Open Sites Research Articles

The Assembly of Cerium(III)-Containing Silicotungstate with Lewis Acid-Base Sites Enables the Selective C3-Alkenylation of Oxindole.

A cerium(III)-containing silicotungstate, [H2N(CH3)2]10NaK[KCe(SiW11O39)2(H2O)]·18.5H2O (CeSiW), was successfully synthesized and characterized. Structure analysis reveals that CeSiW is composed of two {SiW11O39} units connected by one cerium(III) cation to form a typical 1:2 sandwich structure, which is further expanding into a 1D chain linked by K+ ions. The oxygen-enriched surfaces of {SiW11O39} units and open cerium sites provide abundant Lewis base and acid sites in CeSiW. As a result, CeSiW efficiently catalyzed the C3-alkenylation of oxindoles with aldehydes through the simultaneous activation of both reaction substrates on its crystal framework. Various 3-benzylidene-oxindoles are synthesized with excellent yields and high E-selectivity under solvent-free conditions.

Diversidad y distribución de los helechos y licófitos de un bosque subandino del norte de los Andes

Background and aims: Ferns and lycophytes are highly diverse in Neotropical forests, and their distribution is influenced by various biotic and abiotic factors, including disturbance. This study analyzes the effect of some of these factors on the diversity of these plants in a sub-Andean forest. M&M: Four transects of 400 m2 (80×5 m) were established, two in highly disturbed sites, grassland, and stream edge, and two in the forest. Each transect was divided into 16 plots where all terrestrial and epiphytic individuals were recorded. Clustering analyses were performed to recognize the presence of floristic groups, and a canonical correlation analysis was performed to identify how soil chemistry and vegetation structure affect the composition and diversity of these plants. Results: A total of 4935 individuals were found, representing 42 species. Amauropelta rudis (Kunze) Pic. Serm. (2485 individuals) and Asplenium flabellulatum Kunze (1190 individuals) were the dominant terrestrial species. The clustering and ordination analyses revealed that the plots of open sites are more related to each other than to those of the forest. Species of open sites are more correlated with a lower layer of litter, a lower height and coverage of trees or saplings, a higher concentration of aluminum and a lower concentration of sodium. Conclusions: Ferns and lycophytes are influenced by the environmental, structural and disturbance conditions of the site where they grow. Key words Disturbance, diversity, edaphic factors, multivariate analysis, pteridophytes, richness, structural factors.

Cpt1a Drives primed-to-naïve pluripotency transition through lipid remodeling

Metabolism has been implicated in cell fate determination, particularly through epigenetic modifications. Similarly, lipid remodeling also plays a role in regulating cell fate. Here, we present comprehensive lipidomics analysis during BMP4-driven primed to naive pluripotency transition or BiPNT and demonstrate that lipid remodeling plays an essential role. We further identify Cpt1a as a rate-limiting factor in BiPNT, driving lipid remodeling and metabolic reprogramming while simultaneously increasing intracellular acetyl-CoA levels and enhancing H3K27ac at chromatin open sites. Perturbation of BiPNT by histone acetylation inhibitors suppresses lipid remodeling and pluripotency transition. Together, our study suggests that lipid remodeling promotes pluripotency transitions and further regulates cell fate decisions, implicating Cpt1a as a critical regulator between primed-naive cell fate control.

Enhancing photocatalytic performance of rose-shaped Co/Ni bimetallic organic framework for reducing CO2 to CO under visible light

