Search Results (31)

Triple-negative breast cancer (TNBC) remains a major clinical challenge due to its aggressive behavior and lack of targeted therapies. Accurate early prediction of response to neoadjuvant chemotherapy (NACT) is essential for guiding personalized treatment strategies and improving patient outcomes. In this study, we present an attention-based multiple instance learning (MIL) framework designed to predict pathologic complete response (pCR) directly from pre-treatment hematoxylin and eosin (H&E)-stained biopsy slides. The model was trained on a retrospective in-house cohort of 174 TNBC patients and externally validated on an independent cohort (n = 30). It achieved a mean area under the curve (AUC) of 0.85 during five-fold cross-validation and 0.78 on external testing, demonstrating robust predictive performance and generalizability. To enhance model interpretability, attention maps were spatially co-registered with multiplex immunohistochemistry (mIHC) data stained for PD-L1, CD8+ T cells, and CD163+ macrophages. The attention regions exhibited moderate spatial overlap with immune-enriched areas, with mean Intersection over Union (IoU) scores of 0.47 for PD-L1, 0.45 for CD8+ T cells, and 0.46 for CD163+ macrophages. The presence of these biomarkers in high-attention regions supports their biological relevance to NACT response in TNBC. This not only improves model interpretability but may also inform future efforts to identify clinically actionable histological biomarkers directly from H&E-stained biopsy slides, further supporting the utility of this approach for accurate NACT response prediction and advancing precision oncology in TNBC. Full article

This study successfully prepared MIL-101(Fe)@MoS₂ composite photocatalysts via hydrothermal methods to address the efficient removal of refractory organic dyes in dye wastewater. Characterization using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) confirmed that molybdenum disulfide (MoS₂) was uniformly loaded onto the surface of MIL-101(Fe), forming a heterojunction that significantly enhanced light absorption capacity and charge separation efficiency. In a visible-light-driven photo-Fenton system, this material exhibited excellent degradation performance for Congo red (CR). At an initial CR concentration of 50 mg/L, a catalyst dosage of 0.2 g/L, 4 mL of added H₂O₂, and pH 7, CR was completely degraded within 30 min, with the total organic carbon (TOC) removal reaching 72.5%. The material maintained high degradation efficiency (>90%) across a pH range of 3–9, overcoming the traditional Fenton system’s dependency on acidic media. Radical-trapping experiments indicated that superoxide radicals (·O₂⁻) and photogenerated holes (·h⁺) were the primary active species responsible for degradation, revealing a synergistic catalytic mechanism at the heterojunction interface. Recyclability tests showed that the material retained 90.8% degradation efficiency after five cycles, and an X-ray photoelectron spectroscopy (XPS) analysis demonstrated the stable binding of Fe and Mo, preventing secondary pollution. This study provides a scientific basis for developing efficient, stable, and wide-pH adaptable photo-Fenton catalytic systems, contributing significantly to the advancement of green water treatment technologies. Full article

Halide perovskite has shown great potential in photocatalysis owing to its diversity, suitable energy band alignment, rapid charge transfer, and excellent optical properties. However, poor stability, especially under humid conditions, hinders their practical application in photocatalysis. In this work, we report the encapsulation of inorganic–organic hybrid perovskite QDs into MIL-101(Cr) through an in situ growth strategy to prepare a series of MAPbBr₃@MIL-101(Cr) (MA = CH₃NH₃⁺) composites. The perovskite precursors, i.e., MABr and PbBr₂, were successively introduced into the pores of MOF, where the perovskite quantum dots were self-assembled in the confined environment. In photocatalytic CO₂ reduction, 11%MAPbBr₃@MIL-101(Cr) composite displayed the best performance among the composites with a total CO and CH₄ yield of 875 μmol g⁻¹ in 9 h, which was 8 times higher than that of the pure MAPbBr₃. Such high gas production efficiency could be maintained for 78 h at least without structural and morphologic decomposition. The remarkable stability and catalytic activity of composites are mainly due to the synergistic effect and improved electron transfer between MAPbBr₃ and MIL-101(Cr). Moreover, these composites revealed a novel mechanism, showing switched CH₄ selectivity with the controlling of the perovskite location and contents. Those with perovskites encapsulated in the mesopores of MIL-101(Cr) were more preferential for CO production, while those with perovskites encapsulated in both meso- and micropores could produce CH₄ dominantly. Full article

