile nanocarriers developed in this study could be considered for further investigations into their clinical application.

9.
J Imaging Inform Med ; 2024 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-39322814

RESUMEN

Acute leukemia is characterized by the swift proliferation of immature white blood cells (WBC) in the blood and bone marrow. It is categorized into acute lymphoblastic leukemia (ALL) and acute myeloid leukemia (AML), depending on whether the cell-line origin is lymphoid or myeloid, respectively. Deep learning (DL) and artificial intelligence (AI) are revolutionizing medical sciences by assisting clinicians with rapid illness identification, reducing workload, and enhancing diagnostic accuracy. This paper proposes a DL-based novel BSNEU-net framework to detect acute leukemia. It comprises 4 Union Blocks (UB) and incorporates block feature map distortion (BFMD) with switchable normalization (SN) in each UB. The UB employs union convolution to extract more discriminant features. The BFMD is adapted to acquire more generalized patterns to minimize overfitting, whereas SN layers are appended to improve the model's convergence and generalization capabilities. The uniform utilization of batch normalization across convolution layers is sensitive to the mini-batch dimension changes, which is effectively remedied by incorporating an SN layer. Here, a new dataset comprising 2400 blood smear images of ALL, AML, and healthy cases is proposed, as DL methodologies necessitate a sizeable and well-annotated dataset to combat overfitting issues. Further, a heterogeneous dataset comprising 2700 smear images is created by combining four publicly accessible benchmark datasets of ALL, AML, and healthy cases. The BSNEU-net model achieved excellent performance with 99.37% accuracy on the novel dataset and 99.44% accuracy on the heterogeneous dataset. The comparative analysis signifies the superiority of the proposed methodology with comparing schemes.

10.
Nanomicro Lett ; 17(1): 19, 2024 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-39325078

RESUMEN

The synthesis of carbon supporter/nanoscale high-entropy alloys (HEAs) electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engineering of conductive/dielectric genes. Electron migration modes within HEAs as manipulated by the electronegativity, valence electron configurations and molar proportions of constituent elements determine the steady state and efficiency of equivalent dipoles. Herein, enlightened by skin-like effect, a reformative carbothermal shock method using carbonized cellulose paper (CCP) as carbon supporter is used to preserve the oxygen-containing functional groups (O·) of carbonized cellulose fibers (CCF). Nucleation of HEAs and construction of emblematic shell-core CCF/HEAs heterointerfaces are inextricably linked to carbon metabolism induced by O·. Meanwhile, the electron migration mode of switchable electron-rich sites promotes the orientation polarization of anisotropic equivalent dipoles. By virtue of the reinforcement strategy, CCP/HEAs composite prepared by 35% molar ratio of Mn element (CCP/HEAs-Mn2.15) achieves efficient electromagnetic wave (EMW) absorption of - 51.35 dB at an ultra-thin thickness of 1.03 mm. The mechanisms of the resulting dielectric properties of HEAs-based EMW absorbing materials are elucidated by combining theoretical calculations with experimental characterizations, which provide theoretical bases and feasible strategies for the simulation and practical application of electromagnetic functional devices (e.g., ultra-wideband bandpass filter).

11.
Mikrochim Acta ; 191(10): 602, 2024 09 16.
Artículo en Inglés | MEDLINE | ID: mdl-39284945

RESUMEN

A fluorescent and photoelectrochemical (PEC) dual-mode biosensor based on target biorecognition-triggered cyclic amplification was constructed for Kana detection. With the assistance of the catalyzed reaction of exonuclease III, a Kana-aptamer DNA duplex was designed for conducting the cyclic release of G-rich DNA sequence as well as output DNA S2. The released G-rich sequence triggers the fluorescence (FL) of thioflavin T (ThT), the intensity of which is positively correlated with the Kana concentration. The linear range is 0.2 to 30 nM, and the detection limit reaches 0.07 nM. Simultaneously, the released output DNA S2 was captured by Fe3O4@CdTe-probe ssDNA and then combined with methylene blue to realize the transduction of polarity-reversed PEC signal, leading to the sensitive detection of Kana with a linear range of 0.2 to 40 nM and a calculated detection limit of 0.2 nM. The outstanding performance endows the dual-mode biosensor a promising prospect for practical application.