Co-MOF-74, composed of Co salt as the metal source and 2,5-dihydroxyterephthalic acid as the organic ligand, is widely used as a catalyst for the photocatalytic reduction of CO2 due to its open metal sites, high porosity, large specific surface area, and high CO2 adsorption capacity. However, its effectiveness in CO2 conversion is limited by weak electron transfer capabilities and a high rate of electron/hole pair recombination. To address these limitations, a bimetallic strategy was employed to significantly improve the catalytic performance of Co-MOF-74 for photocatalytic CO2 reduction. Stable bimetallic Co/Ni-MOF-74-x (x = 1, 2, 3) with controllable morphology and metal ratios were synthesized by adjusting the molar ratios of Co2+ and Ni2+ and combining them with 2,5-dihydroxyterephthalic acid. The introduction of Ni2+ led to a significant increase in the specific surface area, from 204.999 m2/g (Co/Ni-MOF-74) to 790.873 m2/g (Co/Ni-MOF-74-1). In addition, the band gap of bimetallic Co/Ni-MOF-74-1 was narrowed to 1.4 eV, which enhanced charge transfer. As a result, photocatalytic experiments demonstrated that the CO2 conversion efficiency of bimetallic Co/Ni-MOF-74-1 was significantly improved, reaching 4.539 mmol/g/h, compared to that of the monometallic Co-MOF-74. Finally, a synergistic photocatalytic mechanism involving ligand activation was proposed to explain the reaction process of the bimetallic Co/Ni-MOF-74 catalyst. Meanwhile, this study highlights that the bimetallic strategy is an effective approach to optimizing the performance of MOF catalysts for the photocatalytic reduction of CO2.

Prohibitin 2 orchestrates long noncoding RNA and gene transcription to accelerate tumorigenesis

The spatial co-presence of aberrant long non-coding RNAs (lncRNAs) and abnormal coding genes contributes to malignancy development in various tumors. However, precise coordinated mechanisms underlying this phenomenon in tumorigenesis remains incompletely understood. Here, we show that Prohibitin 2 (PHB2) orchestrates the transcription of an oncogenic CASC15-New-Isoform 2 (CANT2) lncRNA and the coding tumor-suppressor gene CCBE1, thereby accelerating melanoma tumorigenesis. In melanoma cells, PHB2 initially accesses the open chromatin sites at the CANT2 promoter, recruiting MLL2 to augment H3K4 trimethylation and activate CANT2 transcription. Intriguingly, PHB2 further binds the activated CANT2 transcript, targeting the promoter of the tumor-suppressor gene CCBE1. This interaction recruits histone deacetylase HDAC1 to decrease H3K27 acetylation at the CCBE1 promoter and inhibit its transcription, significantly promoting tumor cell growth and metastasis both in vitro and in vivo. Our study elucidates a PHB2-mediated mechanism that orchestrates the aberrant transcription of lncRNAs and coding genes, providing an intriguing epigenetic regulatory model in tumorigenesis.

Water in the micropores of CPO-27 metal-organic frameworks: A comprehensive study

The metal-organic framework CPO-27 exhibits free coordination sites (open metal sites) and can be prepared with a wide range of metals that influence its properties. It is therefore an intriguing structure to study sorption phenomena. We analyze the water resistance and sorption behavior of these frameworks, with particular attention to the sorption mechanism in detail and the structure of the confined water molecules. For this purpose, we use manometric water vapor sorption analysis and FTIR spectroscopy. The respective metal center orchestrates both the adsorption behavior and the arrangement of the water molecules in the micropores of the framework. The extent to which water molecules form hydrogen bonds (with each other and with framework oxygen atoms) plays a crucial role in the stability of the framework towards water. Water adsorption is governed by the coordination of water molecules to the open metal sites (except for CPO-27-Cu) and subsequent H-bonding. A stepwise adsorption of water is observed, with significant differences depending on the choice of metal.

A Magnesium Organic Framework Fluorescent Sensor for Selective Detection of Nitrofuran Antibiotics and Inorganic Pollutants

ABSTRACTA novel 3D magnesium‐based metal organic framework (Mg‐MOF) has been solvothermally synthesized using 5‐(pyridin‐4‐yl)isophthalic acid. The ligand has demonstrated to preserve two types of coordination modes depending on the connection mode of the pyridine group. The uncoordinated pyridine groups provide Lewis base sites (LBSs), whereas the coordinated ones promote to form a rarely reported eight‐connected tetranuclear Mg clusters. Benefiting from the multinuclearity with high number of connections, the framework keeps good performance of high thermal stability until 500°C. Furthermore, the framework exhibits potential open metal sites (OMSs) benefiting from the terminal coordinated water groups of the metal clusters. Owing to the abundant active sites, the Mg‐MOF exhibits good sensitivity to nitrofuran antibiotics and Cr2O72−, with high KSV (at 104 M−1 level) and low limit of detection (LOD) values (∼10−6 M). Density functional theory (DFT) investigation reveals that the interchange of the HOMO–LUMO energy levels of the framework and antibiotics is responsible for the sensing activity. In addition, the Mg‐MOF is greatly recyclable in five cycles while maintaining the structural rigidity and sensing activity, making it a promising luminescence probe material.

