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1.
Proc Natl Acad Sci U S A ; 119(7)2022 02 15.
Artículo en Inglés | MEDLINE | ID: mdl-35131938

RESUMEN

The catalytic depletion of Antarctic stratospheric ozone is linked to anthropogenic emissions of chlorine and bromine. Despite its larger ozone-depleting efficiency, the contribution of ocean-emitted iodine to ozone hole chemistry has not been evaluated, due to the negligible iodine levels previously reported to reach the stratosphere. Based on the recently observed range (0.77 ± 0.1 parts per trillion by volume [pptv]) of stratospheric iodine injection, we use the Whole Atmosphere Community Climate Model to assess the role of iodine in the formation and recent past evolution of the Antarctic ozone hole. Our 1980-2015 simulations indicate that iodine can significantly impact the lower part of the Antarctic ozone hole, contributing, on average, 10% of the lower stratospheric ozone loss during spring (up to 4.2% of the total stratospheric column). We find that the inclusion of iodine advances the beginning and delays the closure stages of the ozone hole by 3 d to 5 d, increasing its area and mass deficit by 11% and 20%, respectively. Despite being present in much smaller amounts, and due to faster gas-phase photochemical reactivation, iodine can dominate (∼73%) the halogen-mediated lower stratospheric ozone loss during summer and early fall, when the heterogeneous reactivation of inorganic chlorine and bromine reservoirs is reduced. The stratospheric ozone destruction caused by 0.77 pptv of iodine over Antarctica is equivalent to that of 3.1 (4.6) pptv of biogenic very short-lived bromocarbons during spring (rest of sunlit period). The relative contribution of iodine to future stratospheric ozone loss is likely to increase as anthropogenic chlorine and bromine emissions decline following the Montreal Protocol.


Asunto(s)
Atmósfera/análisis , Yodo/química , Pérdida de Ozono , Ozono Estratosférico/química , Contaminantes Atmosféricos/química , Regiones Antárticas , Estaciones del Año
2.
Proc Natl Acad Sci U S A ; 119(32): e2201729119, 2022 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-35917351

RESUMEN

The gas-phase formation of new particles less than 1 nm in size and their subsequent growth significantly alters the availability of cloud condensation nuclei (CCN, >30-50 nm), leading to impacts on cloud reflectance and the global radiative budget. However, this growth cannot be accounted for by condensation of typical species driving the initial nucleation. Here, we present evidence that nucleated iodine oxide clusters provide unique sites for the accelerated growth of organic vapors to overcome the coagulation sink. Heterogeneous reactions form low-volatility organic acids and alkylaminium salts in the particle phase, while further oligomerization of small α-dicarbonyls (e.g., glyoxal) drives the particle growth. This identified heterogeneous mechanism explains the occurrence of particle production events at organic vapor concentrations almost an order of magnitude lower than those required for growth via condensation alone. A notable fraction of iodine associated with these growing particles is recycled back into the gas phase, suggesting an effective transport mechanism for iodine to remote regions, acting as a "catalyst" for nucleation and subsequent new particle production in marine air.

3.
Nano Lett ; 24(10): 3036-3043, 2024 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-38415595

RESUMEN

Zinc-iodine batteries (ZIBs) are promising candidates for ecofriendly, safe, and low-cost energy storage systems, but polyiodide shuttling and the complex cathode fabrication procedures have severely hindered their broader commercial usage. Herein, a protocol is developed using phospholipid-like oleylamine molecules for scalable production of Langmuir-Blodgett films, which allows the facile preparation of ZIB cathodes in less than 1 min. The resulting inhomogeneous cathode allows for the continuous conversion of iodine. Moreover, the amine group of the oleylamine molecule at the cathode is capable of producing [OA*I+]I3- charge-transfer complexes with iodine, which facilitates the rapid migration of iodine and results in a highly reversible iodine conversion process. Consequently, the as-prepared ZIBs can deliver over 2000 cycles at 0.5 mA cm-2 with a capacity retention of 75.3%. This work presents a novel, straightforward, and efficient method for the rapid construction of ZIBs.

