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Ion-solvating membranes have been gaining increasing attention as core components of electrochemical energy conversion and storage devices. However, the development of ion-solvating membranes with low ion resistance and high ion selectivity still poses challenges. In order to propose an effective strategy for high-performance ion-solvating membranes, this study conducted a comprehensive investigation on watermelon skin membranes through a combination of experimental research and molecular dynamics simulation. The micropores and continuous hydrogen-bonding networks constructed by the synergistic effect of cellulose fiber and pectin enable the hypodermis of watermelon skin membranes to have a high ion conductivity of 282.3 mS cm-1 (room temperature, saturated with 1 M KOH). The negatively charged groups and hydroxyl groups on the microporous channels increase the formate penetration resistance of watermelon skin membranes in contrast to commercially available membranes, and this is crucial for CO2 electroreduction. Therefore, the confinement of proton donors and negatively charged groups within three-dimensional microporous polymers gives inspiration for the design of high-performance ion-solvating membranes.
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Host-guest complexation offers a promising approach for mitigating surface defects in perovskite solar cells (PSCs). Crown ethers are the most widely used macrocyclic hosts for complexing perovskite surfaces, yet their supramolecular interactions and functional implications require further understanding. Here we show that the dipole moment of crown ethers serves as an indicator of supramolecular interactions with both perovskites and precursor salts. A larger dipole moment, achieved through the substitution of heteroatoms, correlates with enhanced coordination with lead cations. Perovskite films incorporating aza-crown ethers as additives exhibited improved morphology, reduced defect densities, and better energy-level alignment compared to those using native crown ethers. We report power-conversion efficiencies (PCEs) exceeding 25% for PSCs, which show enhanced long-term stability, and a record PCE of 21.5% for host-guest complexation-based perovskite solar modules with an active area of 14.0 cm2.
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Recently, pulsed electrolysis has been demonstrated as an emerging electrochemical technique that significantly promotes the performance of various electrocatalysis applications. The ionic nature of aqueous electrolytes implies a likely change in ionic distribution under these alternating potential conditions. However, despite the well-known importance of cations, the impact of pulsed electrolysis on the cation distribution remains unexplored as well as its influences on the performance. Herein, we explore the cation effects on the pulsed electrochemical CO2 reduction (p-CO2RR) using the most widely utilized alkali metal cations, including Li+, Na+, K+, and Cs+. It is discovered that the nature of cations can significantly influence the product ratio of C2+ over C1 (mostly CH4) during p-CO2RR in an order of Li+< Na+< K+< Cs+, much more profoundly than those of static cases. We report direct experimental evidence for the cation enrichment caused by pulsed electrolysis, depending on the radius of the hydrated ions. With further quasi-in situ analysis of the catalyst surface, the cation-promoted Cu dissolution-and-redeposition process was identified; this is found to alter the surface CuxO/Cu ratio during the pulsed process. We demonstrate that both the cation enrichment and the cation-adjusted surface CuxO/Cu composition impact the C2+/C1 ratio through the control of the surface-adsorbed CO population. These results reveal the presence of pulse-induced cation redistribution in emerging pulsed electrolysis techniques and provide a comprehensive understanding of alkali metal cation effects for improving the selectivity of p-CO2RR.
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The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical (PEC) H2 production devices. Coupling TiO2 with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation. However, the band position of TiO2 could not perfectly match with all p-type semiconductors. Here, taking antimony selenide (Sb2Se3) as an example, a rational strategy was developed by introducing a viologen electron transfer mediator (ETM) containing polymeric film (poly-1,1'-dially-[4,4'-bipyridine]-1,1'-diium, denoted as PV2+) at the interface between Sb2Se3 and TiO2 to regulate the energy band alignment, which could inhibit the recombination of photogenerated charge carriers of interfaces. With Pt as a catalyst, the constructed Sb2Se3/PV2+/TiO2/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of -18.6 mA cm-2 vs. a reversible hydrogen electrode (RHE) and a half-cell solar-to-hydrogen efficiency (HC-STH) of 1.54% at 0.17 V vs. RHE, which was much better than that of the related Sb2Se3/TiO2/Pt photocathode without PV2+ (-9.8 mA cm-2, 0.51% at 0.10 V vs. RHE).
