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This study aimed to investigate the potential of four sea water microalgae, isolated and cultivated at M′diq Bay in Morocco, as a new source of natural antioxidants. These microalgae belong to different classes, including Phaedactylium tricornitum (Bacillariophyceae), Nannochloropsis gaditana (Eustigmatophyceae), Nannochloris sp (Trebouxiophyceae), and Tetraselmis suecica (Chlorodendrophycea). The antioxidant properties were screened by the use of in vitro assays, namely 2,2-difenil-1-picrylhydrazyl, Ferric reducing antioxidant power, and Ferrous ions chelating activity, and compoundidentification was carried out in methanol and acetone extracts of both dried and fresh microalgae biomass by HPLC–PDA–MS analysis. Among the investigated microalgae, Phaedactylium tricornutum was the richest one regarding its carotenoid (especially all-E-fucoxanthin) and phenolic (especially protocatechuic acid) contents, as well as antioxidant activity (65.5%), followed by Nannochloris sp, Tetraselmis suicica, and Nannochloropsis gaditana, with antioxidant activity of 56.8%, 54.9%, and 51.1%, respectively.

During the selective laser melting(SLM) process of IN718, different process parameters have a significant impact on its microstructure. To analyze the interrelationship between process parameters and microstructure, in this study, the relationship between primary dendrite arm spacing(PDAS) and process parameters was established through a solidification model, and the accuracy of the model was verified through experiments. Both the calculation results and the experimental results show that when the laser power increases, PDAS increases accordingly; while as the scanning speed and hatch distance increase, PDAS decreases accordingly; and from the bottom to the top of the molten pool, PDAS gradually increases. At the same time, the top of the molten pool is more sensitive to the change of process parameters, while the middle and bottom are relatively insensitive. These research results are of certain guiding significance for the microstructure regulation of IN718. IN718合金在选区激光熔化(selective laser melting, SLM)过程中, 不同的工艺参数会对其微观组织产生显著影响。为分析工艺参数和微观组织的相互关系, 通过凝固模型建立了一次枝晶间距(primary dendrite arm spacing, PDAS)与工艺参数之间的关系并通过实验验证了模型的准确性。计算结果与实验结果均表明: 当激光功率提高时, PDAS随之增加; 而扫描速度与扫描间距增加时, PDAS随之减小; 从熔池底部至顶部, PDAS呈逐渐增加的趋势, 同时熔池顶部对工艺参数的变化较为敏感, 而中部与底部相对迟钝。研究结果对IN718合金的微观组织调控具有一定的指导意义。