4.
J Lipid Res ; 65(7): 100572, 2024 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-38823780

RESUMEN

Contrast-enhanced computed tomography offers a nondestructive approach to studying adipose tissue in 3D. Several contrast-enhancing staining agents (CESAs) have been explored, whereof osmium tetroxide (OsO4) is the most popular nowadays. However, due to the toxicity and volatility of the conventional OsO4, alternative CESAs with similar staining properties were desired. Hf-WD 1:2 POM and Hexabrix have proven effective for structural analysis of adipocytes using contrast-enhanced computed tomography but fail to provide chemical information. This study introduces isotonic Lugol's iodine (IL) as an alternative CESA for adipose tissue analysis, comparing its staining potential with Hf-WD 1:2 POM and Hexabrix in murine caudal vertebrae and bovine muscle tissue strips. Single and sequential staining protocols were compared to assess the maximization of information extraction from each sample. The study investigated interactions, distribution, and reactivity of iodine species towards biomolecules using simplified model systems and assesses the potential of the CESA to provide chemical information. (Bio)chemical analyses on whole tissues revealed that differences in adipocyte gray values post-IL staining were associated with chemical distinctions between bovine muscle tissue and murine caudal vertebrae. More specific, a difference in the degree of unsaturation of fatty acids was identified as a likely contributor, though not the sole determinant of gray value differences. This research sheds light on the potential of IL as a CESA, offering both structural and chemical insights into adipose tissue composition.

5.
Prostate ; 84(6): 599-604, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38353033

RESUMEN

OBJECTIVES: To compare the effect of biopsy needle disinfection with 10% formalin solution alone and with povidone-iodine rectal cleaning on preventing infectious complications requiring hospitalization. METHODS: The data of 902 patients who underwent prostate biopsy by transrectal route were retrospectively analyzed. Inclusion criteria were prophylactic antibiotic use and negative urine culture before the biopsy. Three groups occurred according to the methods used during the biopsy procedure. In Group 1, 501 patients, biopsy needle disinfection was made using 10% formalin solution during the biopsy procedure. Group 2, 164 patients, applied only prophylactic antibiotics. Group 3, 237 patients, applied both 10% formalin disinfection of the biopsy needle and prebiopsy povidone-iodine rectal cleansing. Hospitalized patients because of infectious complications a month after the biopsy were our outcome measures. RESULTS: Hospitalization rates because of biopsy-related infectious complications, according to Groups 1, 2, and 3, were 2.7%, 8.5%, and 0%, respectively. The best results were observed in Group 3 and the worst in Group 2. CONCLUSIONS: The two nonantibiotic strategies, biopsy needle disinfection with formalin solution and rectal cleaning with povidone-iodine, look more effective when applied together. However, further prospective studies are required to confirm our analysis.


Asunto(s)
Povidona Yodada , Próstata , Masculino , Humanos , Próstata/patología , Estudios Retrospectivos , Biopsia/efectos adversos , Hospitalización , Formaldehído
6.
Cancer ; 130(12): 2215-2223, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38376914

RESUMEN

BACKGROUND: Telomere length is associated with cancer risk and cancer aggressiveness. Radioactive iodine (RAI) therapy for thyroid cancer has raised concerns for second primary malignancy (SPM) in patients with high cumulative doses. The association between RAI dose and peripheral blood leukocyte telomere length was examined. METHODS: A total of 425 patients were included who underwent total thyroidectomy and were followed up for at least 1 year with or without RAI treatment. The relative telomere length (RTL) of the patients was assessed via a quantitative polymerase chain reaction amplification method. RAI doses were divided into five groups on the basis of cumulative dose, and a comparison was made among these groups. RESULTS: The number of patients with RAI treatment was 287 (67.5%), and the cumulative RAI dose was 3.33 GBq (range, 1.11-131.35 GBq). The mean RTL was significantly shorter in the highest RAI group (>22.2 GBq) compared to both the no-RAI and lower dose groups. The association between RAI dose and RTL was positive in the lower RAI group (1.1-3.7 GBq) and negative in the highest RAI group in both univariate and multivariate analyses. We observed 59 (13.9%) SPMs and 20 (4.7%) mortalities, and RTL did not show a significant risk effect for all-cause, thyroid cancer-specific, or SPM-specific mortality. CONCLUSIONS: In patients with thyroid cancer who underwent total thyroidectomy, peripheral blood leukocyte telomere length exhibited a significant association with cumulative RAI dose higher than 22.2 GBq. These results suggest the possibility of telomere length shortening in patients who undergo high-dose RAI treatment.


