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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 317: 124405, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38718746

RESUMO

With the expansion of the application of high-sensitivity Surface-enhanced Raman scattering (SERS) technique, micro SERS-active substrates with rich optical properties and high-level functions are desired. In this study, silver nanorings with nanoscale surface roughness were fabricated as a new type of enclosed quasi-2D micro-SERS-active substrate. Highly-crystalline spherical and hemispherical silver nanoprotrusions were densely and uniformly distributed over the entire surface of the nanorings. The SERS signals were significantly enhanced on the roughened silver nanorings which were mainly derived from the maximal localized surface plasmon resonance (LSPR) points at the junctions between adjacent coupled nanoprotrusions on the roughened nanorings. The mapping image shows a uniform and intense LSPR enhancement over the nanorings, owing to the uniform and dense distribution of silver nanoprotrusions and the resulting uniform distribution of maximal LSPR points on the roughened nanorings. The dark-field spectra further indicated that the single roughened silver nanoring had significant LSPR enhancement, a wide LSPR frequency-range response, and adaptability for SERS enhancement. Notably, both the measured and simulated results demonstrate that the maximal LSPR enhancement at the junctions between the nanoprotrusions, which are distributed on the inner surface of the silver nanoring, is higher than that on the outer surface because of the plasmon-focusing effect of the enclosed silver nanoring, which leads to the lateral asymmetrical distribution of LSPR intensity, indicating more LSPR and SERS features. These results indicate that single roughened silver nanorings exhibit excellent performance as a new type of enclosed quasi-2D silver nanoring micro-SERS-active substrate, microzone LSPR catalysis, and micro/nanodevices.

2.
Nano Lett ; 24(9): 2894-2903, 2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38407042

RESUMO

Harnessing the potential of tumor-associated macrophages (TAMs) to engulf tumor cells offers promising avenues for cancer therapy. Targeting phagocytosis checkpoints, particularly the CD47-signal regulatory protein α (SIRPα) axis, is crucial for modulating TAM activity. However, single checkpoint inhibition has shown a limited efficacy. In this study, we demonstrate that ferrimagnetic vortex-domain iron oxide (FVIO) nanoring-mediated magnetic hyperthermia effectively suppresses the expression of CD47 protein on Hepa1-6 tumor cells and SIRPα receptor on macrophages, which disrupts CD47-SIRPα interaction. FVIO-mediated magnetic hyperthermia also induces immunogenic cell death and polarizes TAMs toward M1 phenotype. These changes collectively bolster the phagocytic ability of macrophages to eliminate tumor cells. Furthermore, FVIO-mediated magnetic hyperthermia concurrently escalates cytotoxic T lymphocyte levels and diminishes regulatory T cell levels. Our findings reveal that magnetic hyperthermia offers a novel approach for dual down-regulation of CD47 and SIRPα, reshaping the tumor microenvironment to stimulate immune responses, culminating in significant antitumor activity.


Assuntos
Hipertermia Induzida , Neoplasias , Humanos , Antígeno CD47 , Regulação para Baixo , Imunoterapia , Fagocitose , Fenômenos Magnéticos , Neoplasias/patologia , Microambiente Tumoral
3.
Biomed Pharmacother ; 170: 115954, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38039753

RESUMO

The potential of Ferrimagnetic vortex iron oxide nanoring-mediated mild magnetic hyperthermia (FVIO-MHT) in solid tumor therapy has been demonstrated. However, the impact of FVIO-MHT on the tumor microenvironment (TME) remains unclear. This study utilized single-cell transcriptome sequencing to examine the alterations in the TME in response to FVIO-MHT in breast cancer. The results revealed the cellular composition within the tumor microenvironment (TME) was primarily modified due to a decrease in tumor cells and an increased infiltration of myeloid cells. Subsequently, an enhancement in active oxygen (ROS) metabolism was observed, indicating oxidative damage to tumor cells. Interestingly, FVIO-MHT reprogrammed the macrophages' phenotypes, as evidenced by alterations in the transcriptome characteristics associated with both classic and alternative activated phenotypes. And an elevated level of ROS generation and oxidative phosphorylation suggested that activated phagocytosis and inflammation occurred in macrophages. Additionally, cell-cell communication analysis revealed that FVIO-MHT attenuated the suppression between tumor cells and macrophages by inhibiting phagocytic checkpoint and macrophage migration inhibitory factor signaling pathways. Inhibition of B2m, an anti-phagocytosis checkpoint, could promote macrophage-mediated phagocytosis and significantly inhibit tumor growth. These data emphasize FVIO-MHT may promote the antitumor capabilities of macrophages by alleviating the suppression between tumor cells and macrophages.