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The anion exchange membrane water electrolysis is widely regarded as the next-generation technology for producing green hydrogen. The OH- conductivity of the anion exchange membrane plays a key role in the practical implementation of this device. Here, we present a series of Z-S-x membranes with dibenzothiophene groups. These membranes contain sulfur-enhanced hydrogen bond networks that link surrounding surface site hopping regions, forming continuous OH- conducting highways. Z-S-20 has a high through-plane OH- conductivity of 182±28â mS cm-1 and ultralong stability of 2650â h in KOH solution at 80 °C. Based on rational design, we achieved a high PGM-free alkaline water electrolysis performance of 7.12â A cm-2 at 2.0â V in a flow cell and demonstrated durability of 650â h at 2â A cm-2 at 40 °C with a cell voltage increase of 0.65â mV/h.
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A water oxidation catalyst Ru-bcs (bcs = 2,2'-bipyridine-6'-carboxylate-6-sulfonate) with a hybrid ligand was reported. Ru-bcs utilizes the electron-donating properties of carboxylate ligands and the on-demand coordination feature of sulfonate ligands to enable a low onset potential of 1.21 V vs. NHE and a high TOF over 1000 s-1 at pH 7. The adaptive chemistry uncovered in this work provides new perspectives for developing molecular catalysts with high efficiency under low driving forces.
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Although the efficacy of chimeric antigen receptor (CAR)-T cell therapy has been widely demonstrated, its clinical application is hampered by the complexity and fatality of its side effects. Cytokine release syndrome (CRS) is the most common toxicity following CAR-T cell infusion, and its symptoms substantially overlap with those of infection. Whereas, current diagnostic techniques for infections are time-consuming and not highly sensitive. Thus, we are aiming to develop feasible and efficient models to optimize the differential diagnosis in clinical practice. This study included 191 febrile patients from our center, including 85 with CRS-related fever and 106 with infectious fever. By leveraging the serum cytokine profile at the peak of fever, we generated differential models using a classification tree algorithm and a stepwise logistic regression analysis, respectively. The first model utilized three cytokines (IFN-ß, CXCL1, and CXCL10) and demonstrated high sensitivity (90% training, 100% validation) and specificity (98.44% training, 90.48% validation) levels. The five-cytokine model (CXCL10, CCL19, IL-4, VEGF, and CCL20) also showed high sensitivity (91.67% training, 95.65% validation) and specificity (98.44% training, 100% validation). These feasible and accurate differentiation models may prompt early diagnosis of infections during immune therapy, allowing for early and appropriate intervention.
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Anion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM-WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1-methyl-3,3-diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the SN2 degradation mechanism dominated. Through acid-catalyzed Friedel-Crafts polymerization, a series of branched poly(aryl-quinuclidinium) (PAQ-x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ-x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall performance. Importantly, PAQ-5 was used in non-noble metal-based AEM-WE, achieving a high current density of 8â A cm-2 at 2â V and excellent stability over 2446â h in a gradient constant current test. Based on the excellent alkaline stability of this diaryl-quinuclidinium group, it can be further considered as a multifunctional building unit to create multi-topological polymers for energy conversion devices used in alkaline environments.
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The last decade has seen rapid development in the field of cellular immunotherapy, particularly in regard to chimeric antigen receptor (CAR)-modified T cells. However, challenges, such as severe treatment-related toxicities and inconsistent quality of autologous products, have hindered the broader use of CAR-T cell therapy, highlighting the need to explore alternative immune cells for cancer targeting. In this regard, natural killer (NK) cells have been extensively studied in cellular immunotherapy and were found to exert cytotoxic effects without being restricted by human leukocyte antigen and have a lower risk of causing graft-versus-host disease; making them favorable for the development of readily available "off-the-shelf" products. Clinical trials utilizing unedited NK cells or reprogrammed NK cells have shown early signs of their effectiveness against tumors. However, limitations, including limited in vivo persistence and expansion potential, remained. To enhance the antitumor function of NK cells, advanced gene-editing technologies and combination approaches have been explored. In this review, we summarize current clinical trials of antitumor NK cell therapy, provide an overview of innovative strategies for reprogramming NK cells, which include improvements in persistence, cytotoxicity, trafficking and the ability to counteract the immunosuppressive tumor microenvironment, and also discuss some potential combination therapies.
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Inhibiting the oxidation of Sn2+ during the crystallization process of Sn-Pb mixed perovskite film is found to be as important as the oxidation resistance of precursor solution to achieve high efficiency, but less investigated. Considering the excellent reduction feature of hydroquinone and the hydrophobicity of tert-butyl group, an antioxidant 2,5-di-tert-butylhydroquinone (DBHQ) was introduced into Sn-Pb mixed perovskite films using an anti-solvent approach to solve this problem. Interestingly, we find that DBHQ can act as function alterable additive during its utilization. On the one hand, DBHQ can restrict the oxidation of Sn2+ during the crystallization process, facilitating the fabrication of high-quality perovskite film; on the other hand, the generated oxidation product 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) can functionalize as defect passivator to inhibit the charge recombination. As a result, this synergetic effect renders the Sn-Pb mixed PSC a power conversion efficiency (PCE) up to 23.0 %, which is significantly higher than the reference device (19.6 %). Furthermore, the unencapsulated DBQH-modified PSCs exhibited excellent long-term stability and thermal stability, with the devices maintaining 84.2 % and 78.9 % of the initial PCEs after aging at 25 °C and 60 °C for 800â h and 120â h under N2 atmosphere, respectively. Therefore, the functional alterable strategy provides a novel cornerstone for high-performance Sn-Pb mixed PSCs.