Asunto(s)
Radioisótopos de Yodo , Leucocitos , Telómero , Neoplasias de la Tiroides , Tiroidectomía , Humanos , Neoplasias de la Tiroides/radioterapia , Neoplasias de la Tiroides/sangre , Neoplasias de la Tiroides/genética , Neoplasias de la Tiroides/patología , Radioisótopos de Yodo/uso terapéutico , Masculino , Femenino , Persona de Mediana Edad , Adulto , Leucocitos/efectos de la radiación , Anciano , Telómero/efectos de la radiación , Acortamiento del Telómero/efectos de la radiación , Adulto Joven , Neoplasias Primarias Secundarias/sangre , Adolescente
7.
Funct Integr Genomics ; 24(3): 114, 2024 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-38862667

RESUMEN

With advances in radioactive particle implantation in clinical practice, Iodine-125 (125I) seed brachytherapy has emerged as a promising treatment for cholangiocarcinoma (CCA), showing good prognosis; however, the underlying molecular mechanism of the therapeutic effect of 125I seed is unclear. To study the effects of 125I seed on the proliferation and apoptosis of CCA cells. CCA cell lines, RBE and HCCC-9810, were treated with reactive oxygen species (ROS) scavenger acetylcysteine (NAC) or the p53 functional inhibitor, pifithrin-α hydrobromide (PFTα). Cell counting kit-8 (CCK-8) assay, 5-bromo-2-deoxy-uridine (BrdU) staining, and terminal deoxynucleotidyl transferase (TdT)-mediated dUTP nick end labeling (TUNEL) assay and flow cytometry assay were performed to test the radiation-sensitivity of 125I seed toward CCA cells at different radiation doses (0.4 mCi and 0.8 mCi). 2,7-dichlorofluorescein diacetate (DCF-DA) assay, real-time quantitative polymerase chain reaction (RT-qPCR), and western blot analysis were performed to assess the effect of 125I seed on the ROS/p53 axis. A dose-dependent inhibitory effect of 125I seeds on the proliferation of CCA cells was observed. The 125I seed promoted apoptosis of CCA cells and induced the activation of the ROS/p53 pathway in a dose-dependent manner. NAC or PFTα treatment effectively reversed the stimulatory effect of 125I seed on the proliferation of CCA cells. NAC or PFTα suppressed apoptosis and p53 protein expression induced by the 125I seed. 125I seed can inhibit cell growth mainly through the apoptotic pathway. The mechanism may involve the activation of p53 and its downstream apoptotic pathway by up-regulating the level of ROS in cells.


Asunto(s)
Apoptosis , Proliferación Celular , Colangiocarcinoma , Radioisótopos de Yodo , Especies Reactivas de Oxígeno , Proteína p53 Supresora de Tumor , Colangiocarcinoma/metabolismo , Colangiocarcinoma/radioterapia , Colangiocarcinoma/patología , Colangiocarcinoma/genética , Colangiocarcinoma/tratamiento farmacológico , Proteína p53 Supresora de Tumor/metabolismo , Proteína p53 Supresora de Tumor/genética , Especies Reactivas de Oxígeno/metabolismo , Apoptosis/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Humanos , Línea Celular Tumoral , Neoplasias de los Conductos Biliares/metabolismo , Neoplasias de los Conductos Biliares/patología , Neoplasias de los Conductos Biliares/genética , Neoplasias de los Conductos Biliares/radioterapia , Acetilcisteína/farmacología , Benzotiazoles/farmacología , Transducción de Señal/efectos de los fármacos
8.
J Comput Chem ; 45(12): 903-914, 2024 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-38165152