Assuntos
Neoplasias da Mama , Hipertermia Induzida , Humanos , Feminino , Neoplasias da Mama/genética , Neoplasias da Mama/terapia , Espécies Reativas de Oxigênio/farmacologia , Macrófagos , Fenômenos Magnéticos , Perfilação da Expressão Gênica , Microambiente Tumoral
4.
Chempluschem ; 89(7): e202300536, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38123532

RESUMO

The carbon nanorings, possessing a radial π system, have garnered significant attention primarily due to their size-dependent photophysical properties and the presence of a unique curved π-conjugated cavity. This is evidenced by the rapid proliferation of publications. Furthermore, the integration of building blocks into CPP skeletons can confer [n]CPPs with novel and exceptional photophysical and electronic characteristics, as well as chiral properties and host-guest interactions, thereby augmenting the diversity of [n]CPPs. Notably, the curved π surface structures and concave cavity of carbon nanorings enable them to host aromatic or non-aromatic guests with a complementarily curved surface, resulting in interesting binary or ternary complexes. This review provides a comprehensive treatment of literature reports on binary and ternary complexes, focusing on both their host-guest interactions and properties. It is important to note that the scope of this review is limited to host-guest chemistry in binary and ternary complexes based on π-conjugated carbon nanorings.

5.
ACS Appl Mater Interfaces ; 15(41): 48015-48026, 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37797325

RESUMO

Proteins unfold in chaotropic salt solutions, a process that is difficult to observe at the single protein level. The work presented here demonstrates that a liquid-based atomic force microscope and graphene liquid-cell-based scanning transmission electron microscope make it possible to observe chemically induced protein unfolding. To illustrate this capability, ferritin proteins were deposited on a graphene surface, and the concentration-dependent urea- or guanidinium-induced changes of morphology were monitored for holo-ferritin with its ferrihydrite core as well as apo-ferritin without this core. Depending on the chaotropic agent the liquid-based imaging setup captured an unexpected transformation of natively folded holo-ferritin proteins into rings after urea treatment but not after guanidinium treatment. Urea treatment of apo-ferritin did not result in nanorings, confirming that nanorings are a specific signature of denaturation of holo-ferritins after exposture to sufficiently high urea concentrations. Mapping the in situ images with molecular dynamics simulations of ferritin subunits in urea solutions suggests that electrostatic destabilization triggers denaturation of ferritin as urea makes direct contact with the protein and also disrupts the water H-bonding network in the ferritin solvation shell. Our findings deepen the understanding of protein denaturation studied using label-free techniques operating at the solid-liquid interface.


Assuntos
Grafite , Guanidina/química , Desnaturação Proteica , Ferritinas , Ureia/química
6.
Biosens Bioelectron ; 237: 115557, 2023 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-37531892

RESUMO

MicroRNA-21 (miRNA-21) is currently the only known oncogenic miRNA that is upregulated in almost all malignant tumors and exhibits a broad spectrum of tumor recognition characteristics. It holds significant value in the early diagnosis, malignant degree assessment, and prognostic evaluation of tumors. In this study, a novel dual-mode self-powered sensing platform is developed using Au nanoparticles/graphdiyne as the electrode substrate and combined with DNA nanoring for highly sensitive and specific detection of miRNA-21. The DNA nanoring structure, which is easy to prepare and contains multiple recognition sites, induces significant electrochemical/colorimetric signal responses of the signaling molecule methylene blue. Under optimal conditions, the linear ranges of the electrochemical and colorimetric detection modes of this self-powered sensor are 0.1 fM-100 pM and 0.1 fM-10 nM, respectively, with the detection limits of 35.1 aM and 61.6 aM (S/N=3). This strategy provides a new reference for the sensitive detection of microRNA and has immense potential for application in the screening and detection of clinical nucleic acid diseases.


Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , MicroRNAs , Biomarcadores Tumorais/genética , Ouro/química , Nanopartículas Metálicas/química , DNA/química , MicroRNAs/genética , Limite de Detecção , Técnicas Eletroquímicas
7.
Angew Chem Int Ed Engl ; 62(28): e202304623, 2023 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-37193936

RESUMO

We report the synthesis and chiroptical properties of novel chiral carbon nanorings Sp-/Rp-[12]PCPP containing a planar chiral [2.2]PCP unit, and demonstrate that Sp-/Rp-[12]PCPP can not only host crown ether 18-Crown-6 to form ring-in-ring complexes with a binding constant 3.35×103  M-1 , but also accommodate the complexes of 18-Crown-6 and S/R-protonated amines to form homochiral S@Sp-/R@Rp- and heterochiral S@Rp-/R@Sp- ternary complexes, displaying significantly larger binding constants of up to 3.31×105  M-1 depending on the chiral guests. Importantly, homochiral S@Sp-/R@Rp- ternary complexes exhibit an enhanced CD signal, while the heterochiral S@Rp-/R@Sp- ones have a constant CD signal compared with the chiral carbon nanorings, respectively, which suggests that homochiral S@Sp-/R@Rp- ternary complexes display a highly narcissistic chiral self-recognition for S/R-protonated chiral amines, respectively. Finally, the chiral ternary complexes can be further applied to determine the ee values of chiral guests. The findings highlight a new application of carbon nanorings in supramolecular sensors, beyond the common recognition of π-conjugated molecules.

8.
Biosens Bioelectron ; 232: 115310, 2023 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-37087985

RESUMO

To achieve sensitive detection of low-content microRNA, photoelectrochemical/electrochromic dual-mode sensor with intrinsically low background signal has been developed, but the two detection modules are usually designed with a series-connected structure, which may cause signal interference and thus affect the detection reliability. To solve the above problems, a decoupled dual-mode bioassay for sensitive miRNA-21 detection with high reliability is constructed in this work, by selecting two capacitors to realize parallel amplification for the two detection modules, supplemented with a 3D DNA nanoring photoelectrode signal amplification strategy. The complete decoupling of the two detection modes, photoelectrochemical and electrochromic, as well as the use of digital multimeter, improves the reliability and accuracy of the sensor, and also frees it from dependence on electrochemical workstation, making detection more intuitive and faster. With simple structure, low cost, good reproducibility, high sensitivity, and easy operation, the capacitor-parallel-amplified decoupled photoelectrochemical/electrochromic dual-mode bioassay has broad application prospect in on-site point-of-care detection of diseases and low-cost clinical diagnosis. The design idea of decoupled dual-mode detector can also be extended to the construction of other dual-mode methods.


Assuntos
Técnicas Biossensoriais , MicroRNAs , MicroRNAs/genética , Reprodutibilidade dos Testes , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Técnicas de Amplificação de Ácido Nucleico/métodos , Limite de Detecção
9.
Chemistry ; 29(35): e202300503, 2023 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-37002639

RESUMO

An approach to modulating the properties of carbon nanorings by incorporating pyrrolo[3,2-b]pyrrole units is of particular interest due to the combined effect of heteroatom and antiaromatic character on electronic properties. The inclusion of units other than phenylene leads to the formation of stereoisomers. In this work, we computationally study how the spatial orientation of monomeric units in the ring affects the properties of cyclic dibenzopyrrolo[3,2-b]pyrroles and their complexes with C60 fullerene. For [4]PP and [4]DHPP, the most symmetrical AAAA isomer is the most stable and forms stronger interactions with fullerene than the isomers where one or two monomeric units are flipped, mostly due to less Pauli repulsion. π-Electron delocalization in the monomeric unit is crucial for directing the electron transfer (from or to nanoring). The energy of excited states with charge transfer depends on the HOMO-LUMO gap, which varies from one stereoisomer to another only for [4]DHPP⊃C60 with aromatic 1,4-dihydropyrrolo[3,2-b]pyrrole units. The rates of electron transfer and charge recombination reactions are relatively weakly dependent of the spatial isomerism of nanorings.