Esophageal cancer (EC) ranks among the most prevalent and lethal malignancies worldwide, and conventional therapeutic modalities, including surgery, radiotherapy, and chemotherapy, are constrained by inherent limitations. Recent advances in nanomedicine have opened new avenues for EC treatment. To achieve efficient and precise tumor eradication, this study developed a pH-responsive composite nanoplatform featuring a hollow architecture to enable high-efficiency loading of photosensitizers and realize multimodal synergistic therapy against EC through the integration of photothermal therapy (PTT), photodynamic therapy (PDT), and chemodynamic therapy (CDT).PurposeEsophageal cancer (EC) ranks among the most prevalent and lethal malignancies worldwide, and conventional therapeutic modalities, including surgery, radiotherapy, and chemotherapy, are constrained by inherent limitations. Recent advances in nanomedicine have opened new avenues for EC treatment. To achieve efficient and precise tumor eradication, this study developed a pH-responsive composite nanoplatform featuring a hollow architecture to enable high-efficiency loading of photosensitizers and realize multimodal synergistic therapy against EC through the integration of photothermal therapy (PTT), photodynamic therapy (PDT), and chemodynamic therapy (CDT).A pH-responsive Cu2-xSe/PDA/IR820 composite nanoplatform was constructed by coating hollow Cu2-xSe nanoparticles with polydopamine PDA and loading the near-infrared photosensitizer IR820. Morphology, crystalline phase, elemental composition, and surface chemistry were characterized by TEM, XRD, XPS, and FT-IR. Photothermal conversion efficiency was quantified under 808 nm laser irradiation. IR820 release kinetics were monitored under different pH conditions of 5.0, 6.0, and 7.0 to assess pH-responsive behavior. In vitro studies on KYSE-150 EC cells included viability by CCK-8 assay, apoptosis by flow cytometry, ROS generation by DCFH-DA probe, mitochondrial membrane potential by JC-1 staining, and cellular uptake analysis. In vivo antitumor efficacy and biosafety were evaluated in an AKR tumor-bearing C57BL/6J mouse model via intratumoral injection and 808 nm laser irradiation, followed by tumor volume measurement, histopathological analysis with H&E, Ki-67, and TUNEL staining, and systemic toxicity assessment.MethodsA pH-responsive Cu2-xSe/PDA/IR820 composite nanoplatform was constructed by coating hollow Cu2-xSe nanoparticles with polydopamine PDA and loading the near-infrared photosensitizer IR820. Morphology, crystalline phase, elemental composition, and surface chemistry were characterized by TEM, XRD, XPS, and FT-IR. Photothermal conversion efficiency was quantified under 808 nm laser irradiation. IR820 release kinetics were monitored under different pH conditions of 5.0, 6.0, and 7.0 to assess pH-responsive behavior. In vitro studies on KYSE-150 EC cells included viability by CCK-8 assay, apoptosis by flow cytometry, ROS generation by DCFH-DA probe, mitochondrial membrane potential by JC-1 staining, and cellular uptake analysis. In vivo antitumor efficacy and biosafety were evaluated in an AKR tumor-bearing C57BL/6J mouse model via intratumoral injection and 808 nm laser irradiation, followed by tumor volume measurement, histopathological analysis with H&E, Ki-67, and TUNEL staining, and systemic toxicity assessment.The hollow Cu2-xSe/PDA/IR820 nanoparticles exhibited a uniform size of approximately 164 nm, excellent colloidal stability, and a high photothermal conversion efficiency of 44.56% under 808 nm laser irradiation. IR820 release displayed pronounced pH sensitivity, with a cumulative release of 23.07% at pH 5.0 within 30 minutes. In vitro, the nanoplatform combined with laser irradiation reduced KYSE-150 cell viability to 1.2% at 100 μg/mL, with an IC50 value of 18.74 μg/mL, induced 28.57% apoptosis, elevated intracellular ROS levels, decreased mitochondrial membrane potential, and depleted glutathione to 335 μmol/gprot. In vivo fluorescence imaging confirmed effective tumor accumulation via the EPR effect, with peak signal at 24 hours post-injection. Combined PTT/PDT/CDT treatment significantly suppressed tumor growth, reducing final tumor volume to 17.8% of the control group, and induced extensive apoptosis and necrosis in tumor tissues. Systemic biosafety evaluations revealed no significant hematological or histopathological abnormalities.ResultsThe hollow Cu2-xSe/PDA/IR820 nanoparticles exhibited a uniform size of approximately 164 nm, excellent colloidal stability, and a high photothermal conversion efficiency of 44.56% under 808 nm laser irradiation. IR820 release displayed pronounced pH sensitivity, with a cumulative release of 23.07% at pH 5.0 within 30 minutes. In vitro, the nanoplatform combined with laser irradiation reduced KYSE-150 cell viability to 1.2% at 100 μg/mL, with an IC50 value of 18.74 μg/mL, induced 28.57% apoptosis, elevated intracellular ROS levels, decreased mitochondrial membrane potential, and depleted glutathione to 335 μmol/gprot. In vivo fluorescence imaging confirmed effective tumor accumulation via the EPR effect, with peak signal at 24 hours post-injection. Combined PTT/PDT/CDT treatment significantly suppressed tumor growth, reducing final tumor volume to 17.8% of the control group, and induced extensive apoptosis and necrosis in tumor tissues. Systemic biosafety evaluations revealed no significant hematological or histopathological abnormalities.Hollow Cu2-xSe/PDA/IR820 composite nanoparticles loaded with IR820 were successfully fabricated and demonstrated remarkable advantages in multimodal combination therapy against EC.ConclusionHollow Cu2-xSe/PDA/IR820 composite nanoparticles loaded with IR820 were successfully fabricated and demonstrated remarkable advantages in multimodal combination therapy against EC.