Self‐Assembly of UiO‐66 on Conjugated Polyelectrolytes: Toward Enhanced Photophysical Properties

AbstractIn this study, the synthesis and characterization of the fluorescent metal–organic framework (MOF)‐polymer composites is reported based on zirconium‐based MOFs (UiO‐66 and UiO‐66(OH)₂) and a conjugated polyelectrolyte, poly(phenylene ethynylene) carboxylate (PPE‐CO₂‐108). The defect‐rich nature of these Zr‐MOFs facilitates strong interactions between the polyelectrolyte's carboxylic acid moieties and the open metal sites on the Zr clusters within the MOF nanoparticles. The composites are prepared by a simple impregnation approach, where MOF nanocrystals suspended in HEPES buffer are added to the polymeric solution under sonication for 10 min. The obtained MOF composites (i.e., UiO‐66‐CPE and UiO‐66 (OH)2‐CPE) are characterized using powder X‐ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Brunauer‐Emmett‐Teller (BET) surface area, zeta potential measurements, and UV–vis spectroscopy. The characterization confirmed the homogeneous distribution of the MOF nanocrystals on the polymer as seen in the SEM images, and the interaction with PPE‐CO₂‐108 is confirmed by the decrease in the surface areas from 1050 to 590 m2 g−1 for UiO‐66‐CPE and from 500 to 137 m2 g−1, for UiO‐66(OH)2‐CPE. Fluorescence microscopy revealed strong fluorescence in the microparticles, confirming robust polymer‐MOF interaction. The composites also exhibit improved photostability of the conjugated polyelectrolyte, suggesting their potential for applications in biomedical imaging and other areas requiring stable and bright fluorescent systems.

A Dinitrogen Divanadium Complex Supported by a Trisamidophosphine Ligand

Comprehensive SummaryThe reaction between tripodal trisamidophosphine ligand H3PN3Ar and V(Mes)3(THF) (Mes = mesityl) yields the vanadium(III) complex (PN3Ar)V (1) with an open site in the axial position, which could coordinate with THF, pyridine, and NH3 to form the corresponding adducts (2—4). The vanadium(III) center is redox‐active, as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction. Notably, a novel dinitrogen divanadium complex with a bridging N2 ligand, {K(THF)}2{[PN3Ar]V}2(μ‐N2) (6), was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N2 atmosphere. The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations. Additionally, these vanadium complexes (1, 5, 6) can serve as catalysts for the conversion of N2 into N(SiMe3)3 in the presence of reductants and Me3SiCl.

Integration of Open Metal Sites in an Amino-Functionalized Sm(III)-Organic Framework toward Enhanced Third-Order Nonlinear Optical Property.

A variety of new inorganic and organic materials have emerged to advance laser technologies and optical engineering. A rational design approach can contribute significantly to fabricating nonlinear optically active metal-organic frameworks (MOFs) by considering the underlying structure-property linkage. Here, it has been embarked on a study of novel samarium(III) MOF, ([Sm2(ata)3(DMF)4]·DMF (ata2-: 2-aminoterephthalate), abbreviated as NH2-Sm-MUM-4) with enhanced nonlinear optical (NLO) properties. The crystal structure of this MOF represents a 6-connected framework with a pcu topology and distinctive characteristics, including open metal sites, free amine groups, and great stability, making it suitable for third-order NLO activity. The nonlinear index of refraction (n2) revealed the self-focusing impacts of NH2-Sm-MUM-4 at different incident intensities. The highest value of n2 and β related to 10 mw power of incident intensity are 5.15 cm2/W and 2.65 cm/W, respectively. As far as the authors know, this is the first study examining the potential systematic structural-property associations in Sm-MOFs considering improved third-order NLO properties.

Ultra-Microporous Fe-MOF with Prolonged NO Delivery in Biological Media for Therapeutic Application.