Assuntos
Fulerenos , Isomerismo , Transporte de Elétrons , Carbono , Pirróis
10.
Angew Chem Int Ed Engl ; 62(18): e202302114, 2023 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-36877745

RESUMO

Rings of porphyrins mimic natural light-harvesting chlorophyll arrays and offer insights into electronic delocalization, providing a motivation for creating larger nanorings with closely spaced porphyrin units. Here, we demonstrate the first synthesis of a macrocycle consisting entirely of 5,15-linked porphyrins. This porphyrin octadecamer was constructed using a covalent six-armed template, made by cobalt-catalyzed cyclotrimerization of an H-shaped tolan with porphyrin trimer ends. The porphyrins around the circumference of the nanoring were linked together by intramolecular oxidative meso-meso coupling and partial ß-ß fusion, to give a nanoring consisting of six edge-fused zinc(II) porphyrin dimer units and six un-fused nickel(II) porphyrins. STM imaging on a gold surface confirms the size and shape of the spoked 18-porphyrin nanoring (calculated diameter: 4.7 nm).

11.
J Mol Graph Model ; 119: 108371, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36502605

RESUMO

The butadiyne-linked six-metalloporphyrin nanoring (Mg6-P6) and it's complex with a hexapyridyl template, Mg6-P6·T6 have a great potential for employment in future nanoelectronic applications such as a nanosensor for small gas molecules. The goal of this study is to scrutinize and improvement of the CO, N2, and O2 gas sensing capacity of Mg6-P6 and Mg6-P6·T6 using DFT calculations at CAM-B3LYP/6-31G (d,p) level of theory. The geometrical structures, binding energies, band gaps, the density of states (DOS), adsorption energies, HOMO and LUMO energies, Fermi level energies (EFL), NBO, FMO and TD-DFT spectrum were calculated to predict gas adsorption properties of Mg6-P6 and Mg6-P6·T6 systems. Based on the calculated adsorption energies and remarkable decrease in the Eg, it is expected that the Mg6-P6 and Mg6-P6·T6 are sensitive to O2 molecule. Surprisingly, the Mg6-P6-O2 and specially the Mg6-P6.T6-O2 record promising values of recovery times for different attempt frequencies. Therefore, the results open a way for the development of a new and selective O2 nanosensor in the presence of CO and N2 gas molecules.


Assuntos
Porfirinas , Modelos Moleculares , Porfirinas/química , Teoria Quântica , Teoria da Densidade Funcional
12.
Front Bioeng Biotechnol ; 10: 1005719, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36277375

RESUMO

Due to no penetration depth limitation, low cost, and easy control, magnetic nanoparticles mediated magnetic hyperthermia therapy (MHT) has shown great potential in experimental and clinal treatments of various diseases. However, the low heating conversion efficiencies and short circulation times are major drawback for most existing magnetic-thermal materials. Additionally, single MHT treatment always leads to resistance and recurrence. Herein, a highly efficient magnetic-thermal conversion, ferrimagnetic vortex nanoring Fe3O4 coated with hyaluronic acid (HA) nanoparticles (Fe3O4@HA, FVNH NPs) was firstly constructed. Additionally, the doxorubicin (DOX) was successfully enclosed inside the FVNH and released remotely for synergetic magnetic-thermal/chemo cancer therapy. Due to the ferrimagnetic vortex-domain state, the ring shape Fe3O4 displays a high specific absorption rate (SAR) under an external alternating magnetic field (AMF). Additionally, antitumor drug (DOX) can be encapsulated inside the single large hole of FVNH by the hyaluronic acid (HA) shell and quickly released in response the tumor acidic microenvironments and AMF. What's more, the non-loaded FVNH NPs show good biocompatibility but high cytotoxicity after loading DOX under AMF. Furthermore, the synthesized FVNH can efficiently reduce the transverse relaxation time and enhance negative magnetic resonance imaging (MRI). The impressive in vivo systemic therapeutic efficacy of FVNH was also proved in this work. Taken together, the results of this study demonstrate that the synthesized FVNH NPs offer the promise of serving as multifunctional theranostic nanoplatforms for medical imaging-guided tumor therapies.

