With the expansion of copper smelting capacity and increasing complexity of ore feedstocks, solid waste generation and associated element enrichment have become more pronounced. Typical copper smelting solid wastes, including copper slag, flue dust, arsenic sulfide sludge, copper anode slime, and black copper sludge, are enriched in valuable elements but also contain hazardous components. Consequently, they have considerable resource potential while posing substantial environmental risks, which render their efficient utilization and safe management essential. This review summarizes the generation characteristics, chemical and mineralogical compositions, and elemental occurrence of five representative copper smelting solid wastes, and evaluates mainstream treatment technologies, including pyrometallurgical, hydrometallurgical, and integrated beneficiation-metallurgical processes. The treatment routes are critically compared in terms of separation efficiency, industrial applicability, and environmental impact, and the major technical bottlenecks are identified. Future research should focus on multi-source waste co-treatment, multi-element recovery, short-process integration, and the directional transformation and high-value utilization of arsenic to achieve coordinated improvements in resource recovery and environmental performance.

Melanoma remains a highly aggressive malignancy with limited response to current immunotherapies due to its immunosuppressive tumor microenvironment. To overcome this limitation, we developed a radiolabeled coordination polymer, 177Lu-GAMP, through the self-assembly of 177Lu3+ with adenosine monophosphate (AMP) and guanosine monophosphate, exhibiting coordination-feature resemblance to the endogenous STING agonist cGAMP, thereby enabling activation of the STING pathway. We further incorporated 177Lu-GAMP into a dissolvable microneedle patch (177Lu-GAMP@MN) for localized, minimally invasive delivery to melanoma lesions. Our results demonstrate that 177Lu-GAMP@MN effectively penetrated the skin and retained at the tumor site, leading to robust STING activation and Gasdermin E-mediated pyroptosis. This, in turn, promoted dendritic cell maturation and enhanced T cell infiltration. In vivo, 177Lu-GAMP@MN significantly suppressed subcutaneous melanoma growth, prolonged survival, and elicited strong antitumor immune responses. When combined with anti-PD-L1 monoclonal antibodies, the treatment achieved synergistic tumor regression, improved effector T cell function, and induced durable immunological memory, demonstrating significant inhibition of both primary and distant tumors in murine models. Collectively, this work presents a transdermal brachytherapeutic-immunomodulatory strategy for melanoma treatment, offering promising potential for enhanced antitumor immunotherapy.

Atopic dermatitis (AD) is a common chronic inflammatory skin disorder characterized by epidermal barrier dysfunction and immune dysregulation, yet effective long-term therapies are limited. Although regulated cell death has been linked to AD, the involvement of copper-dependent cell death (cuproptosis) and its therapeutic relevance in AD have not been explored. Herein, we identify aberrant epidermal upregulation of the copper transporter SLC31A1 as a driver of copper overload and cuproptosis in keratinocytes, which in turn promotes GSDMA-dependent pyroptosis through an α-ketoglutarate (α-KG)/H3K9me3 epigenetic mechanism. To target this pathway, we developed a dual-functional microneedle system composed of calcium phosphate nanoparticles delivering Slc31a1 siRNA and embedded within Bletilla striata polysaccharide microneedles (CaP-siSlc31a1@BSP). This platform enables efficient transdermal gene silencing while BSP simultaneously suppresses STAT3/GSDMA signaling and inflammation. In MC903-induced AD-like mice, CaP-siSlc31a1@BSP markedly alleviated skin inflammation, epidermal hyperplasia and pruritus, accompanied by reduced Th2/Th17 responses. Our study reveals a previously unrecognized cuproptosis-pyroptosis axis in AD and establishes SLC31A1 as a promising therapeutic target. The CaP-siSlc31a1@BSP microneedle offers a synergistic drug-gene transdermal strategy with strong potential for AD treatment.