Nitric oxide (NO), a key element in the regulation of essential biological mechanisms, presents huge potential as therapeutic agent in the treatment and prevention of chronic diseases. Metal-organic frameworks (MOFs) with open metal sites are promising carriers for NO therapies but delivering it over an extended period in biological media remains a great challenge due to i) a fast degradation of the material in body fluids and/or ii) a rapid replacement of NO by water molecules onto the Lewis acid sites. Here, a new ultra-narrow pores Fe bisphosphonate MOF, denoted MIP-210(Fe) or Fe(H2O)(Hmbpa) (H4mbpa = p-xylenediphosphonic acid) is described that adsorbs NO due to an unprecedented sorption mechanism: coordination of NO through the Fe(III) sites is unusually preferred, replacing bound water, and creating a stable interaction with the free H2O and P-OH groups delimiting the ultra-narrow pores. This, associated with the high chemical stability of the MOF in body fluids, enables an unprecedented slow replacement of NO by water molecules in biological media, achieving an extraordinarily extended NO delivery time over at least 70h, exceeding by far the NO kinetics release reported with others porous materials, paving the way for the development of safe and successful gas therapies.

Nourishing Love: Documenting the Cookery and Foodways Collections at the Michigan State University Libraries

Food tells stories. All generations of home cooks share commonalities, from poor to rich, recipes and experiences with food for better or worse “feed” one another. Where the art of culinary prose intersects with the palate, the cookery and foodways collections provide unique avenues into lifestyles, nutrition, and the palatable offerings served across the globe. For more than six decades, the Michigan State University Libraries Stephen O. Murray and Keelung Hong Special Collections (MSU) has sought to share these epic life stories through the extensive cookery and foodways collections. This article examines the depth and breadth of the cookery and foodways collections which began as a working collection for undergraduate students and has ballooned to more than 40,000 titles with the 2021 acquisition of the cookery collection of Sheila and Marilynn Brass. Subsequent access through open digital sites provides a landmark resource on culinary history. Overall, the development of this curated collection materials has resulted in a more dynamic and diverse collection for all users.

Application of a UV nanosecond laser to the rapid and direct photothermal activation of Cu-BTC metal–organic frameworks

Activating metal–organic frameworks (MOFs) to create open coordination sites is crucial for exploiting the functions of MOFs. This study successfully demonstrates the direct activation of Cu-BTC crystals using rapid and efficient heat treatment assisted by a nanosecond pulse laser. Localized thermal energy was irradiated to the surfaces of the MOFs through a photothermal process, which rapidly and effectively removed solvent residues within the structures of the MOFs. The Cu-BTC crystals synthesized through the solvothermal method were activated through a photothermal process, without inducing any structural damage, by irradiating with the second harmonic of a Nd3+:Y3Al5O12 laser with a wavelength of 355 nm. This process occurred most efficiently without any structural collapse at 30 mJ/cm2, and the residues within the MOFs were removed through the photothermal process within approximately 5 min. Thus, the study offers a novel design strategy involving the rapid activation of MOFs.

Solid waste open dumpsite mining in India and sustainable deployment through circular economy

ABSTRACT There are about 3159 open dump sites in India, which cause severe environmental pollution and are a danger to public health. This study demonstrates that the embedded resources in these dumpsites can be recovered profitably. The paper surveys the excavation, segregation, re-cycling and re-use of an open dumpsite containing legacy waste, at a cost of 8 $/m3 of rubbish, recovered, incinerable and inert fractions. A land reclamation of 3.16 ha yielding 1048 tonnes of refuse-derived fuel was achieved. This study demonstrates that dumpsite mining can be profitable while preventing the environmental hazards caused by existing waste dump sites in most Indian cities.

Introducing Noble Gas as Space Holder under High Pressure to Design Porous Titanium Carbides with Open Metal Sites for Hydrogen Storage at Near-Ambient Conditions.

It has been a long-standing challenge to develop high-performance solid-state hydrogen storage materials operated under near-ambient conditions. In this work, we propose a new strategy of using noble gases for space holding to design porous titanium carbides with abundant open metal sites for hydrogen storage. By using machine learning and graph theory-assisted universal structure searching methods, we obtain 28 porous titanium carbides from three precursors (TiC dimer, C atom, and Kr atom) under 30 GPa of pressure. The stability and hydrogen storage performance of the resulting structures are further assessed and validated through density function theory and grand canonical Monte Carlo simulations with a DFT-fitted force field. Finally, p-TiC2 is identified as a promising quasi-molecular hydrogen storage material with capacity of 4.0 wt % and 106.0 g/L at 230 K and 16 bar.