13.
ACS Nano ; 16(11): 18806-18821, 2022 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-36278899

RESUMO

Labeling stem cells with magnetic nanoparticles is a promising technique for in vivo tracking and magnetic targeting of transplanted stem cells, which is critical for improving the therapeutic efficacy of cell therapy. However, conventional endocytic labeling with relatively poor labeling efficiency and a short labeling lifetime has hindered the implementation of these innovative enhancements in stem-cell-mediated regenerative medicine. Herein, we describe an advanced magnetothermal approach to label mesenchymal stem cells (MSCs) efficiently by local induction of heat-enhanced membrane permeability for magnetic resonance imaging (MRI) tracking and targeted therapy of stroke, where biocompatible γ-phase, ferrimagnetic vortex-domain iron oxide nanorings (γ-FVIOs) with superior magnetoresponsive properties were used as a tracer. This approach facilitates a safe and efficient labeling of γ-FVIOs as high as 150 pg of Fe per cell without affecting the MSCs proliferation and differentiation, which is 3.44-fold higher than that by endocytosis labeling. Such a high labeling efficiency not only enables the ultrasensitive magnetic resonance imaging (MRI) detection of sub-10 cells and long-term tracking of transplanted MSCs over 10 weeks but also endows transplanted MSCs with a magnetic manipulation ability in vivo. A proof-of-concept study using a rat stroke model showed that the labeled MSCs facilitated MRI tracking and magnetic targeting for efficient replacement therapy with a significantly reduced dosage of 5 × 104 transplanted cells. The findings in this study have demonstrated the great potential of the magnetothermal approach as an efficient labeling technique for future clinical usage.


Assuntos
Nanopartículas de Magnetita , Transplante de Células-Tronco Mesenquimais , Células-Tronco Mesenquimais , Acidente Vascular Cerebral , Ratos , Animais , Rastreamento de Células/métodos , Imageamento por Ressonância Magnética/métodos , Acidente Vascular Cerebral/diagnóstico por imagem , Acidente Vascular Cerebral/terapia , Acidente Vascular Cerebral/metabolismo , Transplante de Células-Tronco Mesenquimais/métodos
14.
J Comput Chem ; 43(19): 1276-1285, 2022 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-35644831

RESUMO

By means of density functional theory calculations, the encapsulation capabilities of a series of azobenzen-containing photoresponsive nanoring hosts (labeled as host 1, 2, 3, 4, 5 and 6 according to the number of the azo unit, respectively) for fullerene C60 were surveyed. Interestingly and abnormally, it is found that the host 5, of which the diameter is only 1.218 nm, can form stable full inclusion complex with C60 . However, irrespective of their cavity sizes (11.98 ~ 12.94 Å) of the hosts, the structures 1 ~ 4 and 6 were all disable to form inclusion complex with C60 . In this paper, the group-number-composition-selective full inclusion host-guest interaction of the azobenzene-containing nanorings with fullerene C60 is firstly presented. The calculated interaction energies, together with the detection and visualization of the weak interaction regions, provided evidences for the host-guest binding based on relative strong repulsion interaction in the full inclusion complex. Analysis on the frontier orbital feature of the host-guest systems suggests that under the electron excited condition, the chemical activity may be transferred from host 5 to guest C60 by formation of the floating host-guest complex, and the chemical reactivity of the host 5 can be passivated via formation of the full inclusion host-guest complex. Additionally, UV-vis-NIR and 1 H NMR spectra of the hosts before and after the formations of the complexes have been simulated and discussed qualitatively, which may be helpful for further experimental investigations in future.