Selective removal of toxic metals such as thallium (Tl) from smelting wastes is imperative for pollution control and resource recycling. However, conventional high-temperature roasting suffers from severe co-volatilization of valuable constituents and extreme energy demands. Herein, we proposed a sulfate-mediated chlorination roasting strategy that overcomes the high-temperature and low-selectivity limitations. Tl removal fraction reaches 99.5% with <10% valuable metals loss under 500 °C, decreasing by approximately 600 °C compared with conventional methods. The high temperature needed in conventional treatment originates from the high activation energy barrier caused by poor thermal stability of sodium oxides, which is generated during NaCl-driven Tl2O3 chlorination. Introducing metal sulfates stabilizes sodium as thermally stable Na2SO4, thereby significantly reducing activation energy barrier and enabling efficient Tl chlorination at lower temperatures. Applying this strategy to industrial Tl-containing sludge achieves 94.1% Tl separation with <5% valuable metals loss at 600 °C, offering an energy-efficient approach for pollution control of complex smelting wastes.

Sustainable recovery of iron from iron-rich copper slag flotation tailings (CSFT) is critical for mitigating environmental burdens and meeting the growing demand for iron resources. The rapid expansion of the lithium iron phosphate (LFP) industry has led to a growing demand for its key precursor, ferrous oxalate dihydrate (FeC2O4·2H2O). In this study, a choline chloride-oxalic acid deep eutectic solvent (ChCl-Oxa DES), formulated from relatively inexpensive constituents and exhibiting short-term reusability, was developed for the efficient leaching of Fe from CSFT and its subsequent conversion into battery-grade FeC2O4·2H2O. Pure Fe2SiO4 and Fe3O4 were employed as model phases to decouple phase-dependent effects and identify rate limiting steps. Fe leaching was found to be jointly constrained by the structural resistance of the Fe-O-Si framework and the reduced diffusion flux induced by DES viscosity. Under the optimized conditions, the Fe leaching efficiency reached 99%, while Si, Al, and Ca leaching remained low. By precisely regulating Fe valence and leachate pH, selective oxalate complexation and direct crystallization of FeC2O4·2H2O from the leachate were achieved. The DES also exhibited excellent recyclability, retaining 97% Fe leaching efficiency after three reuse cycles. This work provides a feasible pathway for efficient Fe recovery from CSFT and its high-value conversion into battery-grade iron salt precursors using a biodegradable, low cost, and recyclable solvent system.

Large quantities of hazardous arsenic sulfide sludges are stockpiled in China, posing significant environmental risks. As a new stabilization method for arsenic sulfide sludge treatment, hydrothermal stabilization has attracted increasing attention. However, direct hydrothermal treatment requires harsh operating conditions and often achieves unsatisfactory stabilization performance. This study proposed a sulfur-enhanced hydrothermal method for an improved stabilization of arsenic sulfide sludge under milder conditions. After treatment, the leaching concentration of arsenic was reduced to below 0.1 mg/L, well below the limit specified in the hazardous waste identification standard. Compared with the initial arsenic sulfide sludge and the product of traditional hydrothermal treatment, the new sulfur-assisted hydrothermal treatment method achieved toxicity reduction of approximately 8620 and 150 times, respectively. Furthermore, by integrating preliminary quantum chemical calculations with detailed analyses of morphology, phase composition, and molecular structure, the mechanism of sulfur-enhanced stabilization was elucidated. The findings demonstrate that elemental sulfur participated in the hydrothermal process and promoted the formation of a dense, glass-like sulfur-arsenic matrix with markedly improved immobilization capacity. This study provides both theoretical support and practical guidance for mitigating the stockpiling challenges of arsenic sulfide sludge.

Psoriasis is a chronic immune-mediated skin disorder driven by abnormal keratinocyte proliferation and inflammation, and the dysregulation of copper transport is increasingly recognized as a key metabolic driver and potential therapeutic target in psoriasis. Herein, we identified solute carrier family 31 member 1 (SLC31A1) as a pivotal molecular switch connecting cuproptosis and ferroptosis, two interconnected forms of regulated cell death that synergistically promote psoriatic pathology. Upregulated SLC31A1 induces copper accumulation and elevates α-ketoglutarate (α-KG), activating KDM5B-dependent histone demethylation and repressing FTH1 transcription, thereby amplifying ferroptotic damage and inflammation. To therapeutically target this axis, we developed a nanoparticle-incorporated microneedle system (CaP-siSlc31a1@MN) enabling localized, efficient and minimally invasive siRNA delivery through the psoriatic barrier. The dissolvable microneedles with favorable mechanical performance ensured precise epidermal deposition, while biomineralized calcium phosphate (CaP) nanoparticles facilitated intracellular uptake and siRNA release. In vitro and in vivo studies confirmed that CaP-siSlc31a1@MN effectively silenced Slc31a1, inhibited cuproptosis and ferroptosis, suppressed IL17A-driven inflammation and restored epidermal homeostasis. Overall, this study introduces a first-in-class transdermal gene-silencing nanoplatform that integrates metabolic regulation with anti-inflammatory therapy for precision psoriasis treatment.