Diagnostic markers are desperately needed for the early detection of pancreatic ductal adenocarcinoma (PDA). We describe sets of markers expressed in temporal order in mouse models during pancreatitis, PDA initiation and progression. Cell type specificity and the differential expression of PDA markers were identified by screening single cell (sc) RNAseq from tumor samples of a mouse model for PDA (KIC) at early and late stages of PDA progression compared to that of a normal pancreas. Candidate genes were identified from three sources: (1) an unsupervised screening of the genes preferentially expressed in mouse PDA tumors; (2) signaling pathways that drive PDA, including the Ras pathway, calcium signaling, and known cancer genes, or genes encoding proteins that were identified by differential mass spectrometry (MS) of mouse tumors and conditioned media from human cancer cell lines; and (3) genes whose expression is associated with poor or better prognoses (PAAD, oncolnc.org). The developmental progression of PDA was detected in the temporal order of gene expression in the cancer cells of the KIC mice. The earliest diagnostic markers were expressed in epithelial cancer cells in early-stage, but not late-stage, PDA tumors. Other early markers were expressed in the epithelium of both early- and late-state PDA tumors. Markers that were expressed somewhat later were first elevated in the epithelial cancer cells of the late-stage tumors, then in both epithelial and mesenchymal cells, or only in mesenchymal cells. Stromal markers were differentially expressed in early- and/or late-stage PDA neoplasia in fibroblast and hematopoietic cells (lymphocytes and/or macrophages) or broadly expressed in cancer and many stromal cell types. Pancreatitis is a risk factor for PDA in humans. Mouse models of pancreatitis, including caerulein treatment and the acinar-specific homozygous deletion of differentiation transcription factors (dTFs), were screened for the early expression of all PDA markers identified in the KIC neoplasia. Prognostic markers associated with a more rapid decline were identified and showed differential and cell-type-specific expression in PDA, predominately in late-stage epithelial and/or mesenchymal cancer cells. Select markers were validated by immunohistochemistry in mouse and human samples of a normal pancreas and those with early- and late-stage PDA. In total, we present 2165 individual diagnostic and prognostic markers for disease progression to be tested in humans from pancreatitis to late-stage PDA.

The synthesis of a family of chiral and enantiomerically pure pyridyl‐diamide (pda) ligands that upon complexation with europium [Eu(CF3SO3)3] result in chiral complexes with metal centered luminescence is reported; the sets of enantiomers giving rise to both circular dichroism (CD) and circularly polarized luminescence (CPL) signatures. The solid‐state structures of these chiral metallosupramolecular systems are determined using X‐ray diffraction showing that the ligand chirality is transferred from solution to the solid state. This optically favorable helical packing arrangement is confirmed by recording the CPL spectra from the crystalline assembly by using steady state and enantioselective differential chiral contrast (EDCC) CPL Laser Scanning Confocal Microscopy (CPL‐LSCM) where the two enantiomers can be clearly distinguished. Enantiopure formation of chiral self‐templated lanthanide supramolecular structures gives rise to CPL when probed both in solution and the solid state demonstrating chirality transfer.

Zinc oxide (ZnO) nanostructures are widely used in optical sensors and biosensors. Functionalization of these nanostructures with polymers enables optical properties of ZnO to be tailored. Polydopamine (PDA) is a highly biocompatible polymer, which can be used as a versatile coating suitable for application in sensor and biosensor design. In this research, we have grown ZnO-based nanorods on the surface of ITO-modified glass-plated optically transparent electrodes (glass/ITO). Then the deposition of the PDA polymer layer on the surface of ZnO nanorods was performed from an aqueous PDA solution in such a way glass/ITO/ZnO-PDA structure was formed. The ZnO-PDA composite was characterized by SEM, TEM, and FTIR spectroscopy. Then glucose oxidase (GOx) was immobilized using crosslinking by glutaraldehyde on the surface of the ZnO-PDA composite, and glass/ITO/ZnO-PDA/GOx-based biosensing structure was designed. This structure was applied for the photo-electrochemical determination of glucose (Glc) in aqueous solutions. Photo-electrochemical determination of glucose by cyclic voltammetry and amperometry has been performed by glass/ITO/ZnO-PDA/GOx-based biosensor. Here reported modification/functionalization of ZnO nanorods with PDA enhances the photo-electrochemical performance of ZnO nanorods, which is well suited for the design of photo-electrochemical sensors and biosensors.

Manipulating the thermal decomposition behavior of energetic materials is the key to further pushing the combustion performance of solid rocket propellants. Herein, atomically dispersed Pb single atoms on polydopamine (PDA‐Pb) are demonstrated, which display unprecedented catalytic activity toward the thermal decomposition of cyclotrimethylenetrinitramine (RDX). Impressively, RDX‐based propellants with the addition of PDA‐Pb catalyst exhibit substantially enhanced burning rates (14.98 mm s−1 at 2 MPa), which is 4.8 times faster than that without PDA‐Pb and represents the best catalytic performance among Pb‐based catalysts. Moreover, it also possesses low‐pressure exponents in broad pressure ranges, which can enable more stable and safer combustion in solid rocket engines. Theoretical calculation unravels the efficient catalytic activity is stemmed from the enhanced interfacial electronic coupling between RDX and PDA‐Pb via orbital level engineering. More importantly, PDA‐Pb also presents similar catalytic behavior toward the decomposition of nitrocellulose, suggesting its broad catalytic generality. This work can open up new opportunities in the field of energetic compound combustion by exploring Pb‐based single atom catalysts and beyond. Atomically dispersed Pb single atoms on polydopamine (PDA‐Pb) display excellent catalytic activity towards the thermal decomposition of energetic materials. The addition of PDA‐Pb can substantially decrease the thermal decomposition temperature and consequently boost the burning rate of the propellants. Theoretical calculations reveal the efficient catalytic activity is stemmed from the enhanced interfacial electronic coupling via orbital level engineering.