RESUMEN

Theoretical investigation of thermodynamic stability and bonding features of possible isomers of the molecular and ionic complexes of pyridine with molecular iodine and iodine monochloride IX (X = I,Cl) is presented. M06-2X DFT functional is found to provide bond distances and dissociation energies which are close to those obtained at high-level ab initio CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz benchmark computations for the most stable isomers, formed via donation of a lone pair of nitrogen atom of pyridine to the iodine atom. These isomers are by 23-33 kJ mol-1 (in case of I2) and by 39-56 kJ mol-1 (in case of ICl) more stable than other molecular complexes. T-shaped π-σ* bonded isomers turn out to be energetically comparable with van der Waals bound compounds. Among the ionic isomers, structures featuring [IPy2]+ cation with I3 - or ICl2 - counterions are more stable. Oligomerization favors ionic isomers starting from the tetrameric clusters of the composition (IX)4Py4.

9.
Small ; 20(26): e2310475, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38229534

RESUMEN

Zinc-iodine batteries (Zn-I2) are extremely attractive as the safe and cost-effective scalable energy storage system in the stationary applications. However, the inefficient redox kinetics and "shuttling effect" of iodine species result in unsatisfactory energy efficiency and short cycle life, hindering their commercialization. In this work, Ni single atoms highly dispersed on carbon fibers is designed and synthesized as iodine anchoring sites and dual catalysts for Zn-I2 batteries, and successfully inhibit the iodine species shuttling and boost dual reaction kinetics. Theoretical calculations indicate that the reinforced d-p orbital hybridization and charge interaction between Ni single-atoms and iodine species effectively enhance the confinement of iodine species. Ni single-atoms also accelerate the iodine conversion reactions with tailored bonding structure of I─I bonds and reduced energy barrier for the dual conversion of iodine species. Consequently, the high-rate performance (180 mAh g-1 at 3 A g-1), cycling stability (capacity retention of 74% after 5900 cycles) and high energy efficiency (90% at 3 A g-1) are achieved. The work provides an effective strategy for the development of iodine hosts with high catalytic activity for Zn-I2 batteries.

10.
Small ; : e2310865, 2024 Apr 28.
Artículo en Inglés | MEDLINE | ID: mdl-38678537

RESUMEN

Photopharmacology, incorporating photoswitches such as azobenezes into drugs, is an emerging therapeutic method to realize spatiotemporal control of pharmacological activity by light. However, most photoswitchable molecules are triggered by UV light with limited tissue penetration, which greatly restricts the in vivo application. Here, this study proves that 131I can trigger the trans-cis photoisomerization of a reported azobenezen incorporating PROTACs (azoPROTAC). With the presence of 50 µCi mL-1 131I, the azoPROTAC can effectively down-regulate BRD4 and c-Myc levels in 4T1 cells at a similar level as it does under light irradiation (405 nm, 60 mW cm-2). What's more, the degradation of BRD4 can further benefit the 131I-based radiotherapy. The in vivo experiment proves that intratumoral co-adminstration of 131I (300 µCi) and azoPROTC (25 mg kg-1) via hydrogel not only successfully induce protein degradation in 4T1 tumor bearing-mice but also efficiently inhibit tumor growth with enhanced radiotherapeutic effect and anti-tumor immunological effect. This is the first time that a radioisotope is successfully used as a trigger in photopharmacology in a mouse model. It believes that this study will benefit photopharmacology in deep tissue.