Abstract Atopic dermatitis (AD) is a chronic inflammatory skin disorder in which keratinocyte (KC)-derived thymic stromal lymphopoietin (TSLP) orchestrates pathogenic crosstalk between epithelial cells and immune cells. Here, we present a boron-doped copper single-atom nanomaterial (Cu/NC-B) designed to achieve a dual functional blockade of the TSLP signaling axis, offering a more comprehensive therapeutic intervention. Therapeutically, Cu/NC-B significantly alleviated MC903-induced AD-like lesions, showing efficacy comparable to that of crisaborole (CB) with a superior safety profile. Single-cell transcriptomics analysis revealed that Cu/NC-B selectively targets a previously uncharacterized, highly inflammatory KC subpopulation (KC_Spinous_Tslp), thereby disrupting a critical cellular node in AD pathology. At the molecular level, Cu/NC-B exerts its effects through two complementary pathways: epigenetic repression of TSLP via nicotinamide adenine dinucleotide (NAD+)-dependent activation of SIRT1/3 and competitive antagonism of the TSLP receptor (TSLPR). Our work establishes Cu/NC-B as a dual-action nanotherapeutic capable of concurrently suppressing TSLP transcription and disrupting its receptor engagement, thereby proposing a targeted intervention for AD treatment.

High recombination rates and sluggish charge transfer severely limit the efficiency of photocatalytic CO2 reduction. Herein, a vacancy-regulated two-dimensional b-AsP/CN type-I heterojunction was constructed via a liquid-phase exfoliation-assembly strategy to address these challenges. The heterostructure exhibits optimized textural properties with increased surface area and pore volume, along with enhanced CO2 adsorption capacity, providing abundant accessible active sites. More importantly, the built-in electric field (IEF) and the local polarization electric field (PEF) by As/P vacancies can synergistically accelerate carrier separation and transfer, thereby enhancing the photocatalytic activity for CO2 reduction. The b-AsP/CN heterojunction exhibits much lower dark current and stronger photocurrent, demonstrating rapid photogenerated charge transfer at the interface between b-AsP and CN. The significantly decreased PL intensity of b-AsP/CN heterojunction indicates the much lower possibility of charge recombination. The fluorescence lifetime of b-AsP/CN was measured to be 2.10 ns, higher than that of CN (1.85 ns), suggesting more carriers are involved in photocatalytic reactions. Photocatalytic reduction results showed efficient conversion of CO2 into CO and CH4. Among them, the b-AsP/ CN-10 composite exhibited the highest CO yield (68.92 mu mol g-1 h-1) and good structural-performance stability, with a yield selectivity and cycle efficiency of CO products both exceeding 90%. This work provides insights into designing high-performance two-dimensional heterojunctions for solar-to-fuel conversion.

This study aims to clarify the non-linear reaction pathways and competitive interactions in the reductive pyrolysis of Acidic Water Treatment Gypsum (AWTG), which are currently impeded by complex impurity compositions. Representative AWTG was synthesized using log-normal distribution analysis of industrial data, and its pyrolysis mechanisms were systematically investigated via TG-MS, XRD, and SEM-EDS under varying carbon-to-sulfur (C/S) ratios. The results demonstrate that the final speciation of iron and arsenic is governed by the interplay between initial speciation and the reducing atmosphere. Based on the raw material formation process, the evolution of three distinct impurity forms was elucidated: (1) species in the Ca-S-O matrix, (2) As-Fe co-precipitates, and (3) independent mineral phases. Specifically, the in-situ generation of CaO and CaFe2O4 acts as a reduction barrier, constituting the predominant mechanism for arsenic immobilization in carbon-deficient environments. These findings provide a theoretical foundation for raw material selection and targeted impurity control in the industrial valorization of heavy metal gypsum.

