The high ductility of Mg has posed major challenges for nanofabrication utilizing mechanical ball-milling. While the addition of organic solvents is effective, it has been unclear how they improve the ball-milling effect by modifying the material’s surface properties. Herein, we report that the solvent-mediated partial ionicity plays an important role in enhancing the nanosizing effect of Mg87.5Ni5.5Y7 alloy. This approach enables the Mg87.5Ni5.5Y7 particles to be 88 times smaller than those of the solvent-free procedure. The Mg87.5Ni5.5Y7 nanoparticles underwent complete dehydrogenation in 3 min at 300 °C and in 17 min at 240 °C, which can be stably cycled at least for 500 times. Solvent (THF) adsorption on Mg induces Mgδ+‒Mgδ− dipole structure. This increases the surface hardness of Mg-based alloy and maximizes the ball milling-driven structural deformation, thereby facilitating ion migration. Mg‒Mg bond breaking is caused by the resulting Coulombic repulsion between Mg atoms. These findings provide an affordable approach for nanoparticle fabrication of highly ductile materials. The work highlights the role of solvent-mediated ionicity in modifying surface hardness of Mg-Ni-Y alloy, which facilitates the production of nanoparticles ~88 times smaller than milled powder without solvent processing, resulting in a scalable production method for metallic nanoparticles.
Current surface modification strategies for electrospun materials always require covalent conjugation technology, which is relatively inefficient and might damage the bioactivity and structure of peptides and proteins. Here we introduce the use of surface-induced self-assembly technology to modify electrospun materials, which is a simple but efficient noncovalent-based process. Results show that the peptide NapFFGRGD forms burr-like structures on the surface of PCL fibers, reducing the water contact angle of the fibers. Adjusting the peptide sequence and salt concentration affects the self-assembly and surface properties of modified PCL fibers. Additionally, we demonstrate the potential application of this surface modification technique for enhancing cellular responses in tissue engineering applications. The research provides valuable insights into the surface modification of PCL fibers and offers a new method for improving the biological compatibility of materials in tissue engineering.
Effective mild-temperature photothermal therapy (MTPTT) requires photothermal agents with high photothermal conversion efficiency (PCE) and balanced fluorescence quantum yield to enable efficient tumor treatment while minimizing damage to surrounding healthy tissues. In this study, we designed donoru2013acceptoru2013donor structured dyes, 4,4u2019-((6,7-di(thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline-4,9-diyl)bis(thiophene-5,2-diyl))bis(N,N-bis(4-methoxyphenyl)aniline) (IT-STPA) and 4,4u2019-((6,7-di(furan-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline-4,9-diyl)bis(thiophene-5,2-diyl))bis(N,N-bis(4-methoxyphenyl)aniline) (IT-OTPA), featuring furan-modified thiadiazolo-quinoxaline for near-infraredu2013II (NIR-II) fluorescence imaging and enhanced PCE. The furan and thiophene modifications promoted aggregation-induced emission, resulting in strong fluorescence emission (1 000u20131 400 nm) while maintaining a high PCE of 48.5%. IT-OTPA was encapsulated into nanoparticles for improved aqueous dispersion and combined with the HSP70 inhibitor apoptozole (APZ) to form OTAPZ nanoparticles. The efficacy of this combination was evaluated both in vitro and in vivo, showing efficient tumor targeting and effective MTPTT under NIR laser irradiation. This study presents a promising approach for enhancing MTPTT through balanced photothermal and fluorescence properties, offering new possibilities for cancer treatment.
Introducing oxygen vacancies (OVs) is an effective strategy to address the intrinsic limitations of photocatalytic semiconductor systems. Herein, cobalt-ion-doped cerium oxide nanocomposites namely CoCeOx-1 and CoCeOx-2, were constructed by two methods to systematically study the effects of OV formation, location and concentration on the photocatalytic degradation performance of antibiotics. CoCeOx-1, obtained by a one-step method, has abundant OVs and a narrowed band gap (BG), whereas CoCeOx-2, formed through a two-step process, has reduced OVs concentration and an enlarged BG compared to CeO2. Surprisingly, CoCeOx-2 exhibits much higher photocatalytic degradation efficiency, with 3CoCeO(x)-2 achieving 73.10 % degradation of Norfloxacin (NFX) and 85.69 % of cefazolin (CFZ) under 320 nm < lambda < 780 nm light, showing outstanding cyclic stability in neutral aqueous solution. The analysis of degradation products and photogenerated reactive oxygen species (ROS) reveals the probable mechanism and pathway of antibiotic degradation, clarifying the origin of its excellent catalytic activity. The study highlights that a larger specific surface area and especially a higher concentration of photoinduced ROS and a long-lived charge-separated state from the shallow energy levels of the OVs are the main causes for the high photocatalytic degradation efficiency.