A Chemically Robust 2D Ni-MOF as an Efficient Heterogeneous Catalyst for One-Pot Synthesis of Therapeutic and Bioactive 2-Amino-3-Cyano-4H-Pyran Derivatives.

Despite possessing numerous catalytic advantages of MOFs, developing 2D frameworks having excellent chemical stability along with new catalytic properties, remains a grand challenge. Herein, by employing a mixed ligand synthetic approach, we have constructed a 2D Ni-MOF, IITKGP-52, which exhibits excellent framework robustness in open air, water, as well as over a wide range of pH solutions (2-12). Benefitting from its robustness and abundant Lewis acidic open metal sites, IITKGP-52 is explored in catalyzing the heterogeneous three-component condensation reaction for the tandem synthesis of bioactive 2-amino-3-cyano-4H-pyran derivatives with low catalytic loading, greater compatibility for a wide range of substrates, excellent recyclability and superior catalytic efficiency than the previously employed homo and heterogeneous systems. IITKGP-52inaugurates the employment of MOF-based catalysts for one-pot synthesis of therapeutic and bioactive 2-amino-3-cyano-4H-pyran derivatives.

Evaluating environmental and economic benefits of using biochar in concrete: A life cycle assessment and multi-criteria decision-making framework

While several studies have assessed the applicability of using biochar in cement mortar and concrete preparation based on the best mechanical properties, this evaluation method should be improved to consider the techno-economic feasibility and the environmental impacts. To address this research gap, this study attempts to compare between the conventional concrete with 100 % cement as a control mixture (CM) and dumping of sludge into open sites (scenario_1), and biochar concrete using alum sludge biochar (ASB) as a partial cement replacement (scenario_2), regarding the project life cycle assessment (LCA) and economic feasibility. A multi-criteria decision-making (MCDM) framework was used to assign scores to the environmental LCA criteria, material functional performance tests, and cost considerations. The two scenarios were arranged in SimaPro LCA software, and then the different criteria were analyzed using the TOPSIS technique to choose the best alternative. The study demonstrated that the functional properties of the cement mixture containing 5 % of ASB were almost comparable to those of CM, owing to the presence of significant amounts of quartz (SiO2) that bonded strongly with cement molecules. This ASB mixture also enjoyed the least environmental impacts, reducing the global warming potential (GWP) by 32.2 % compared with the CM scenario. The scores of the “Cost” criterion, considering the price of raw materials, energy, production, and maintenance, for the two alternatives were almost comparable, depicting that scenario_2 achieved the highest closeness coefficient of 0.95 in the MCDM overall scoring. This study concluded that biochar could be incorporated into cementitious mixtures due to its lower impact on global warming to maintain a sustainable and economic concrete industrial strategy. Future studies should focus on studying the long-term durability of the biochar-based concrete mixtures and integrating into the MCDM strategy; in addition, determining the correlation between sustainable construction implementation and sustainable development goals achieved.

Electrochemical Synthesis of Metal‐Organic Frameworks Based on Zinc(II) and Mixed Ligands Benzene‐1,4‐Dicarboxylate (BDC) and 4,4′‐Bipyridine (Bpy) and its Preliminary Study on CO2 Adsorption Capacities

AbstractEfficient and environmentally friendly synthesis methods for metal‐organic frameworks (MOFs) have emerged as a compelling topic in the organometallic field. In this study, we successfully electro‐synthesized a MOF based on mixed ligands, benzene‐1,4‐dicarboxylate (BDC) and 4,4′‐bipyridine (Bpy), denoted as MOF‐508b, and investigated its CO2 adsorption capacity, comparing it with that of Zn‐BDC and Zn‐Bpy coordination polymers. Unlike the circular shapes of Zn‐BDC and Zn‐Bpy, MOF‐508 adopts a three‐dimensional structure upon binding with the pillar ligand, featuring mesoporous pore sizes. MOF‐508b demonstrates superior stability at room temperature, exhibiting a thermal stability of 400 °C. The CO2 capture potential of the materials was assessed under low‐pressure conditions at room temperature. The pillared layer of MOF‐508b results in the reduction of open metal sites, facilitating the binding of active CO2 through coordination, thereby influencing its optimum CO2 adsorption capacity (2.51 mmol g−1), which was found to be lower than that of Zn‐Bpy (3.83 mmol g−1) and Zn‐BDC (4.46 mmol g−1). The adsorption mechanism on MOF‐508b follows the Weber‐Morris model, emphasizing diffusion within particles over direct attachment to the material surface.