11.
Small ; 20(12): e2307021, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-37940629

RESUMEN

Electrochemically reversible conversion of I2/I- redox couple in a controllable iodine speciation manner is the eternal target for practical metal-iodine batteries. This contribution demonstrates an advanced polyiodide-free Zn-I2 battery achieved by the bidirectional confined redox catalysis-directed quasi-solid iodine conversion. A core-shell structured iodine cathode is fabricated by integrating multiporous Prussian blue nanocubes as a catalytic mediator, and the polypyrrole sheath afforded a confinement environment that favored the iodine redox. The zincate Znx+1FeIII/II[Fe(CN)6]y has substantially faster zinc-ion intercalation kinetics and overlapping kinetic voltage profiles compared with the I2/ZnI2 redox, and behave as a redox mediator that catalyze reduction of polyiodides via chemical redox reactions during battery discharging and an exemplary reaction is Zn(I3)2+2Znx+1FeII[Fe(CN)6]y=3ZnI2+2ZnxFeIII[Fe(CN)6]y,ΔG=-19.3 kJ mol-1). During the following recharging process, the electrodeposited ZnI2 can be facially activated by iron redox hotspots, and the ZnxFe[FeIII/II(CN)6]y served as a cation-transfer mediator and spontaneously catalyze polyiodides oxidation (Zn(I3)2+2ZnxFe[FeIII(CN)6]y=3I2+2Znx+1Fe[FeII(CN)6]y,ΔG = -7.72 kJ mol-1), manipulating the reversible one-step conversion of ZnI2 back to I2. Accordingly, a flexible solid-state battery employing the designed cathode can deliver an energy density of 215 Wh kgiodine -1.

12.
Small ; 20(16): e2308175, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38032163

RESUMEN

The safe and efficient management of hazardous radioactive iodine is significant for nuclear waste reprocessing and environmental industries. A novel supramolecular framework compound based on cucurbit[8]uril (Q[8]) and 4-aminopyridine (4-AP) is reported in this paper. In the single crystal structure of Q[8]-(4-AP), two 4-AP molecules interact with the outer surface of Q[8] and the two other 4-AP molecules are encapsulated into the Q[8] cavity to form the self-assembly Q[8]-(4-AP). Iodine adsorption experiments show that the as-prepared Q[8]-(4-AP) not only has a high adsorption capacity (1.74 g· g-1) for iodine vapor but also can remove the iodine in the organic solvent and the aqueous solution with the removal efficiencies of 95% and 91%, respectively. The presence of a large number of hydrogen bonds between the iodine molecule and the absorbent, as seen in the single crystal structure of iodine-loaded Q[8]-(4-AP) (I2@Q[8]-(4-AP)), is thought to be responsible for the exceptional iodine adsorption capacity of the material. In addition, the adsorption-desorption tests reveal that the self-assembly material has no significant loss of iodine capture capacity after five cycles, indicating that it has sufficient reusability.

13.
Small ; 20(8): e2307863, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-37822157

RESUMEN

The low energy efficiency and limited cycling life of rechargeable Zn-air batteries (ZABs) arising from the sluggish oxygen reduction/evolution reactions (ORR/OERs) severely hinder their commercial deployment. Herein, a zeolitic imidazolate framework (ZIF)-derived strategy associated with subsequent thermal fixing treatment is proposed to fabricate dual-atom CoFe─N─C nanorods (Co1 Fe1 ─N─C NRs) containing atomically dispersed bimetallic Co/Fe sites, which can promote the energy efficiency and cyclability of ZABs simultaneously by introducing the low-potential oxidation redox reactions. Compared to the mono-metallic nanorods, Co1 Fe1 ─N─C NRs exhibit remarkable ORR performance including a positive half-wave potential of 0.933 V versus reversible hydrogen electrode (RHE) in alkaline electrolyte. Surprisingly, after introducing the potassium iodide (KI) additive, the oxidation overpotential of Co1 Fe1 ─N─C NRs to reach 10 mA cm-2 can be significantly reduced by 395 mV compared to the conventional destructive OER. Theoretical calculations show that the markedly decreased overpotential of iodide oxidation can be ascribed to the synergistic effects of neighboring Co─Fe diatomic sites as the unique adsorption sites. Overall, aqueous ZABs assembled with Co1 Fe1 ─N─C NRs and KI as the air-cathode catalyst and electrolyte additive, respectively, can deliver a low charging voltage of 1.76 V and ultralong cycling stability of over 230 h with a high energy efficiency of ≈68%.