In environmental chemistry, photocatalysts for eliminating organic contaminants in water have gained significant interest. Our study introduces a unique heterostructure combining MIL-101(Cr) and bismuth oxyiodide (Bi₅O₇I). We evaluated this nanostructure’s efficiency in adsorbing and degrading tetracycline (TC) under visible light. The Bi₅O₇I@MIL-101(Cr) composite, with a surface area of 637 m²/g, prevents self-aggregation seen in its components, enhancing visible light absorption. Its photocatalytic efficiency surpassed Bi₅O₇I and MIL-101(Cr) by 33.4 and 9.2 times, respectively. Comprehensive analyses, including scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirmed the successful formation of the heterostructure with defined morphological characteristics. BET analysis demonstrated its high surface area, while X-ray diffraction (XRD) confirmed its crystallinity. Electron spin resonance (ESR) tests showed significant generation of reactive oxygen species (ROS) like h⁺ and·•O₂⁻ under light, crucial for TC degradation. The material maintained exceptional durability over five cycles. Density functional theory (DFT) simulations and empirical investigations revealed a type I heterojunction between Bi₅O₇I and MIL-101(Cr), facilitating efficient electron–hole pair separation. This study underscores the superior photocatalytic activity and stability of Bi₅O₇I@MIL-101(Cr), offering insights into designing innovative photocatalysts for water purification. Full article

The conventional synthesis of the Metal–Organic Framework (MOF) MIL-101(Cr)-SO₃H employs hydrofluoric acid as the modulator, posing handling challenges due to its irritating, corrosive, and toxic nature, as well as its reactivity with glass and metals. This study aims to find a new hydrofluoric acid-free synthesis route for MIL-101(Cr)-SO₃H, proposing acetic acid and nitric acid as modulator alternatives. Four MIL-101(Cr)-SO₃H samples were prepared: one without any modulator and the other three using a similar volume of either hydrofluoric acid, acetic acid, or nitric acid as the modulator. The so-obtained mass yield ranked as follows: without any modulator (32.6%) > acetic acid (29.6%) > nitric acid (25.2%) >> hydrofluoric acid (2.2%), whereas the total pore volume and BET surface area followed the order: hydrofluoric acid (0.87 cm³ g⁻¹, 1862 m² g⁻¹) > nitric acid (0.81 cm³ g⁻¹, 1554 m² g⁻¹) > acetic acid (0.72 cm³ g⁻¹, 1374 m² g⁻¹) > without any modulator (0.69 cm³ g⁻¹, 1342 m² g⁻¹). Despite the superior texture parameters obtained using hydrofluoric acid, the low synthesis yield and associated risks make this route non-viable. Acetic or nitric acid-based synthesis offers a promising alternative with a drastically higher yield, safer handling, and reduced environmental impact. In an attempt to improve the textural properties of the hydrofluoric acid-free MOFs, a series of samples were produced with increasing amounts of acetic acid, achieving BET surface areas of up to 1504 m² g⁻¹ and pore volumes of up to 0.81 cm³ g⁻¹. Full article

This study intended to fabricate a novel Fenton-like catalyst by supporting the rod-like MIL-88A and the magnetic tin ferrite nanoparticles (SnFe₂O₄) on the MXene sheets (MIL-88A/SnFe₂O₄@MXene). The well fabrication and determination of the MIL-88A/SnFe₂O₄@MXene properties were investigated using SEM, XPS, VSM, Zeta potential, XRD, and FTIR tools. The Fenton-like degradation reaction of CR by MIL-88A/SnFe₂O₄@MXene was thoroughly studied to identify the optimal proportions of the catalyst components, the impact of CR and H₂O₂ concentrations, as well as the effect of raising the temperature and the pH medium of the catalytic system and the catalyst dosage. Kinetics studies were executed to analyze the decomposition of CR and H₂O₂ using First-order and Second-order models. Furthermore, the degradation mechanism was proposed based on the scavenging test that proceeded in the presence of chloroform and t-butanol, in addition to the XPS analysis that clarified the participation of the containing metal species: Fe, Sn, and Ti, and the formation of a continual redox cycle. The obtained intermediates during the CR degradation were defined by GC–MS. A recyclability test was performed on MIL-88A/SnFe₂O₄@MXene during five runs of the Fenton-like degradation of CR molecules. Finally, the novel MIL-88A/SnFe₂O₄@MXene Fenton-like catalyst could be recommended as a propitious heterogeneous catalyst with a continuous redox cycle and a recyclability merit. Full article