Novel Bacterial Consortium for Mitigation of Odor and Enhance Compost Maturation Rate of Municipal Solid Waste: A Step Toward a Greener Economy

Composting is an integral component of sustainable Municipal Solid Waste (MSW) management within the circular bio-economy platform. However, it faces challenges due to malodorous emissions that impact environmental and societal equilibrium. The present study aims to minimize odorous emissions and expedite compost maturation using a novel, efficient microbial consortium. Bacteria sourced from open dump sites in Sri Lanka were carefully screened based on concurrent enzyme production. Five developed consortia were tested for their performance in reducing malodors during the composting process of MSW. Consortium No. 5 (C5), comprised of Bacillus haynesii, Bacillus amyloliquefaciens, and Bacillus safensis, demonstrated outstanding performance with a significant (p < 0.05) reduction in odorous emissions. Additionally, consortium C5 exhibited impressive control over gas emissions, maintaining VOC, CH4, NH3, and H2S concentrations within ranges of 0.5-6 ppm, 0.5-0.8 ppm, 0.3-0.5 ppm, and 0.5-0.6 ppm, respectively, compared to control concentrations of 4.5-10.2 ppm, 0.5-5.5 ppm, 0.3-5.5 ppm, and 0.5-6.4 ppm, respectively. Additionally, comprehensive Electronic nose (E-nose) analysis substantiated C5’s efficiency in attenuating Methane-Aliphatic compounds, Sulfur and Aromatic compounds, along with low-polarity aromatic and alkane compounds, all with statistical significance (p < 0.05). Further, the developed consortium could reduce the composting time from 110 ± 10 days to 17 ± 3 days, offering a sustainable solution for global MSW management.

Investigating the Structure of Defects in Heterometallic Zeolitic Imidazolate Frameworks ZIF-8(Zn/Cd) and Its Interaction with CO2 Using First-Principle Calculations

Inducing defect in metal-organic frameworks (MOFs) is one of the strategies to modify the structure and properties of this functional material. Defect may occur in a pristine MOF due to missing organic linkers, metal centres and/or other structural behaviours. In this study, the structure of defects in multicomponent MOFs especially heterometallic MOFs of zeolitic imidazolate framework (ZIF-8(Zn/Cd)) was examined to unveil the possible preference defect formation due to missing 2-methylimidazolate (MeIm) and metal centres of Cd2+ and Zn2+. Assuming defect formation due to the reaction between ZIF-8(Zn/Cd) and water, MeIm linker removal is energetically lower than removing metal centres of either Cd2+ or Zn2+. But, the MeIm linker is easier to be removed when it is connected to Cd2+ (Cd-MeIm-Cd) than when it is connected to Zn2+ (Zn-MeIm-Zn). Defect in ZIF-8(Zn/Cd) affects the band gap energy to give slightly lower value than it in pristine ZIF-8(Zn/Cd). Non-covalent interaction (NCI) and interaction region indicator (IRI) analyses were also performed to indicate possible intermolecular forces such as van der Waals and attractive forces present in non-defective and defective ZIF-8(Zn/Cd). The presence of defects in mixed-metal ZIF-8(Zn/Cd) was also tested for its potential use on CO2 adsorption. The interaction energy of CO2 inside defective ZIF-8(Zn/Cd) indicates an exothermic behaviour where CO2 molecule has a preference to be adsorbed inside the framework. This is especially when the capping agents at the defective ZIF-8(Zn/Cd) sites are removed to give open metal sites. This study provides insight how defects in multicomponent MOFs might presence affecting the structural and properties changes. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).