Asunto(s)
Aptámeros de Nucleótidos , Técnicas Biosensibles , Técnicas Electroquímicas , Exodesoxirribonucleasas , Kanamicina , Límite de Detección , Exodesoxirribonucleasas/química , Técnicas Biosensibles/métodos , Kanamicina/análisis , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Aptámeros de Nucleótidos/química , Espectrometría de Fluorescencia/métodos , Colorantes Fluorescentes/química
12.
ACS Appl Mater Interfaces ; 16(40): 53873-53880, 2024 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-39324336

RESUMEN

Hybrid organic-inorganic molecular ferroelectrics (HOIMFs) have garnered significant attention owing to their potential applications in optoelectronic and spintronic devices. However, HOIMFs with high Curie temperature (Tc), narrow bandgap (Eg), excellent stability, and high breakdown voltage are still very rare. Herein, we present a novel lead-halide molecular ferroelectric, (1,4-butanediammonium)PbI4 (1), synthesized hydrothermally. 1 exhibits a ferroelectric-to-paraelectric phase transition with a high Curie temperature of 485 K, a room temperature ferroelectric hysteresis loop with a robust saturation polarization of 3.9 µC/cm2 and strong coercivity of 33 kV/cm, and a typical semiconductor behavior with a direct bandgap of 2.28 eV. Switchable photovoltaic effect was observed in 1-based device with a fast response time of ∼2 ms and high breakdown electric field of 80 kV/cm. Dramatically enhanced photovoltaic performance has been achieved by manipulating the ferroelectric polarization, resulting in a maximum photovoltage of Voc ∼ 0.84 V and a photocurrent of Jsc ∼ 33.31 nA/cm2 under standard AM 1.5 G illumination. This study offers a bright avenue for advancing high-Tc lead-halide molecular ferroelectrics with promising potentials in photodetectors, data storage, and logical switching devices.

13.
Anal Chim Acta ; 1328: 343172, 2024 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-39266195

RESUMEN

BACKGROUND: The use of pesticides to protect crops has long been an important measure to provide healthy and safe agricultural products, but excess pesticides flow into fields and rivers, causing environmental pollution. Earlier methods utilizing organic solvent liquid-liquid microextraction for pesticide residue detection were not environmentally friendly. Therefore, it is significant to find a greener and more convenient detection method to determine pesticide residues. RESULTS: A new method was established to detect three triazole fungicides (TFs), including myclobutanil, epoxiconazole and tebuconazole, in environmental water samples. And the determination was conducted using a high-performance liquid chromatography with the ultraviolet detector (HPLC-UV). The switchable deep eutectic solvent (SDES) can be reversibly switched between hydrophilic and hydrophobic states through temperature modulation. Additionally, the method exhibited excellent linearity for all target analytes within the concentration range of 10-2000 µg L-1, with satisfactory R2 values (≥0.9975). The limits of detection (LODs) ranged from 2.3 to 2.6 µg L-1, and the limits of quantification (LOQs) ranged from 7.8 to 8.7 µg L-1. The accuracy of the method was assessed through intra-day and inter-day precision tests, yielding relative standard deviations (RSDs) in the ranges of 2.8%-6.7% and 2.2%-7.5%, respectively. Density functional theory (DFT) results indicated that hydrogen bonding is a significant factor affecting the binding of DES with triazoles. Three different green assessment tools were used to prove that the SDES-HLLME method had good greenness and broad applicability. SIGNIFICANCE: This is a homogeneous liquid-liquid microextraction (HLLME) method based on the upper critical solution temperature (UCST) type switchable deep eutectic solvent program, which can complete the extraction within a few minutes without dispersant. In terms of pesticide detection, the analytical method is simple and more conducive to environmental protection.

14.
Nano Lett ; 24(40): 12515-12521, 2024 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-39347814

RESUMEN

Reproducing neural functions with artificial nanofluidic systems has long been an aspirational goal for neuromorphic computing. In this study, neural functions, such as neural activation and synaptic plasticity, are successfully accomplished with a polarity-switchable nanofluidic memristor (PSNM), which is based on the anodized aluminum oxide (AAO) nanochannel array. The PSNM has unipolar memristive behavior at high electrolyte concentrations and bipolar memristive behavior at low electrolyte concentrations, which can emulate neural activation and synaptic plasticity, respectively. The mechanisms for the unipolar and bipolar memristive behaviors are related to the polyelectrolytic Wien (PEW) effect and ion accumulation/depletion effect, respectively. These findings are beneficial to the advancement of neuromorphic computing on nanofluidic platforms.