Insufficient infiltration or dysfunction of lymphocytes in the tumor immune microenvironment is considered to be a contributing factor to poor immunotherapy outcomes in solid tumors. Necroptosis, a form of immunogenic cell death, has attracted increasing interest because of its unique role in regulating tumor immune responses. CL-387785, a third-generation EGFR inhibitor, has been reported to inhibit tumors by regulating the cell cycle and inducing apoptosis; however, the underlying mechanisms remain unclear. In this study, we demonstrated that CL-387785 effectively suppressed the malignant phenotype of melanoma and lung cancer and confirmed that cancer cells undergo necroptosis, as evidenced by morphological and protein-level analyses. Further in vivo and in vitro experiments revealed that CL-387785 enhances tumor cell killing by immune cells by inducing CD80 expression on the tumor cell surface, thereby increasing CD8+ T lymphocyte function. Detailed mechanistic studies indicated that CL-387785 targets TRADD, recruiting RIPK1 to induce necroptosis in tumor cells, with subsequent nuclear translocation of NF-κB, which regulates CD80 transcription. In conclusion, our findings indicate that CL-387785 induces necroptosis in tumor cells via the TRADD/RIPK1/NF-κB/CD80 signaling pathway, thereby sensitizing tumors to anti-PD-1 therapy. These results suggest that CL-387785 is a promising candidate for increasing tumor immunotherapy efficacy.

Background Chronic spontaneous urticaria (CSU) is a relapsing, immune‐mediated skin disease. However, the role of monocytes in its pathogenesis and clinical significance remains unclear. Objective This study aimed to investigate the correlation between peripheral blood monocyte counts and clinical features in CSU patients, as well as to explore their potential predictive value for the therapeutic efficacy of second‐generation H1‐antihistamines (sgAHs) and omalizumab. Methods Two independent patient cohorts were included: Cohort 1 was utilized to evaluate sgAHs treatment efficacy, while Cohort 2 was employed to analyze omalizumab efficacy in CSU patients. Results A total of 656 and 105 CSU patients were enrolled in Cohort 1 and Cohort 2, respectively. Baseline peripheral blood monocyte levels were significantly associated with treatment outcome in both cohorts (OR = 0.005, p < 0.001; OR = 0.07, p = 0.005, respectively). Furthermore, compared to baseline levels, peripheral blood monocyte counts decreased significantly in both cohorts ( p < 0.0001 and p = 0.0205, respectively). In Cohort 2, fast‐responders, but not slow‐responders or non‐responders, exhibited a significantly greater reduction in monocyte counts post‐treatment ( p = 0.0031 for fast‐responders, p = 0.5285 for slow‐responders, and p = 0.7565 for non‐responders, respectively). Conclusion Baseline monocyte counts were significantly correlated with the therapeutic efficacy of both sgAHs and omalizumab in CSU patients. Trial Registration: Chinese Clinical Trial Registry: ChiCTR‐OCH‐14004518

Psoriasis is a chronic inflammatory skin disorder characterized by abnormal keratinocyte (KC) differentiation and proliferation, along with infiltration of various immune cells into the skin. Both internal and external perturbations can disrupt endoplasmic reticulum (ER) homeostasis, leading to ER stress and activation of the unfolded protein response (UPR) pathways. Although the UPR is known to participate in normal epidermal KC differentiation, its regulatory role in psoriasis remains poorly understood. In this study, we observed significant attenuation of UPR pathways specifically IRE1α-XBP1s and PERK signaling in psoriasis lesions. Administration of ER stress inducers (TM and BFA) alleviated psoriasis-like phenotypes in an imiquimod (IMQ)-induced mouse model. Furthermore, knockdown of Grp78 in KCs activated both IRE1α-XBP1s and PERK pathways, thereby improving KC differentiation in vitro. Notably, combining of Grp78 knockdown with ER stress inducers synergistically enhanced KC differentiation through UPR activation. Together, these findings indicate that the ER stress response promotes epidermal KC differentiation. Targeted activation of UPR pathways may thus represent a novel therapeutic strategy to improve KC differentiation in psoriasis.

