Sub-diffraction limited nanogroove fabrication of 30 nm features on diamond films using 800 nm femtosecond laser irradiation.

By controlling the 800 nm fs laser energy and applying an isopropyl alcohol environment, controlled sub-diffraction limited lithography with a characteristic structure of approximately 30 nm was achieved on the surface of diamond films, and diamond gratings with a period of 200 nm were fabricated. The fabrication of single grooves with a feature size of 30 nm demonstrates the potential for patterning periodic or nonperiodic structures, and the fabrication of 200 nm periodic grating structures demonstrates the ability of the technique to withstand laser proximity effects. This enhances the technology of diamond film nanofabrication and broadens its potential applications in areas such as optoelectronics and biology.

Temporal-spatial dynamics of electronic plasma in a femtosecond laser-induced sapphire microstructure.

In this study, the time-spatial evolution of single-pulse femtosecond laser-induced plasma in sapphire is studied by using femtosecond time-resolved pump-probe shadowgraphy. Laser-induced sapphire damage occurred when the pump light energy was increased to 20 µJ. Based on its shadowgraphy image, the threshold electron density can be estimated to be about 2.48×1020 c m -3. The evolution law of the transient peak electron density and its spatial position as femtosecond laser propagation in sapphire were researched. The transitions from single-focus to multi-focus as the laser focus shifted from the surface to a deeper part were observed from the transient shadowgraphy images. The focal point distance in multi-focus increased as the focal depth increased. The distributions of femtosecond laser-induced free electron plasma and the final microstructure were consistent with each other.

Fe3+@PDOPA­b­PSar Nanoparticles for Magnetic Resonance Imaging and Cancer Chemotherapy.

Purpose: Chemotherapy treatments for cancer are always accompanied by a low concentration of drug delivered in the tumor area and severe side effects including systemic toxicity. Improving the concentration, biocompatibility, and biodegradability of regional chemotherapy drugs is a pressing challenge in the field of materials. Methods: N-Phenyloxycarbonyl-amino acids (NPCs) which exhibit significant tolerance to nucleophiles, such as water and hydroxyl-containing compounds, are promising monomers for the synthesis of polypeptides and polypeptoids. Cell line and mouse models were used to comprehensively explore how to enhance the tumor MRI signal and evaluate the therapeutic effect of Fe@POS-DOX nanoparticles. Results: In this study, poly(3,4-dihydroxy-L-phenylalanine)-b-polysarcosine (PDOPA-b-PSar, simplified as POS) was synthesized by the block copolymerization of DOPA-NPC with Sar-NPC. Fe@POS-DOX nanoparticles were prepared in order to utilize the strong chelation of catechol ligands to iron (III) cations and the hydrophobic interaction between DOX and DOPA block to deliver chemotherapeutics to tumor tissue. The Fe@POS-DOX nanoparticles exhibit high longitudinal relaxivity (r 1 = 7.06 mM-1·s-1) and act as T 1-weighted magnetic resonance (MR) imaging contrast agents. Further, the main focus was improving tumor site-specific bioavailability and achieving therapeutic effects through the biocompatibility and biodegradability of Fe@POS-DOX NPs. The Fe@POS-DOX treatment exhibited excellent antitumor effects. Conclusion: Upon intravenous injection, Fe@POS-DOX delivers DOX specifically to the tumor tissues, as revealed by MR, and leads to the inhibition of tumor growth without overt toxicity to normal tissues, thus displaying considerable potential for use in clinical applications.

Integrated manganese (III)-doped nanosystem for optimizing photothermal ablation: Amplifying hyperthermia-induced STING pathway and enhancing antitumor immunity.

Despite the great promise initially demonstrated by photothermal ablation (PTA) therapy, its inability to completely ablate large tumors is problematic, because this has been found to result in residual tumors at ablation margins and bring a relative high rate of subsequent recurrences and metastases. To address this issue, we herein report a smart photothermal nanosystem (PBM) based on FDA-approved Prussian blue (PB) nanoparticles, doped with Mn (III) to suppress the tumor debris left by incomplete ablation. Notably, our study demonstrated that PTA-induced hyperthermia plays a crucial role in initiating the cGAS-STING pathway by generating damaged cytosolic DNA. This PBM nanosystem, which consumes glutathione and continuously releases Mn(II), further amplifies the PTA-induced cGAS-STING pathway in CT26 colon and 4T1 breast tumor models. Moreover, treatment with PBM following PTA boosted the robust immune response in situ and extended to the whole body with a remarkable suppression effect on both local residual and distant tumors. This work, which improves the antitumor efficacy of nonablated areas utilizing hyperthermia-enhanced immune therapy, may therefore provide a promising adjuvant antitumor strategy for the issue of incomplete ablation. STATEMENT OF SIGNIFICANCE: This work discovered, for the first time, that photothermal ablation-induced hyperthermia plays a crucial role in initiating the cGAS-STING pathway. Taking advantage of this finding, we developed a smart photothermal material (PBM) tailored for incomplete tumor ablation. This integrated Mn(III)-doped nanosystem (PBM) demonstrated superior therapeutic benefits due to the thermal ablation process and immune enhancement. As the photothermal ablation-induced cGAS-STING pathway was triggered, the released Mn(III) consumes GSH while continuously transferred to Mn(II), which further amplified STING activation and facilitated a more robust antitumor immunity, thereby remarkably inhibiting both local residual and distant tumors in virtue of the biological changes under thermal ablation.

Fabrication of microgrooves in PMN-PT using femtosecond laser irradiation and acid etching.