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BACKGROUND & AIMS: This study aims to assess the nutritional status of patients during the different phases of the Chimeric Antigen Receptor (CAR)-T cell therapy and to identify prominent risk factors of hypoalbuminemia in patients after CAR-T treatment. The clinical consequences of malnutrition in cancer patients have been highlighted by growing evidence from previous clinical studies. Given CAR-T cell therapy's treatment intensity and possible side effects, it is important to provide patients with sufficient medical attention and support for their nutritional well-being. METHODS: This study was conducted from May 2021 to December 2021 among patients undergoing CAR-T cell therapy at the Bone Marrow Transplantation Center in The First Affiliated Hospital of Zhejiang University School of Medicine. Logistic regression analysis was performed to investigate the risk factors associated with hypoalbuminemia. Participants were divided into the cytokine release syndrome (CRS) group (n = 60) and the non-CRS group (n = 11) to further analyze the relationship between hypoalbuminemia and CRS. RESULTS: CRS (OR = 13.618; 95% CI = 1.499-123.709; P = 0.013) and baseline albumin (ALB) (OR = 0.854; 95% CI = 0.754-0.967; P = 0.020) were identified as the independent clinical factors associated with post-CAR-T hypoalbuminemia. According to the nadir of serum albumin, hypoalbuminemia occurred most frequently in patients with severe CRS (78.57%). The nadir of serum albumin (r = - 0.587, P < 0.001) and serum albumin at discharge (r = - 0.315, P = 0.01) were negatively correlated for the duration of CRS. Furthermore, patients with hypoalbuminemia deserved longer hospitalization (P = 0.04). CONCLUSIONS: CRS was identified as a significant risk factor associated with post-CAR-T hypoalbuminemia. An obvious decline in serum albumin was observed as the grade and duration of CRS increase. However, further research is still needed to elucidate the mechanisms of CRS-associated hypoalbuminemia.
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Neoplasias Hematológicas , Hipoalbuminemia , Receptores Quiméricos de Antígenos , Humanos , Síndrome de Liberación de Citoquinas/tratamiento farmacológico , Síndrome de Liberación de Citoquinas/etiología , Hipoalbuminemia/complicaciones , Inmunoterapia Adoptiva/efectos adversos , Neoplasias Hematológicas/terapia , Neoplasias Hematológicas/tratamiento farmacológico , Factores de Riesgo , Albúmina Sérica , Tratamiento Basado en Trasplante de Células y TejidosRESUMEN
Delicate interface modification is necessary for improving the photovoltaic performance of a perovskite solar cell (PSC). Herein, two asymmetric small molecules, termed BTD-DA and BTD-PA are designed and synthesized to govern the perovskite/Spiro-OMeTAD interface. The molecule BTD-PA featuring a donor-acceptor-acceptor (D-A-A') configuration shows a larger molecule dipole and a better effect on defect passivation and energy level regulation through the strong interaction between the pyridine group in BTD-PA and the surficial uncoordinated Pb2+. Consequently, the PSCs based on the BTD-PA treatment harvest a champion power conversion efficiency (PCE) of 24.46% for a 0.09 cm2 active area and 22.46% for the 1 cm2 device. Moreover, the long-term stability of FAPbI3 PSCs is also significantly improved because of the enhanced hydrophobicity and the inhibited phase transition of the FAPbI3 film with BTD-PA treatment. Our research provides a new strategy for interfacial engineering to boost the PCE and stability of the FAPbI3 PSCs.
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Despite considerable research efforts on photoelectrochemical water splitting over the past decades, practical application faces challenges by the absence of efficient, stable, and scalable photoelectrodes. Herein, we report a metal-halide perovskite-based photoanode for photoelectrochemical water oxidation. With a planar structure using mesoporous carbon as a hole-conducting layer, the precious metal-free FAPbBr3 photovoltaic device achieves 9.2% solar-to-electrical power conversion efficiency and 1.4 V open-circuit voltage. The photovoltaic architecture successfully applies to build a monolithic photoanode with the FAPbBr3 absorber, carbon/graphite conductive protection layers, and NiFe catalyst layers for water oxidation. The photoanode delivers ultralow onset potential below 0 V versus the reversible hydrogen electrode and high applied bias photon-to-current efficiency of 8.5%. Stable operation exceeding 100 h under solar illumination by applying ultraviolet-filter protection. The photothermal investigation verifies the performance boost in perovskite photoanode by photothermal effect. This study is significant in guiding the development of photovoltaic material-based photoelectrodes for solar fuel applications.