The synergistic and enhanced bath smelting of primary ores with secondary resources is a key strategy to address the paradox of resource scarcity and recycling of secondary resources in zinc metallurgy. However, due to the high melting temperature of high zinc slags (Zn > 25 %), bath smelting below 1250 degrees C has not yet been practically implemented. This study proposes a new approach for reducing the melting temperature of high zinc slags by tailoring slag composition and co-smelting secondary resources to promote synergistic melting. The melting properties and regulation mechanisms of high zinc slags were systematically investigated through FactSage thermodynamic calculations, in-situ observation using an ash fusion temperatures auto detecting system, and quenching experiments. The results reveal that CaO/SiO2 and FeO/SiO2 mass ratio are the primary factors influencing the melting temperature. Excessively high or low CaO/SiO2 and FeO/SiO2 promote the formation of high melting point phases such as zincite, spinel, willemite and melilite, thereby increasing the melting temperature. Components from secondary resources, such as B2O3, Na2O and Cu2O, can significantly reduce the content of high melting point phase in the melting process, and reduce the melting temperature, while MgO, Cr2O3, etc., have the opposite effect. The melting temperature of co-smelting high zinc slag with 15 % sludge and 4 % borax was reduced over 125 degrees C. In industrial pilot-scale trial exceeding 20 tons, the flow temperature of high zinc slag containing 27.08 % zinc was 1118 degrees C. This study establishes technical foundations for low-energy and clean co-smelting of secondary resources with primary ores.

Cobalt is an important accompanying element in copper sulfide concentrates and a critical metal for lithium-ion batteries. Understanding its distribution during copper smelting is therefore essential for improving cobalt recovery. In this study, the distribution behaviour of cobalt during copper smelting was investigated by combining thermodynamic calculations with laboratory smelting experiments. The thermodynamic results show that, under high-temperature equilibrium conditions, increasing matte copper grade, decreasing matte iron content, and increasing oxygen partial pressure reduce cobalt partitioning to matte and favour its transfer to slag in oxidised forms. Laboratory smelting experiments at 1300 degrees C under O2-enriched gas injection were conducted to validate the thermodynamic predictions. The results indicate that cobalt is distributed between matte and slag through both chemical dissolution and physical entrainment. Under the present experimental conditions, the cobalt mass distribution ratio was higher at moderate-to-low matte grade and lower oxygen enrichment concentration, whereas higher matte grade and higher oxygen enrichment concentration promoted cobalt transfer to slag. SEM-EDS analysis further showed that cobalt in the solidified slag mainly occurs in secondary precipitates, including Fe-Ca-Si-O silicates and spinel solid solutions. These findings improve the understanding of cobalt distribution behaviour during copper smelting and provide guidance for optimising cobalt recovery. Le cobalt est un & eacute;l & eacute;ment d'accompagnement important dans les concentr & eacute;s de sulfure de cuivre et un m & eacute;tal critique pour les batteries lithium-ion. Comprendre sa distribution lors de la fusion du cuivre est donc essentiel pour am & eacute;liorer la r & eacute;cup & eacute;ration du cobalt. Dans cette & eacute;tude, on a examin & eacute; le comportement de distribution du cobalt lors de la fusion du cuivre en combinant des calculs thermodynamiques et des exp & eacute;riences de fusion en laboratoire. Les r & eacute;sultats thermodynamiques montrent que, dans des conditions d'& eacute;quilibre & agrave; haute temp & eacute;rature, l'augmentation de la teneur en cuivre de la matte, la diminution de sa teneur en fer et l'augmentation la pression partielle d'oxyg & egrave;ne r & eacute;duisent la s & eacute;gr & eacute;gation du cobalt dans la matte et favorisent son transfert vers le laitier sous forme oxyd & eacute;e. On a r & eacute;alis & eacute; des exp & eacute;riences de fusion en laboratoire & agrave; 1300 degrees C sous injection de gaz enrichi en O2 pour valider les pr & eacute;dictions thermodynamiques. Les r & eacute;sultats indiquent que le cobalt est distribu & eacute; entre la matte et le laitier par dissolution chimique et entra & icirc;nement physique. Dans les conditions exp & eacute;rimentales actuelles, le rapport de distribution massique du cobalt & eacute;tait plus & eacute;lev & eacute; pour une qualit & eacute; de matte faible & agrave; mod & eacute;r & eacute;e et une plus faible concentration d'enrichissement en oxyg & egrave;ne, tandis qu'une qualit & eacute; de matte plus & eacute;lev & eacute;e et une concentration d'enrichissement en oxyg & egrave;ne plus & eacute;lev & eacute;e favorisaient le transfert du cobalt vers le laitier. Une analyse MEB-EDS a en outre montr & eacute; que le cobalt dans le laitier solidifi & eacute; se pr & eacute;sente principalement dans des pr & eacute;cipit & eacute;s secondaires, incluant des silicates de Fe-Ca-Si-O et des solution solides de spinelle. Ces r & eacute;sultats am & eacute;liorent la compr & eacute;hension du comportement de distribution du cobalt lors de la fusion du cuivre et fournissent des indications pour optimiser la r & eacute;cup & eacute;ration du cobalt.