15.
ACS Nano ; 18(36): 24682-24704, 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39185924

RESUMEN

Smart polymeric switchable adhesives represent a rapidly emerging class of advanced materials, exhibiting the ability to undergo on-demand transitioning between "On" and "Off" adhesion states. By selectively tuning external stimuli triggers (including temperature, light, electricity, magnetism, and chemical agents), we can engineer these materials to undergo reversible changes in their bonding capabilities. The strategic design selection of stimuli is a pivotal factor in the design of switchable adhesive systems. This review outlines recent advancements in the field of smart switchable polymeric adhesives over the past decade with a focus on the selection of stimulus triggers. These systems are further categorized into one of four adhesion switching mechanisms upon initiation by a specific stimuli-trigger: (i) interfacial adhesion, (ii) stiffness, (iii) contact area, or (iv) suction-based switching. Evaluation of adhesion switching performance across systems is primarily made based on three key metrics: (i) maximum adhesion strength, (ii) switch ratio, and (iii) switch time. Different stimuli and mechanisms offer distinct advantages and limitations, influencing the performance characteristics and applicability of these materials across domains such as detachable biomedical devices, robotic grippers, and climbing robots. This review thus offers a perspective on the present advancements and challenges in this emerging field, along with insights into future directions.

16.
Nano Lett ; 24(35): 11012-11019, 2024 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-39186248

RESUMEN

Ferroelectric catalysts are known for altering surface catalytic activities by changing the direction of their electric polarizations. This study demonstrates polarization-switchable electrochemistry using layered bismuth oxyselenide (L-Bi2O2Se) bifunctional microreactors through ferroelectric modulation. A selective-area ionic liquid gating is developed with precise control over the spatial distribution of the dipole orientation of L-Bi2O2Se. On-chip microreactors with upward polarization favor the oxygen evolution reaction, whereas those with downward polarization prefer the hydrogen evolution reaction. The microscopic origin behind polarization-switchable electrochemistry primarily stems from enhanced surface adsorption and reduced energy barriers for reactions, as examined by nanoscale scanning electrochemical cell microscopy. Integrating a pair of L-Bi2O2Se microreactors consisting of upward or downward polarizations demonstrates overall water splitting in a full-cell configuration based on a bifunctional catalyst. The ability to modulate surface polarizations on a single catalyst via ferroelectric polarization switching offers a pathway for designing catalysts for water splitting.

17.
Int J Biol Macromol ; 277(Pt 4): 134386, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39111498

RESUMEN

In this study, an amphiphilic polymer (Bio-HA(TPE-CN)-mPEG) was designed and synthesized, which was fabricated by introducing hydrophobic aggregation-induced emission (AIE) fluorophore, acid-labile imine bond, methoxy poly (ethylene glycol) (mPEG) and tumor targeting ligand biotin to the backbone of hyaluronic acid. The polymer could self-assemble into micelles and solubilize hydrophobic anticancer drugs. In vitro drug release study indicated that the micelles could disassemble rapidly under acidic environment. The involvement of biotin and HA could enhance the cellular uptake of micelles by tumor cells. Modification of micelles by mPEG could minimize non-specific protein adsorption. Fluorescence studies indicated that the micelles exhibited excellent AIE features and emitted intense long-wavelength fluorescence. More excitingly, the micelles were red emissive in the normal physiological environment, but switched to blue fluorescence in the acidic tumor environment, which could be further applied for real-time monitoring and quantification of the drug release. The in vivo antitumor efficacy study demonstrated the superior antitumor activity of the PTX-loaded micelles. The Bio-HA(TPE-CN)-mPEG micelles were promising drug carriers for chemotherapy and bioimaging.