The potential benefits of microwave irradiation for fructose dehydration into 5 hydroxymethylfurfural (5-HMF) have been quantified over a sulfonated metal–organic framework (MOF), MIL 101(Cr)-SO₃H. The effects of temperature (140–170 °C), batch time (5–300 min), and catalyst-to-substrate ratio (0.1–0.01 g/g) were systematically mapped. After 10 min of microwave (MW) irradiation at 140 °C in a DMSO–acetone reaction medium, practically complete fructose conversion was obtained with a 70% yield of 5-HMF. Without MW, i.e., using conventional heating (CH) at the same conditions, the fructose conversion was limited to 13% without any 5-HMF yield. Rather, 90 min of CH was required to reach a similarly high conversion and yield. The profound impact of moving from CH towards MW conditions on the reaction kinetics, also denoted as the microwave effect, has been quantified through kinetic modeling via a change in the Gibbs free energy of the transition state. The modeling results revealed an eight-fold rate coefficient enhancement for fructose dehydration owing to MW irradiation, while the temperature dependence of the various reaction steps almost completely disappeared in the investigated range of operating conditions. Full article

Organic semiconductors are promising materials for the photocatalytic treatment of pollutants and organic synthesis. Herein, MIL-53(Fe)@perylene diimide (PDI) organic heterojunctions were constructed by ultrasonic assembly using PDI as the co-catalyst, and PDI organic supramolecular material was uniformly distributed on the surfaces of MIL-53(Fe). The most effective M53@PDI-20 organic heterojunctions achieved 72.7% photodegradation of rhodamine B (10 mg/L) within 50 min and a 99.9% reduction in Cr(VI) (10 mg/L) for 150 min, and the corresponding apparent degradation rate constants were higher than a single component. Meanwhile, the conversion rate of benzyl alcohol over M53@PDI-20 achieved 91.5% for 5 h with a selectivity of above 90% under visible light exposure, which was more than double that of PDI. The well-matched band structures and the strong π–π bonding interactions between MIL-53(Fe) and PDI can increase the electron delocalization effect to facilitate the transfer and separation of photogenerated carriers. Lots of oxidative reactive species (h+, •O²⁻ and •OH) also played a great contribution to the strong oxidation capacity over the heterojunctions system. This work suggests that MIL-53(Fe)@PDI organic heterojunctions may be a promising material for pollutant removal and organic synthesis. Full article

The present work introduces a new sorbent, so-called PANI/MIL100(Fe), for removing Pb (II) and Cr (VI) from wastewater. The successful preparation of PANI/MIL100(Fe) was verified via Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET) characterizations. This adsorptive material showed a microporous structure with surface area magnitudes of up to 261.29 m²/g, a total pore volume of 0.2124 cm³/g, and a pore size distribution of around 1.2 nm. The maximum adsorption capacities of PANI/MIL100(Fe) for Cr (VI) (pH = 2) and Pb (II) (pH = 6) were obtained as 72.37 and 81.76 mg/g, respectively. The isotherm modeling assessments illustrated that the sorption of Pb (II) and Cr (VI) was consistent with the Sips model (R² > 0.99), while the adsorption kinetics were suited to a pseudo-second-order model (R² > 0.95). Thermodynamic studies of both metal ions demonstrated the spontaneous and endothermic nature of the process. The reusability of the PANI/MIL100(Fe) indicated promising adsorption properties for Pb (II) and Cr (VI) up to three cycles. Moreover, the XRD and FT-IR spectroscopy results after adsorption/desorption showed excellent stability of the adsorbent and physisorption mechanism, wherein electrons were exchanged between the PANI/MIL-100(Fe) and Pb (II) and Cr (VI). Finally, the findings suggested that PANI/MIL100(Fe) can be considered an efficient and environmentally friendly adsorbent to remove Pb (II) and Cr (VI) from wastewater. Full article