15.
Biomed Pharmacother ; 150: 112926, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35427819

RESUMO

Nowadays, about 30% of magnetic resonance imaging (MRI) exams need contrast agents (CAs) to improve the sensitivity and quality of the images for accurate diagnosis. Here, a multifunctional nano-agent with ring-like vortex-domain iron oxide as core and gadolinium oxide as shell (vortex nanoring Fe3O4 @Gd2O3, abbreviated as VNFG) was firstly designed and prepared for highly enhanced T1-T2 dual-modality magnetic resonance imaging (MRI)-guided magnetic thermal cancer therapy. After thorough characterization, the core-shell structure of VNFG was confirmed. Moreover, the excellent heat generation property (SAR=984.26 W/g) of the proposed VNFG under alternating magnetic fields was firmly demonstrated. Furthermore, both in vitro and in vivo studies have revealed a good preliminary indication of VNFG's biological compatibility, dual-modality enhancing feature and antitumor efficacy. This work demonstrates that the proposed VNFG can be a high-performance tumor diagnosis and theranostic treatment agent and may have great potential for clinical application in the future.


Assuntos
Hipertermia Induzida , Neoplasias , Meios de Contraste/química , Gadolínio , Humanos , Imageamento por Ressonância Magnética/métodos , Neoplasias/diagnóstico por imagem , Neoplasias/terapia , Nanomedicina Teranóstica/métodos
16.
ACS Appl Mater Interfaces ; 14(7): 9454-9463, 2022 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-35142212

RESUMO

Vanadium monoxide (VO) is a promising candidate as an anode for lithium-ion batteries due to its high theoretical capacity, low cost, and considerable electronic conductivity. Unfortunately, a large volume change during electrochemical processes obstructs its practical application. In this work, a composite of VO nanorings grown on a porous carbon architecture is prepared via a topochemical self-reduction approach. When used as an anode for lithium-ion batteries, improved redox kinetics from enhanced electronic conduction and the corresponding fast lithium-ion diffusion is observed to greatly promote the electrochemical performance of lithium-ion batteries. The resulting composite delivered a reversible capacity of 336 mA h g-1 after 400 cycles at 10 A g-1 with a capacity retention of 85%, owing to the synergistic effect of VO nanorings and porous carbon in alleviating volume changes that result in a long-term cycling ability at a high current density. At 20 A g-1, the composite anode exhibited a rate capability of 235 mA h g-1, superior to all VO-based electrodes reported in the literature. Furthermore, a full cell was first fabricated by employing VO@C-2 as the anode and LiFePO4 as the cathode, which exhibited a capacity of 213 mA h g-1 after 100 cycles at 0.1 A g-1, indicating the potential of VO as an anode for practical application.

17.
Front Bioeng Biotechnol ; 9: 721617, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34395410

RESUMO

Photothermal/magnetothermal-based hyperthermia cancer therapy techniques have been widely investigated, and associated nanotechnology-assisted treatments have shown promising clinical potentials. However, each method has some limitations, which have impeded extensive applications. For example, the penetration ability of the photothermal is not satisfactory, while the heating efficiency of the magnetothermal is very poor. In this study, a novel magnetite vortex nanoring nanoparticle-coated with polypyrrole (denoted as nanoring Fe3O4@PPy-PEG) was first synthesized and well-characterized. By combining photothermal and magnetothermal effects, the performance of the dual-enhanced hyperthermia was significantly improved, and was thoroughly examined in this study. Benefiting from the magnetite vortex nanoring and polypyrrole, Fe3O4@PPy-PEG showed excellent hyperthermia effects (SAR = 1,648 Wg-1) when simultaneously exposed to the alternating magnetic field (300 kHz, 45 A) and near-infrared (808 nm, 1 W cm-2) laser. What is more, nanoring Fe3O4@PPy-PEG showed a much faster heating rate, which can further augment the antitumor effect by incurring vascular disorder. Besides, Fe3O4@PPy-PEG exhibited a high transverse relaxation rate [60.61 mM-1 S-1 (Fe)] at a very low B0 field (0.35 T) and good photoacoustic effect. We believe that the results obtained herein can significantly promote the development of multifunctional nanoparticle-mediated magnetic and photo induced efficient hyperthermia therapy.