Asunto(s)
Portadores de Fármacos , Sistemas de Liberación de Medicamentos , Liberación de Fármacos , Ácido Hialurónico , Micelas , Ácido Hialurónico/química , Concentración de Iones de Hidrógeno , Humanos , Animales , Portadores de Fármacos/química , Ratones , Polietilenglicoles/química , Fluorescencia , Línea Celular Tumoral , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/administración & dosificación , Antineoplásicos/farmacocinética , Neoplasias/tratamiento farmacológico , Neoplasias/patología
18.
Adv Mater ; 36(39): e2406459, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-39118581

RESUMEN

Here, a trident molecule doping strategy is introduced to overcome both cohesion-adhesion trade-off and adhesion-switchability conflict, transforming commercial polymers into tough yet photo-switchable adhesives. The strategy involves initial rational design of new trident photoswitch molecules namely TAzo-3 featuring azobenzene and hydroxy-terminated alkyl chains involved rigid-soft tri-branch structure, and subsequent doping into commercial polycaprolactone (PCL) via simple blending. Unique design enables TAzo-3 as a versatile dopant, not only regulating the internal and external supramolecular interaction to balance cohesion and interface adhesion for tough bonding, but also affording marked photothermal effect to facilitate rapid adhesive melting for great photo-switchability. Thus, the optimal TAzo-3-doped PCL (TAzo-3@P) displays markedly-improved bonding performance on diverse substrates compared to linear azobenzene-doped PCL and pure PCL. Impressively, TAzo-3@P on polymethyl methacrylate (PMMA) attains large room-temperature adhesion strength of 6.7 MPa - surpassing most reported adhesives and many commercial adhesives on PMMA, along with easy photo-induced detachment with remarkable switch ratio of 2.09 × 105. Besides, TAzo-3@P can also act as "permanent" adhesives for only adhesion, demonstrating excellent multi-reusability, anti-freezing and waterproof ability. Mechanism studies unveil that the switchable adhesion is closely linked with the dopant molecule structure while rigid-soft coupled trident structures and hydroxy-terminated alkyl chains are key factors.

19.
ACS Nano ; 18(35): 23968-23978, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39177029

RESUMEN

Transfer printing is a technology widely used in the production of flexible electronics and vertically stacked devices, which involves the transfer of predefined electronic components from a rigid donor substrate to a receiver substrate with a stamp, potentially avoiding the limitations associated with lithographic processes. However, the stamps typically used in transfer printing have several limitations related to unwanted organic solvents, substantial loading, film damage, and inadequate adhesion switching ratios. This study introduces a thermally responsive phase-change stamp for efficient and damage-free transfer printing inspired by the adhesion properties observed during water freezing and ice melting. The stamp employs phase-change composites and simple fabrication protocols, providing robust initial adhesion strength and switchability. The underlying mechanism of switchable adhesion is investigated through experimental and numerical studies. Notably, the stamp eliminates the need for extra preload by spontaneously interlocking with the ink through in situ melting and crystallization. This minimizes ink damage and wrinkle formation during pickup while maintaining strong initial adhesion. During printing, the stamp exhibits a sufficiently weak adhesion state for reliable and consistent release, enabling multiscale, conformal, and damage-free transfer printing, ranging from nano- to wafer-scale. The fabrication of nanoscale short-channel transistors, epidermal electrodes, and human-machine interfaces highlights the potential of this technique in various emerging applications of nanoelectronics, nano optoelectronics, and soft bioelectronics.

20.
ACS Nano ; 18(34): 23310-23319, 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39158149

RESUMEN

Ferroelectric all-inorganic halide perovskite nanocrystals with both spontaneous polarization and visible light absorption are promising candidates for designing ferroelectric photovoltaic applications. It remains a challenge to realize ferroelectric photovoltaic devices with all-inorganic halide perovskites that can be operated in the absence of an external electric field. Here we report that a popular all-inorganic halide perovskite nanocrystal, CsPbBr3, exhibits a ferroelectricity-driven photovoltaic effect under visible light in the absence of an external electric field. Pristine CsPbBr3 nanocrystals exhibit intrinsic ferroelectric key properties with a notable saturated polarization of ∼0.15 µC/cm2 and a high Curie temperature of 462 K, driven by the stereochemical activity of the Pb(II) lone pair. Furthermore, application of an external electric field allows the photovoltaic effect to be enhanced and the spontaneous polarization to be switched with the direction of the electric field. CsPbBr3 nanocrystals exhibit a robust fatigue performance and a prolonged photoresponse under continuous illumination in the absence of an external electric field. These findings establish all-inorganic halide perovskite nanocrystals as potential candidates for designing photoferroelectric devices by coupling optical functionalities and ferroelectric responses.

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