14.
Small ; 20(2): e2305217, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37661581

RESUMEN

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

15.
Small ; 20(15): e2307484, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38050936

RESUMEN

Green synthesis of stable metal-organic frameworks (MOFs) with permanent and highly ordered porosity at room temperature without needing toxic and harmful solvents and long-term high-temperature reactions is crucial for sustainable production. Herein, a rapid and environmentally friendly synthesis strategy is reported to synthesize the complex topological bismuth-based-MOFs (Bi-MOFs), [Bi9(C9H3O6)9(H2O)9] (denoted CAU-17), in water under ambient conditions by surfactant-mediated sonochemical approach, which could also be applicable to other MOFs. This strategy explores using cetyltrimethylammonium bromide (CTAB) amphiphilic molecules as structure-inducing agents to control the removal of non-coordinated water (dehydration) and enhance the degree of deprotonation of the ligands, thereby regulating the coordination and crystallization in aqueous solutions. In addition, another two new strategies for synthesizing CAU-17 by crystal reconstruction and one-step synthesis in binary solvents are provided, and the solvent-induced synthesis mechanism of CAU-17 is studied. The as-prepared CAU-17 presents a competitive iodine capture capability and effective delivery of the antiarrhythmic drug procainamide (PA) for enteropatia due to the broad pH tolerance and the unique phosphate-responsive destruction in the intestine. The findings will provide valuable ideas for the follow-up study of surfactant-assisted aqueous synthesis of MOFs and their potential applications.

16.
Small ; : e2311181, 2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38361209

RESUMEN

Efficient capture and storage of radioactive I2 is a prerequisite for developing nuclear power but remains a challenge. Here, two flexible Ag-MOFs (FJI-H39 and 40) with similar active sites but different pore sizes and flexibility are prepared; both of them can capture I2 with excellent removal efficiencies and high adsorption capacities. Due to the more flexible pores, FJI-H39 not only possesses the record-high I2 storage density among all the reported MOFs but also displays a very fast adsorption kinetic (124 times faster than FJI-H40), while their desorption kinetics are comparable. Mechanistic studies show that FJI-H39 can undergo induced-fit transformations continuously (first contraction then expansion), making the adsorbed iodine species enrich near the Ag(I) nodes quickly and orderly, from discrete I- anion to the dense packing of various iodine species, achieving the very fast adsorption kinetic and the record-high storage density simultaneously. However, no significant structural transformations caused by the adsorbed iodine are observed in FJI-H40. In addition, FJI-H39 has excellent stability/recyclability/obtainability, making it a practical adsorbent for radioactive I2 . This work provides a useful method for synthesizing practical radioactive I2 adsorbents.

17.
Small ; : e2400265, 2024 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-38660825

RESUMEN

Two titanium-based MOFs MIL-125 and MIL-125_NH2 are synthesized and characterized using high-temperature powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), N2 sorption, Fourier transformed infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet-visible spectroscopy (UV-Vis), and electron paramagnetic resonance (EPR). Stable up to 300 °C, both compounds exhibited similar specific surface areas (SSA) values (1207 and 1099 m2 g-1 for MIL-125 and MIL-125_NH2, respectively). EPR signals of Ti3+ are observed in both, whith MIL-125_NH2 also showing ─NH2 ●+ signatures. Both MOFs efficiently adsorbed iodine in continuous gas flow over five days, with MIL-125 trapping 1.9 g.g-1 and MIL-125_NH2 trapping 1.6 g.g-1. MIL-125_NH2 exhibited faster adsorption kinetics due to its smaller band gap (2.5 against 3.6 eV). In situ Raman spectroscopy conducted during iodine adsorption revealed signal evolution from "free" I2 to "perturbed" I2, and I3 -. TGA and in situ Raman desorption experiments showed that ─NH2 groups improved the stabilization of I3 - due to an electrostatic interaction with NH2 ●+BDC radicals. The Albery model indicated longer lifetimes for iodine desorption in I2@MIL-125_NH2, attributed to a rate-limiting step due to stronger interaction between the anionic iodine species and the ─NH2 ●+ radicals. This study underscores how MOFs with efficient charge separation and hole-stabilizer functional groups enhance iodine stability at higher temperatures.