Coffee is one of the world’s most popular beverages, and its consumption generates copious amounts of waste. The most relevant by-product of the coffee industry is the spent coffee grounds, with 6 million tons being produced worldwide per year. Although generally treated as waste, spent coffee grounds are a rich source of several bioactive compounds with applications in diverse industrial fields. The present work aimed at the analysis of spent coffee grounds from different geographical origins (Guatemala, Colombia, Brazil, Timor, and Ethiopia) for the identification of bioactive compounds with industrial interest. For this purpose, the identification and quantification of the bioactive compounds responsible for the antioxidant activity attributed to the spent coffee grounds were attempted using miniaturized solid-phase extraction (µ-SPEed), combined with ultrahigh-performance liquid chromatography with photodiode array detection (UHPLC-PDA). After validation of the µ-SPEed/UHPLC-PDA method, this allowed us to conclude that caffeine and 5-caffeoylquinic acid (5-CQA) are the most abundant bioactive compounds in all samples studied. The total phenolic content (TPC) and antioxidant activity are highest in Brazilian samples. The results obtained show that spent coffee grounds are a rich source of bioactive compounds, supporting its bioprospection based on the circular economy concept closing the loop of the coffee value chain, toward the valorization of coffee by-products.

An extensive fibroinflammatory stroma rich in macrophages is a hallmark of pancreatic cancer. In this disease, it is well appreciated that macrophages are immunosuppressive and contribute to the poor response to immunotherapy; however, the mechanisms of immune suppression are complex and not fully understood. Immunosuppressive macrophages are classically defined by the expression of the enzyme Arginase 1 (ARG1), which we demonstrated is potently expressed in pancreatic tumor-associated macrophages from both human patients and mouse models. While routinely used as a polarization marker, ARG1 also catabolizes arginine, an amino acid required for T cell activation and proliferation. To investigate this metabolic function, we used a genetic and a pharmacologic approach to target Arg1 in pancreatic cancer. Genetic inactivation of Arg1 in macrophages, using a dual recombinase genetically engineered mouse model of pancreatic cancer, delayed formation of invasive disease, while increasing CD8 + T cell infiltration. Additionally, Arg1 deletion induced compensatory mechanisms, including Arg1 overexpression in epithelial cells, namely Tuft cells, and Arg2 overexpression in a subset of macrophages. To overcome these compensatory mechanisms, we used a pharmacological approach to inhibit arginase. Treatment of established tumors with the arginase inhibitor CB-1158 exhibited further increased CD8 + T cell infiltration, beyond that seen with the macrophage-specific knockout, and sensitized the tumors to anti-PD1 immune checkpoint blockade. Our data demonstrate that Arg1 drives immune suppression in pancreatic cancer by depleting arginine and inhibiting T cell activation.

Seaweed is an important food widely consumed in Asian countries. Seaweed has a diverse array of bioactive compounds, including dietary fiber, carbohydrate, protein, fatty acid, minerals and polyphenols, which contribute to the health benefits and commercial value of seaweed. Nevertheless, detailed information on polyphenol content in seaweeds is still limited. Therefore, the present work aimed to investigate the phenolic compounds present in eight seaweeds [Chlorophyta (green), Ulva sp., Caulerpa sp. and Codium sp.; Rhodophyta (red), Dasya sp., Grateloupia sp. and Centroceras sp.; Ochrophyta (brown), Ecklonia sp., Sargassum sp.], using liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LC-ESI-QTOF-MS/MS). The total phenolic content (TPC), total flavonoid content (TFC) and total tannin content (TTC) were determined. The antioxidant potential of seaweed was assessed using a 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay, a 2,2′-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) free radical scavenging assay and a ferric reducing antioxidant power (FRAP) assay. Brown seaweed species showed the highest total polyphenol content, which correlated with the highest antioxidant potential. The LC-ESI-QTOF-MS/MS tentatively identified a total of 54 phenolic compounds present in the eight seaweeds. The largest number of phenolic compounds were present in Centroceras sp. followed by Ecklonia sp. and Caulerpa sp. Using high-performance liquid chromatography-photodiode array (HPLC-PDA) quantification, the most abundant phenolic compound was p-hydroxybenzoic acid, present in Ulva sp. at 846.083 ± 0.02 μg/g fresh weight. The results obtained indicate the importance of seaweed as a promising source of polyphenols with antioxidant properties, consistent with the health potential of seaweed in food, pharmaceutical and nutraceutical applications.