A simple method of fabricating Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) deep grooves with high aspect ratios using an 800-nm femtosecond laser with chemical-selective etching is demonstrated. The 567-µm-deep grooves with aspect ratios of approximately 35 were obtained with no cracks or thermal affected zone. The morphologies and chemical compositions of grooves were analyzed by a scanning electron microscope with an energy dispersive x-ray spectrometer. The formation mechanism of PMN-PT grooves is attributed to the chemical reactions of hydrochloric acid (HCl) and laser-induced structural changes (LISCs). PMN-PT in LISC became amorphous or mixtures of metal oxide from crystal and all the compounds could react with concentrated HCl and form soluble matter, leaving no precipitation. Furthermore, influences of laser irradiation parameters on depths and aspect ratios of grooves are studied.

A Topology-Defined Polyester Elastomer from CO2 and 1,3-Butadiene: A One-Pot-One-Step "Scrambling Polymerizations" Strategy.

It is significant and challenging to use CO2 to produce polymeric materials, especially with olefins. Here, a novel strategy named "scrambling polymerizations" is designed and performed for the copolymerization of a CO2 -and-1,3-butadiene-derived valerolactone, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL), with ϵ-caprolactone (CL) to prepare polyesters. Anionic ring-opening polymerization of CL and conjugated addition oligomerization of EVL take place individually to form PCL and EVL oligomers, respectively. Then EVL oligomers insert into PCL by transesterification resulting in polyester P(CL-co-EVL) with a tunable topology and composition. The non-cytotoxic and degradable polyester network with elongation at break of >600 % can be used as an elastomer. We propose a method to provide polyester elastomers from CO2 and olefins for the first time, and expand the potential of transformation from sustainable feedstocks to polymeric materials.

Development of a Novel MR Colonography via Iron-Based Solid Lipid Nanoparticles.

PURPOSE: To develop an iron-based solid lipid nanoparticle (SLN) absorbable by the intestinal wall and assess the differential diagnostic value of intestinal lesions in magnetic resonance imaging (MRI). METHODS: SLNs were prepared with the simultaneous loading of trivalent Fe ions (Fe3+), levodopa methyl ester (DM), and fluorescein isothiocyanate (FITC). We evaluated the particle size, loading rate, encapsulation efficiency, and cytotoxicity of SLNs. The T1 contrast effects of the FeDM-FITC-SLNs and gadolinium-based contrast agent (GBCA) were compared in different mouse models: acute ulcerative colitis (AUC), chronic ulcerative colitis (CUC), colon adenocarcinoma (COAD), and normal control. MRI was performed in the same mouse with intravenous injection of GBCA on day 1 and enema of FeDM-FITC-SLNs on day 2. The signal-to-noise ratios (SNRs) were compared using one-way analysis of variance. Tissues were then collected for histology. RESULTS: The average particle size of FeDM-FITC-SLN was 220 nm. The mean FeDM loading rate was 94.3%, and the encapsulation efficiency was 60.3%. The relaxivity was 4.02 mM-1·s-1. After enema with FeDM-FITC-SLNs, MRI showed the following contrast enhancement duration: AUC = COAD > normal > CUC. Confocal fluorescence microscopy confirmed that FeDM-FITC-SLNs were mainly distributed in the intestinal mucosa and tumor capsule. CONCLUSION: Iron-based SLNs are promising alternatives for contrast enhancement at T1-weighted MRI and will help in the differential diagnosis of intestinal bowel diseases (IBDs).

Biodegradable Polysarcosine with Inserted Alanine Residues: Synthesis and Enzymolysis.

Polysarcosine (PSar), a water-soluble polypeptoid, is gifted with biodegradability via the random ring-opening copolymerization of sarcosine- and alanine-N-thiocarboxyanhydrides catalyzed by acetic acid in controlled manners. Kinetic investigation reveals the copolymerization behavior of the two monomers. The random copolymers, named PaS, with high molecular weights between 5.3 and 43.6 kg/mol and tunable Ala molar fractions varying from 6 to 43% can be degraded by porcine pancreatic elastase within 50 days under mild conditions (pH = 8.0 at 37 °C). Both the biodegradation rate and water solubility of PaS depend on the content of Ala residues. PaS with Ala fractions below 43% are soluble in water, while the one with 43% Ala self-assembles in water into nanoparticles. Moreover, PaS are noncytotoxic at the concentration of 5 mg/mL. The biodegradability and biocompatibility endow the Ala-containing PSar with the potential to replace poly(ethylene glycol) as a protective shield in drug-delivery.

Temporal-spatial dynamics of electronic plasma in femtosecond laser induced damage.

In this study, transient temporal-spatial evolutions of femtosecond (fs) laser pulse-induced filaments and electronic plasma when laser induced damage occurred in fused silica were investigated using fs time-resolved pump-probe shadowgraphy. The transient peak electron density increased and then decreased as delay time of probe beam increased. Its corresponding spatial positions moved from the sample surface to the inside of the sample, but remained at the nonlinear focus for a relatively long time. The maximum electron density increased as pump energies increased and then became saturated at 8 µJ, above which laser-induced material damage occurred. The material damage threshold electron density was approximately 1.27×1020 cm-3. The laser-induced material damage position corresponded to the position of the maximum electron density. Furthermore, the material damage was extended from the nonlinear focus to the deeper parts of the sample at pump energies above 8 µJ. This tendency agreed well with the spatial distribution of the maximum transient electron density at each propagation depth, implying that the fs time-resolved pump-probe shawdowgraphy is a meaningful tool for predicting the distribution of laser-induced microstructures in ultrafast laser micromachining.