18.
Small ; 20(27): e2311083, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38268236

RESUMEN

Although metal-organic polyhedra (MOPs) expansion has been studied to date, it is still a rare occurrence for their porous intermolecular assembly for iodine capture. The major limitation is the lack of programmable and controllable methods for effectively constructing and utilizing the exterior cavities. Herein, the goal of programmable porous intermolecular assembly is realized in the first family of aluminum oxo polyhedrons (AlOPs) using ligands with directional H-bonding donor/acceptor pairs and auxiliary alcohols as structural regulation sites. The approach has the advantage of avoiding the use of expensive edge-directed ditopic and face-directed tritopic ligands in the general synthesis strategy of MOPs. Combining theoretical calculations and experiments, the intrinsic relationship is revealed between alcohol ligands and the growth mechanism of AlOPs. The maximum I2 uptake based on the mass gain during sorption corresponds to 2.35 g g-1, representing the highest reported I2 sorption by an MOP. In addition, it can be easily regenerated and maintained the iodine sorption capacity, revealing its further potential application. This method of constructing stable and programmable porous materials will provide a new way to solve problems such as radionuclide capture.

19.
Small ; 20(20): e2307666, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38279566

RESUMEN

Discovery of new topology covalent organic frameworks (COFs) is a mainstay in reticular chemistry and materials research because it not only serves as a stepwise guide to the designed construction of covalent-organic architectures but also helps to comprehend function from structural design point-of-view. Proceeding on this track, the first 3D COF, TUS-38, with the topology is constructed by reticulating a planar triangular 3-c node of D3h symmetry with a tetragonal prism 8-c node of D2h symmetry via [3 + 8] reversible imine condensation reaction. TUS-38 represents a twofold interpenetrated multidirectional pore network with a high degree of crystallinity and structural integrity. Interestingly, stemming from the nitrogen-rich s-triazine rings with electron-deficient character and ─C â• N─ linkages composing the TUS-38 framework that benefit to the charge-transfer and hence dipole-dipole electrostatic interactions between the framework and iodine in addition to exclusive topological characteristics of the exotic the net, TUS-38 achieves an exemplary capacity for iodine vapor uptake reaching 6.3 g g-1. Recyclability studies evidence that TUS-38 can be reused at least five times retaining 95% of its initial adsorption capacity; while density functional theory (DFT) calculations have heightened the understanding of the interactions between iodine molecules and the framework.

20.
Small ; : e2402527, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38888122

RESUMEN

Aqueous zinc-iodine batteries are promising candidates for large-scale energy storage due to their high energy density and low cost. However, their development is hindered by several drawbacks, including zinc dendrites, anode corrosion, and the shuttle of polyiodides. Here, the design of 2D-shaped tungsten boride nanosheets with abundant borophene subunits-based active sites is reported to guide the (002) plane-dominated deposition of zinc while suppressing side reactions, which facilitates interfacial nucleation and uniform growth of zinc. Meanwhile, the interfacial d-band orbits of tungsten sites can further enhance the anchoring of polyiodides on the surface, to promote the electrocatalytic redox conversion of iodine. The resulting tungsten boride-based I2 cathodes in zinc-iodine cells exhibit impressive cyclic stability after 5000 cycles at 50 C, which accelerates the practical applications of zinc-iodine batteries.

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