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Introducing fluorine (F) groups into a passivator plays an important role in enhancing the defect passivation effect for the perovskite film, which is usually attributed to the direct interaction of F and defect states. However, the interaction between electronegative F and electron-rich passivation groups in the same molecule, which may influence the passivation effect, is ignored. We herein report that such interactions can vary the electron cloud distribution around the passivation groups and thus changing their coordination with defect sites. By comparing two fluorinated molecules, heptafluorobutylamine (HFBM) and heptafluorobutyric acid (HFBA), we find that the F/-NH2 interaction in HFBM is stronger than the F/-COOH one in HFBA, inducing weaker passivation ability of HFBM than HFBA. Accordingly, HFBA-based perovskite solar cells (PSCs) provide an efficiency of 24.70 % with excellent long-term stability. Moreover, the efficiency of a large-area perovskite module (14.0â cm2 ) based on HFBA reaches 21.13 %. Our work offers an insight into understanding an unaware role of the F group in impacting the passivation effect for the perovskite film.
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Developing alternative electrolysis techniques is crucial for advancing electrocatalysis in addition to tremendous efforts of material developments. Recently, pulse electrochemical CO2 reduction reaction (CO2RR) has demonstrated dramatic selectivity improvement toward multicarbon (C2+) products compared to potentiostatic electrochemical CO2RR, yet the underlying mechanisms remain little understood. Herein, we develop a fast time-resolved in situ Raman spectroscopic method with a time resolution of 0.25 s. We reveal that pulse electrolysis improves the C2+ selectivity of CO2RR through dynamic controls of the surface CuxO/Cu composition that would be unachievable under potentiostatic electrolysis. The population of the surface-adsorbed CO intermediate (COads) is characterized to be the determining factor in controlling reaction selectivity, which depicts the C2+/C1 selectivity of CO2RR under pulse conditions. Meanwhile, the vibrational character of COads, despite transforming dynamically between the low-frequency and high-frequency modes is characterized not to be the key factor in controlling the reaction selectivity. Such an active control of catalyst surface compositions and reaction intermediates enabled by pulse electrolysis offer a general way of regulating the electrocatalysis performance of broad electrochemical reactions beyond CO2RR.
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Electricity-driven organo-oxidations have shown an increasing potential recently. However, oxygen evolution reaction (OER) is the primary competitive reaction, especially under high current densities, which leads to low Faradaic efficiency (FE) of the product and catalyst detachment from the electrode. Here, we report a bimetallic Ni-Cu electrocatalyst supported on Ni foam (Ni-Cu/NF) to passivate the OER process while the oxidation of 5-hydroxymethylfurfural (HMF) is significantly enhanced. A current density of 1000â mA cm-2 can be achieved at 1.50â V vs. reversible hydrogen electrode, and both FE and yield keep close to 100 % over a wide range of potentials. Both experimental results and theoretical calculations reveal that Cu doping impedes the OH* deprotonation to O* and hereby OER process is greatly passivated. Those instructive results provide a new approach to realizing highly efficient biomass upgrading by regulating the OER activity.
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Chimeric antigen receptor T (CAR-T) cell therapy is highly effective in inducing complete remission in haematological malignancies. Severe cytokine release syndrome (CRS) is the most significant and life-threatening adverse effect of this therapy. This multi-centre study was conducted at six hospitals in China. The training cohort included 87 patients with multiple myeloma (MM), an external validation cohort of 59 patients with MM and another external validation cohort of 68 patients with acute lymphoblastic leukaemia (ALL) or non-Hodgkin lymphoma (NHL). The levels of 45 cytokines on days 1-2 after CAR-T cell infusion and clinical characteristics of patients were used to develop the nomogram. A nomogram was developed, including CX3CL1, GZMB, IL4, IL6 and PDGFAA. Based on the training cohort, the nomogram had a bias-corrected AUC of 0.876 (95% CI = 0.871-0.882) for predicting severe CRS. The AUC was stable in both external validation cohorts (MM, AUC = 0.907, 95% CI = 0.899-0.916; ALL/NHL, AUC = 0.908, 95% CI = 0.903-0.913). The calibration plots (apparent and bias-corrected) overlapped with the ideal line in all cohorts. We developed a nomogram that can predict which patients are likely to develop severe CRS before they become critically ill, improving our understanding of CRS biology, and may guide future cytokine-directed therapies.