The (310)-oriented beta-Ga2O3 substrate serves as a promising close-packed plane for epitaxial growth and devices fabrication. Dislocations, which are major crystal defects in beta-Ga2O3, negatively impact the performance and reliability of electronic devices. In this paper, we investigated dislocations on the (310) plane by X-ray topography, transmission electron microscopy, chemical etching and atomic force microscopy. Our findings confirm the formation of mixed dislocation loops generated during simultaneously nucleation in the crystal growth process via the casting method. These loops are primarily composed of screw-type dislocations with a Burgers vector b = <010 > on the {001} slip plane and the corresponding etch pits delineated by H3PO4 solution are water droplet like arrays along [130] orientation on the (310) plane. DFT calculations revealed the < 010 > / {001} was the easiest slip system in beta-Ga2O3 and the crystallographic features of the water droplet like pit were thoroughly explained. This comprehensive analysis offers valuable insights for optimizing processing techniques to reduce dislocations and enhance material quality for device applications.
Defect-enriched mesoporous CuO nanosheets (NSs) were constructed to investigate the cooperative photo-Fenton and photothermal-Fenton catalysis on degradation of fluoroquinolones (FQ) antibiotics. The oxygen vacancies provide abundant active sites to bind the substrates and inhibit charge recombination, by all means to enhance Fenton-like activity. Two disparate spectral selective functions of photoexcitation and photothermal conversion were achieved on CuO NS, which to promote the Fenton activity synergistically. Visible light induced photoexcitation to facilitate the generation of Cu+ and & sdot;OH, while near-infrared light converted into heat to promote charge separation and accelerate medium transport. Ultimately, as a unitary catalyst system, the CuO NS integrated the Lewis acid catalysis, Fenton-like catalysis and photothermal catalysis that rapidly and sustainably degraded antibiotics under near-neutral conditions. In this paper, a defects-rich mesoporous CuO nanosheet (NSs) with full spectrum absorption was synthesized. Based on its photofenton-like activity, it can achieve rapid degradation of fluoroquinolone antibiotics. In this process, the mechanism of different wavelengths of light in promoting Fenton-like reaction was deeply explored. image
We report a theranostic nanocapsule, working entirely in the near-infrared (NIR) region for photothermal therapy (PTT) with the ability to remotely record the temperature in real time. These nanocapsules are synthesized by a one-pot approach, simultaneously coencapsulating bay-substituted dicyclohexylaminoperylene diimide (sPDI) as an optical heater and rationally designed multifunctional LiLuF4:10 mol % Nd3+@LiLuF4 core@shell downshifting NPs (DSNPs), as both ratiometric luminescent thermometers and imaging probes. Upon laser irradiation, the sPDI aggregates convert light to heat via nonradiative relaxation, inducing a local temperature increase and eradicating MCF-7 breast cancer cells. Accurate temperature sensing is achieved in situ by the luminescence of the DSNPs. In addition, a positive contrast enhancement is found in the computer tomography (CT) images of the cancer cells under investigation, owing to the presence of Lu3+ in the DSNPs, demonstrating the potential for image-guided PTT.
AbstractPhotothermal agents (PTAs) with ultra‐high photothermal conversion efficiency (PCE) activated upon near‐infrared (NIR) laser irradiation can heat up and destroy tumor cells under low‐intensity laser excitation to allow safe and efficient tumor therapy. Herein, an organic PTA with an outstanding PCE of 89.6% is developed from rationally designed perylene diimide (PDI) with electron‐donating cyclohexylamine moiety at the bay‐positions of its skeleton and chiral phenethylamine (PEA) moiety at its N terminals, termed here PEAPDI. The strong intermolecular interaction between the PDI skeletons induced by PEA together with the intramolecular charge transfer from cyclohexylamine to PDI skeleton severely quenches the fluorescence emission from PEAPDI and significantly enhances its NIR absorption, resulting in super NIR–photothermal conversion. PEAPDI molecules are subsequently encapsulated within silica nanocapsules (SNCs), creating PEAPDI@SNC. Characterized by its small hydrodynamic diameter, monodispersity, high PDI encapsulation efficiency, colloidal stability, and biocompatibility, PEAPDI@SNC exhibits prolonged blood circulation and enhanced permeability and retention effect, enabling targeted accumulation at the tumor site. An in vivo study using a 4T1 tumor–bearing mice model illustrates the agent's potent tumor ablation capability without side effects at low dosage under NIR laser irradiation (808 nm). The findings demonstrate PEAPDI@SNC's significant potential as a PTA for tumor treatment.