The MIL-100(Cr), PW12@MIL-100(Cr) and PW4@MIL-100(Cr) catalysts were prepared and characterized through XRD, FTIR, BET, SEM, EDS and Raman spectroscopy. A comparison of the catalytic properties of the synthesized materials in the epoxidation of FAMEs with hydrogen peroxide was made. The PW4@MIL-100(Cr) catalyst exhibited the highest catalytic activity and provided a high selectivity for the formation of epoxides. The effects of the reaction temperature, catalyst loading, reaction time and FAME:hydrogen peroxide molar ratio on the reaction performance were investigated, and the optimal process conditions were determined. An epoxide yield of 73% with a selectivity of 77% could be obtained using PW4@MIL-100(Cr) after 4 h at 40 °C. The catalytic stability test showed that PW4@MIL-100(Cr) could be easily separated and reused without any treatment for at least five consecutive cycles without a loss of activity or selectivity. Full article

Light olefins are important raw materials in the petrochemical industry for the production of many chemical products. In the past few years, remarkable progress has been made in the synthesis of light olefins (C2–C4) from methanol or syngas. The separation of light olefins by porous materials is, therefore, an intriguing research topic. In this work, single-component ethylene (C₂H₄) and propylene (C₃H₆) gas adsorption and binary C₃H₆/C₂H₄ (1:9) gas breakthrough experiments have been performed for three highly porous isostructural metal–organic frameworks (MOFs) denoted as Fe₂M-L (M = Mn²⁺, Co²⁺, or Ni²⁺), three representative MOFs, namely ZIF-8 (also known as MAF-4), MIL-101(Cr), and HKUST-1, as well as an activated carbon (activated coconut charcoal, SUPELCO^©). Single-component gas adsorption studies reveal that Fe₂M-L, HKUST-1, and activated carbon show much higher C₃H₆ adsorption capacities than MIL-101(Cr) and ZIF-8, HKUST-1 and activated carbon have relatively high C₃H₆/C₂H₄ adsorption selectivity, and the C₂H₄ and C₃H₆ adsorption heats of Fe₂Mn-L, MIL-101(Cr), and ZIF-8 are relatively low. Binary gas breakthrough experiments indicate all the adsorbents selectively adsorb C₃H₆ from C₃H₆/C₂H₄ mixture to produce purified C₂H₄, and 842, 515, 504, 271, and 181 cm³ g⁻¹ C₂H₄ could be obtained for each breakthrough tests for HKUST-1, activated carbon, Fe₂Mn-L, MIL-101(Cr), and ZIF-8, respectively. It is worth noting that C₃H₆ and C₂H₄ desorption dynamics of Fe₂Mn-L are clearly faster than that of HKUST-1 or activated carbon, suggesting that Fe₂M-L are promising adsorbents for C₃H₆/C₂H₄ separation with low energy penalty in regeneration. Full article

TiO₂ has been hampered by drawbacks such as rapid photoelectron and hole recombination and a wide energy band gap of 3.2 eV. In this study, MIL-101(Cr)@TiO₂ was synthesised without any mineraliser (HF) as part of material modification approach to overcome those pitfalls. The composite was well characterized by XRD, FT-IR, TEM, XPS, BET, TGA, and Raman spectroscopy. Under optimal synthesis conditions, the 9.17% MIL-101(Cr)@TiO₂ composite exhibited 99.9% CBZ degradation after 60 min under UV-A irradiation. This can be attributed to the delayed recombination of photo-generated h⁺ and e⁻ and a reduced band gap energy of 2.9 eV. A Type II heterojunction structure was proposed for the composite using the Mulligan function of electronegativity with the calculated E_cb and E_vb. Besides, trapping experiments and ESR spectroscopy confirmed O₂^•− as the main ROS for CBZ degradation. The effects of the operating parameters such as pH, UV intensity, composite dosage, and initial pollutant concentration were also evaluated. The scavenging effects of inorganic and organic constituents of pharmaceutical wastewater on the process were also evaluated, with HCO₃⁻, CO₃²⁻, and THF having more significant inhibition on the overall CBZ degradation. The degradation pathways of CBZ were also proposed based on detected intermediates with the aid of LC/MS/MS. The composite illustrated reusability and stability without considerable loss in the degradation performance after repeated runs. This work builds on the development of more effective photocatalysts and provides a glimpse into applications for similar MOF heterojunction photocatalysts. Full article