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Neoplasias Hematológicas , Linfoma no Hodgkin , Mieloma Múltiple , Leucemia-Linfoma Linfoblástico de Células Precursoras , Receptores Quiméricos de Antígenos , Humanos , Receptores Quiméricos de Antígenos/uso terapéutico , Síndrome de Liberación de Citoquinas/tratamiento farmacológico , Inmunoterapia Adoptiva/efectos adversos , Neoplasias Hematológicas/terapia , Inmunoterapia , Leucemia-Linfoma Linfoblástico de Células Precursoras/tratamiento farmacológico , Linfoma no Hodgkin/tratamiento farmacológico , Mieloma Múltiple/tratamiento farmacológicoRESUMEN
Background aims: B-cell maturation antigen (BCMA)-targeted chimeric antigen receptor-T cell (CAR-T) therapy is used for refractory or relapsed multiple myeloma (r/r MM). However, CAR-T-related tumor lysis syndrome (TLS) has been observed. We aimed to elucidate the incidence, clinical and laboratory characteristics, and prognosis of CAR-T cell-related TLS. Methods: Patients (n=105) with r/r MM treated with BCMA-targeted CAR-T cell therapy were included. Patient characteristics, laboratory parameters, and clinical outcomes were assessed. Results: Eighteen (17.1%) patients developed TLS after BCMA-targeted CAR-T cell therapy. The median time till TLS onset was 8 days. Patients with TLS had steep rise in uric acid (UA), creatinine, and lactate dehydrogenase (LDH) within 6 days following CAR-T cell infusion and presented earlier and persistent escalation of cytokines (C-reactive protein [CRP], interleukin-6 [IL-6], interferon-γ [IFN-γ], and ferritin levels). All 18 patients had cytokine release syndrome (CRS), of which 13 (72.2%) developed grade 3-4 CRS. Three of 18 patients (16.7%) developed immune effector cell-associated neurotoxicity syndrome (ICANS): two patients with grade 1 ICANS and one with grade 2 ICANS. TLS development had a negative effect on the objective response rate (77.8% in the TLS group vs. 95.4% in the non-TLS group, p<0.01). During the median follow-up of 15.1 months, the median PFS was poorer of patients with TLS (median: 3.4 months in the TLS group vs. 14.7 months in the non-TLS group, p<0.001, hazard ratio [HR]=3.5 [95% confidence interval [CI] 1.5-8.5]). Also, TLS development exhibited significant effects on OS (median: 5.0 months in the TLS group vs. 39.8 months in the non-TLS group, p<0.001, hazard ratio [HR]=3.7 [95% CI 1.3-10.3]). TLS was associated with a higher tumor burden, elevated baseline creatinine and UA levels, severe CRS, pronounced CAR-T cell expansion, and corticosteroid use. Conclusion: TLS is a frequently observed CAR-T therapy complication and negatively influences clinical response and prognosis. Close monitoring for TLS should be implemented during CAR-T cell therapy, especially for those at high TLS risk.
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Mieloma Múltiple , Receptores Quiméricos de Antígenos , Síndrome de Lisis Tumoral , Humanos , Mieloma Múltiple/tratamiento farmacológico , Antígeno de Maduración de Linfocitos B , Síndrome de Lisis Tumoral/etiología , Síndrome de Lisis Tumoral/terapia , Incidencia , Creatinina , Pronóstico , Tratamiento Basado en Trasplante de Células y TejidosRESUMEN
Many enzymes use adaptive frameworks to preorganize substrates, accommodate various structural and electronic demands of intermediates, and accelerate related catalysis. Inspired by biological systems, a Ru-based molecular water oxidation catalyst containing a configurationally labile ligand [2,2':6',2â³-terpyridine]-6,6â³-disulfonate was designed to mimic enzymatic framework, in which the sulfonate coordination is highly flexible and functions as both an electron donor to stabilize high-valent Ru and a proton acceptor to accelerate water dissociation, thus boosting the catalytic water oxidation performance thermodynamically and kinetically. The combination of single-crystal X-ray analysis, various temperature NMR, electrochemical techniques, and DFT calculations was utilized to investigate the fundamental role of the self-adaptive ligand, demonstrating that the on-demand configurational changes give rise to fast catalytic kinetics with a turnover frequency (TOF) over 2000 s-1, which is compared to oxygen-evolving complex (OEC) in natural photosynthesis.