The galactomannan from Antrodia cinnamomea (AC) is characterized as one of the important bioactive components that exhibits potential immunostimulatory propriety. The biological function of its corresponding oligosaccharide fragments has not been revealed yet. In this study, we reported the first chemical synthesis of the series of oligosaccharide fragments related to AC galactomannan via the convergent glycosylation strategy. The preliminary immunological evaluation of these synthesized AC oligosaccharides disclosed that the backbone tetrasaccharide 1d showed the best immunomodulatory ability on enhancing proliferation, phagocytosis and cytokines secretion of Raw264.7 macrophages in vitro, indicating its immense potential as an immunostimulant candidate.
In recent years, the diagnosis and treatment at the early stages significantly raise the survival rate of breast cancer patients. Moreover, antibody drugs pave the way toward precision target therapy. However, the treatment and survival of triple-negative breast cancer (TNBC) patients is still worrying, which needs further understanding and study. During the last several years, nanomaterials attracted extensive research interests in TNBC diagnosis and therapy. In this review, we summarize recent advances of nanomaterial-based strategies for diagnosing and treating TNBC. Specifically, treatments for TNBC utilizing nanomaterials are classified into monotherapy, combined therapy, and multimodal therapy based on the complexity of the treatment. Nanomaterials also offer the opportunity to integrating diagnosis with treatment, which are introduced and summarized in this review. By summarizing the design principles in detail, some insights into the challenges and opportunities are provided to inspire further research and clinical translation in this field. The scope of this review is to summarize the development of nanomaterials for diagnosis and treatment of TNBC, and to discuss future directions to improve the clinical outcome of TNBC patients.
A cross-dipole n-n close-stacking of 1,7-diphenylazophenol (AZO) perylene diimides (PDI, AZO-PDIs) formed in a single-crystal integrating good ambipolar charge transport and aggregation-induced emission (AIE) behaviors has been unveiled. The weak electron donating and moderate steric hindrance of AZOs endows AZO-PDIs with crossed Donor-Acceptor-Donor (D-A-D) structures, which facilitates the charge injection of both electrons and holes and a distinct cross-dipole n-n close-packing with the distance of only 3.29 angstrom. Accordingly, the wave function overlaps and electronic coupling of PDI cores are significantly enhanced to provide a quasi-1D charge transport channel, resulting in ambipolar performance with the hole and electron mobility of 6.74 cm2 V-1 s- 1 and 5.96 cm2 V-1 s- 1 respectively. The average conductivity of 0.5 S m- 1 has further confirmed the good charge transport properties of the single crystals. Moreover, it also exhibits AIE behaviors due to the weak transition dipole resonance induced by the cross-dipole stacking of a large rotation angle (79.8 degrees) and restriction of intra-molecular rotation of the bulk AZOs. This work initially provides a promising strategy for achieving both charge transport and AIE performance on account of D-A-D molecules with crossed conformations at the molecular level and efficient n-overlaps induced by cross-dipole stacking at the supramolecular level.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Development of organic molecules with high photothermal conversion efficiency (PCE) in the near-infrared (NIR) window is a vital yet challenging topic in the field of photothermal therapy. A series of thionated perylenediimides (PDI-4CHA-S) derivatives have been synthesized by replacing carboxylic oxygens in imides with sulfur atoms, providing chances to unravel the effect of thionation on the photophysical properties toward photothermal agents (PTAs) with high PCE. In the presence of the electron-donating substituents at the bayposition, sulfur atoms participate the intramolecular charge transfer (ICT), which induces remarkable redshift in the absorption maximum. Meanwhile, the ICT together with the heavy atoms effect of sulfur atoms promotes the intersystem crossing (ISC), resulting in the generation of the active oxygen species (ROS) upon photoexcitation. Interestingly, the quantum yield of ROS decrease with increasing the number of S-substitutes, which is the resultant of the attenuated ICT in the case of multiple S-substitution. Overall, the promotion in ISC due to thionation is negligible compared to the quenching of the radiation transition and enhancement of the absorption coefficient caused by ICT, hence the energy of the excited PDI-4CHA-S molecules is depleted mainly in the form of heat, leading to the ultrahigh PCE of 88.0% under 808 nm laser irradiation. In particular, the trithionated PDI4CHA-3S performs surprisingly high PCE in the second near-infrared (NIR-II) window (1064 nm). The superior photothermal effect and excellent photostability of the thionated PDI derivative provide them promising photothermal agents for NIR photothermal therapy.