The synthesis of highly dispersed metal nanoparticles supported on metal–organic frameworks has been widely studied as a means to provide high-performance heterogeneous catalysts. Here, a Ru-nanoparticles-supported MIL-101(Cr) catalyst was prepared via a diamine and oxo-centered trimeric ruthenium cluster ([Ru₃(μ₃-O)(μ-CH₃COO)₆(H₂O)₃]CH₃COO), Ru₃ cluster sequential grafting, followed by alcohol reduction. Ethylenediamine (ED) acted as the linker, coordinating with unsaturated sites on both MIL-101(Cr) and the Ru₃ cluster to produce Ru₃-ED-MIL-101(Cr), after which selective alcohol reduction process provided the Ru/ED-MIL-101(Cr) catalyst. The synthesized Ru/ED-MIL-101(Cr) catalyst contained small, finely dispersed Ru nanoparticles, and the structural integrity of ED-MIL-101(Cr) was maintained. The Ru/ED-MIL-101(Cr) catalyst was tested for the transfer hydrogenation of benzene using isopropanol as the hydrogen source, where it was shown to outperform other Ru-based catalysts. Full article

This study investigates the production and performance of a novel nanofiltration membrane for removal of cationic dye (Methylene blue) and multivalent cations. These positively charged membranes are made by dispersing a modified cationic metal–organic framework, Cl-MIL-101(Cr), into the polyvinyl alcohol matrix as a membrane skin layer. To this end, the mobile anion (Cl⁻) embedded in the MIL-101(Cr) structure plays a role to create a positive partial charge on the membrane. In this study, the effects of MOF content and their types on the membrane structure were considered by FTIR, XRD, FESEM, Zeta potential and water contact angle. The results have shown that membranes filled with Cl-MIL-101(Cr) attained higher permeate flux and rejection than those of MIL-101(Cr). Particularly, this study indicates that the low irreversible resistance (19.49%) and high flux return ratio (80.50%) have been related to the membrane containing 15% cationic Cl-MIL-101(Cr). However, this membrane rejected more than 30.41% of AlCl₃ salt and 99.08% of methylene blue with approximate permeate flux of 20 L/m²·h. It is recommended that the fabricated membrane be placed in the flow path process of cationic dyes purification. Full article

Membranes with excellent separation performance and stability are needed for organic solvent nanofiltration in industrial separation and purification processes. Here we reported a newly PPSU-MoS₂/PA-MIL-101(Cr) composite membrane with high permeance, good selectivity and stability. The MIL-101(Cr) was introduced in the polyamide (PA) layer via the PIP/TMC interfacial polymerization process on a microporous PPSU-MoS₂ substrate. At a small doping amount of 0.005 wt% MIL-101(Cr), the PPSU-MoS₂/PA-MIL-101(Cr) composite membrane exhibited a high methanol permeance of 12.03 L m⁻² h⁻¹ bar⁻¹, twice higher than that of the pristine membrane without sacrificing selectivity. Furthermore, embedding MIL-101(Cr) notably enhanced the stability of the composite membrane, with permeance only decreasing by 8% after a long time operation of 80 h (pristine membrane decreased by 25%). This work demonstrated a composite membrane modified by MIL-101(Cr) with superior separation performance, which provides potential application of MOF materials for high-performance membranes in organic solvent nanofiltration and a theoretical foundation for future research in studying MOF’s influence on membrane properties. Full article