Introduction: The Patient Acceptable Symptom State (PASS), a patient-reported outcome measure, has demonstrated correlations with disease severity in various conditions, including psoriasis and scleroderma. However, the clinical relevance of PASS in the context of chronic spontaneous urticaria (CSU) remains to be fully elucidated. Objectives: This study aimed to determine the prevalence of PASS among CSU patients, identify potential predictors, and establish the weekly urticaria activity score (UAS7) threshold for PASS. Methods: Demographic and clinical data from CSU patients were prospectively collected. PASS attainment was assessed using a single-item questionnaire. Logistic regression analysis and interaction effects analysis were employed to identify predictors associated with achieving PASS (PASS-Y) or failing to achieve PASS (PASS-N). The UAS7 threshold corresponding to PASS was determined through receiver operating characteristic (ROC) curve analysis. Results: A total of 161 CSU patients were enrolled in this study. Among them, 70.5% exhibited non-severe disease activity (UAS7<28) and achieved PASS-Y. Logistic regression analysis revealed a significant association between UAS7 scores and PASS status (AOR=1.105, P<0.001). Female patients with severe disease activity (UAS7≥ 28) were significantly less likely to achieve PASS-Y compared to their male counterparts (AOR=3.514, P=0.042). ROC analysis identified a UAS7 threshold of 21.5 for predicting PASS, with an area under the curve (AUC) of 0.821. Conclusions: In patients with CSU, PASS demonstrates a strong correlation with UAS7 scores and is straightforward to implement. It may serve as a valuable complementary tool to UAS7 in clinical settings, facilitating a rapid, patient-centered assessment of disease activity.

Chronic stress and sympathetic signaling, mediated by the β2-adrenergic receptor (ADRB2), are implicated in cancer progression. In melanoma, a neural crest-derived malignancy, the interplay between neuroendocrine signals and tumor cell plasticity remains poorly understood. Elucidating how ADRB2 activation translates into pro-tumorigenic transcriptional programs is crucial for developing novel therapeutics. We combined genetic and pharmacological ADRB2 modulation in melanoma models with transcriptomics, mechanistic assays, and patient sample analysis. ADRB2 inhibition suppressed tumor growth by arresting the cell cycle and inducing apoptosis. Transcriptomic analysis revealed MAGEA1 as the most downregulated gene upon ADRB2 knockout. Mechanistically, ADRB2 signaling via the PKA pathway upregulated and promoted the nuclear translocation of the transcription factor SOX10. SOX10, in turn, directly bound to the MAGEA1 promoter to drive its transcription. In clinical specimens, high expression of ADRB2, SOX10, and MAGEA1 correlated with poorer patient prognosis. Our study defines a novel ADRB2-PKA-SOX10-MAGEA1 signaling axis that critically promotes melanoma growth. This axis positions ADRB2 as a key node linking neuroendocrine stress signals to the core transcriptional machinery governing melanoma cell proliferation and survival. Targeting ADRB2 presents a promising therapeutic strategy to counteract stress-induced melanoma progression.