A bismuth-based organic–inorganic hybrid single crystal with a chiral nature is constructed, which has a large shear piezoelectric coefficient of 46.54 pC N −1 with an electromechanical coupling coefficient over 40%.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Antibacterial strategies based on reactive oxygen species (ROS) have opened up a new avenue for overcoming the great challenges of antibiotics topic including lack of broad-spectrum antibiotics and the emergence of super-resistant bacteria. Herein, we leveraged a strategy of constructing synergistic catalytic active sites to develop a simple yet efficient Fenton-like active nanocomposite, and investigated its catalysis mechanism and antibacterial performance thoroughly. This strategy provides a new direction for boosting the catalytic activity of nanocomposite catalysts for wide application. Specifically, by uniformly loading copper oxide and ceria onto the surface of silica nanocapsules (SiO2 NCs), we fabricated a bimetallic oxide nanocomposite Cu0.75Ce0.62O2@SiO2 NC, which performed superior Fenton-like capability in a wide pH range without additional exogenetic hydrogen peroxide (H2O2). Such excellent catalytic activity was originated from the charge interaction between the two metal oxide components, where formation of Cu+ and oxygen vacancies (OVs) was mutually reinforcing, resulting in a synergistic effect to produce H2O2 and catalyze the generation of •OH under the slight acid condition (pH = 6.0). In view of the outstanding Fenton-like activity, the Cu0.75Ce0.62O2@SiO2 NC was employed in antimicrobial testing, which demonstrated exceptional high in vitro antimicrobial efficacy against both the S. aureus and E. coli in a neutral environment (pH = 7.4). The excellent performance of the bimetallic nanocomposite Cu0.75Ce0.62O2@SiO2 NC, including its facile and mild preparation, high water-solubility and stability, superior catalytic and antimicrobial performances, manifests a promising broad-spectrum antibiotic that can be anticipated to deal with the contamination of the environment by bacteria.
The present report uncovers the Fenton-like and solar-Fenton activity of nickel-coordinated phthalocyanines and their potential as antibacterial agents. In particular, two NiPcs, one achiral and the other chiral, with both having similar molecular structures, are designed. Both compounds aggregate to form crystals with large diversity in molecular stacking. The crystal grown from the achiral NiPc demonstrates superior Fenton-like activity especially under NIR-light illumination, and also exhibits efficient antibacterial activity in vitro toward both E. coli and S. aureus. On the contrary, the crystal formed from stacked chiral molecules demonstrates weak Fenton-like reactivity and is inefficient for bacterial disinfection. By examining the differences between the two crystals, we have disclosed the mechanism of the Fenton-like reactivity of the NiPcs associated with molecular aggregation. Moreover, the chiral NiPc and its crystal provide a good platform to inspect the correlation between the functions, for instance the antibacterial activity between the chiral selections. This work indicates that controlling small differences in molecular structure can provide an effective way to achieve specific functions, such as Fenton-like activity, of organic semiconductors.
Ion migration, an intrinsic property that cannot be suppressed by device encapsulation, is of great importance to the long-term stability of perovskite solar cells. Herein, we synthesize a polyethylene glycol-modified fullerene (PCBHGE) and then incorporate it into perovskite absorber layers. It is found that PCBHGE can stabilize [PbI6](4-) octahedral frameworks by forming Lewis acid-base pairs. Decoupling the efficient defect passivation of the fullerene core, ion migration is suppressed significantly in the as-fabricated devices. As a result, our state-of-the-art device demonstrates a highest efficiency of 23.19%. Most importantly, the device with PCBHGE can retain 87% of its maximum efficiency after 206 days. Tracked at the maximum power point under a continuous bias, the device efficiency hardly decreases in the first 212 h with a UV filter and can retain 80% of its initial efficiency after the next 600 h under full spectrum illumination including UV light.