18.
Angew Chem Int Ed Engl ; 60(45): 24080-24088, 2021 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-34260804

RESUMO

Large conjugated rings with persistent currents are novel promising structures in molecular-scale electronics. A six-porphyrin nanoring structure that allegedly sustained an aromatic ring current involving 78π electrons was recently synthesized. We provide here compelling evidence that this molecule is not aromatic, contrary to what was inferred from the analysis of 1 H-NMR data and computational calculations that suffer from large delocalization errors. The main reason behind the absence of an aromatic ring current in these nanorings is the low delocalization in the transition from the porphyrins to the bridging butadiyne linkers, which disrupts the overall conjugated circuit. These results highlight the importance of choosing a suitable computational method to study large conjugated molecules and the appropriate aromaticity descriptors to identify the part of the molecule responsible for the loss of aromaticity.

19.
ACS Nano ; 15(7): 12180-12188, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34170108

RESUMO

Conventional photolithography, due to its scalability, robustness, and straightforward processes, has been widely applied to micro- and nanostructure manufacturing in electronics, optics, and biology. However, optical diffraction limits the ultimate resolution of conventional photolithography, which hinders its potential in nanoscale patterning for broader applications. Here, we introduce a derivative of conventional photolithography for nanoscale patterning called dual-layer photolithography (DLPL), which is based on the controlled exposure and development of overlapping positive and negative photoresists. In a typical experiment, substrates are sequentially coated by two layers of photoresists (both positive and negative). Then, we purposefully control the exposure time to generate slightly larger features in the positive photoresist than those in the negative photoresist. After development, their overlapping areas become the final features, which outline the original features. We demonstrate line widths down to 300 nm here, which can be readily improved with more precise control. By adjusting the lithography parameters and material deposition, the feature sizes, shapes (e.g., rings, numbers, letters), line widths (300-900 nm), and materials (e.g., SiO2, Cr, and Ag) of these features can be independently controlled. Combined with anisotropic etching, more complex three-dimensional nanostructures can be fabricated as well, as we demonstrate here with Si. We further fabricate photodetectors as an example application to show that these nanostructures fabricated by DLPL can be used to promote light-trapping MAPbI3 perovskite films to achieve good photoelectric properties. This strategy is not limited to ultraviolet photolithography and may also be incorporated into other energetic beam-based lithographic approaches, including deep and extreme ultraviolet photolithographies and electron beam lithography, to enhance their resolution.

20.
Nanomaterials (Basel) ; 11(5)2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33924777

RESUMO

The development of optical systems is heading to multi-branch circuit design and miniaturization. A beam splitter is a common device for dividing an incident beam into two separate beams. Conventional beam splitters are constructed using coated prisms or glass plate. Their bulky size, right-angled output direction, and fixed splitting ratio greatly limit the design of optical arrangement and also hinder the system integration. Here, an all-dielectric metasurface composed of symmetric nano-rings as a beam splitter are designed by Finite-Difference Time-Domain method. By changing the inner and outer radiuses of the nano-rings, the wavefront phase of the emergence beam can be adjusted to form a phase gradient, and the incident beam of arbitrary polarization is divided into two beams according to the designed transmittance and angle. The initial phase of the emergence beam can be changed by adjusting the refractive index of the substrate or adding the silicon film to the substrate, and the splitting ratio can be adjusted from 0.5:1 to 1:1. The simulation demonstrates that the metasurface-based beam splitter is independent of polarization and the power efficiency is over 92% with a compact area of 33.6 µm × 33.6 µm. This compact metasurface-based beam splitter has promising potential for enabling new types of compact optical systems and advancing metasurface-based functional integrated photonic applications.

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