Proton Conducting Metal-Organic Frameworks (MOFs) via Post Synthetic Transmetallation and Water Induced Structural Transformations.

Post Synthetic Modification (PSM) of Metal-Organic Frameworks (MOFs) is a crucial strategy for developing new MOFs with enhanced functional properties compared to their parent one. PSM can be accomplished through various methods:1) modification of organic linkers; 2) exchange of metal ions or nodes; and 3) inclusion or exchange of solvent/guest molecules. Herein, PSM of bimetallic and monometallic MOFs containing biphenyl dinitro-tetra-carboxylates (NCA) are demonstrated. The tetra carboxylate NCA, produces monometallic Cd-MOF-1 and Cu-MOF-1 and bimetallic CoZn-MOF in solvothermal reactions with the corresponding metal salts. The CoZn-MOF undergoes post-synthetic transmetallation with Cd(NO3)2 and Cu(NO3)2 in aqueous solution to yield Cd-MOF-2 and Cu-MOF-2, respectively. Additionally, green crystals of Cu-MOF-1 found to undergo a single-crystal-to-single-crystal (SCSC) transformation to blue crystals of Cu-MOF-3 upon dipped into water at room temperature. These MOFs demonstrate notable proton conductivities ranging from 10-3 to 10-4 S cm-1 under variable temperatures and humidity levels. Among them, Cu-MOF-3 achieves the highest proton conductivity of 1.36×10-3 S cm-1 at 90 °C and 98 % relative humidity, attributed to its continuous and extensive hydrogen bonding network, which provides effective proton conduction pathways within the MOF. This work highlights a convenient strategy for designing proton-conducting MOFs via post-synthetic modification.

Bimetallic Organic Frameworks via In Situ Solvothermal Sol-Gel-Crystal and Sol-Crystal Transformation as Durable Electrocatalysts for Oxygen Reduction Reaction.

The in situ solvothermal conversion of metal-organic gels (MOGs) to crystalline metal-organic frameworks (MOFs) represents a versatile and ingenious strategy that has been employed for the synthesis of MOF materials with specific morphologies, high yield, and improved functional properties. Herein, we have adopted an in situ solvothermal conversion of bimetallic MOGs to crystalline bimetallic MOFs with the aim of introducing a redox-active metal heterogeneity into the monometallic counterpart. The formation of bimetallic NiZn-MOF and CoZn-MOF via in situ solvothermal sol-gel-crystal and sol-crystal transformation is found to depend on the solvent systems used. The sol-to-gel-to-crystal transformation of NiZn-MOF via the formation of NiZn-MOG is found to occur through the gradual disruption of gel fibers leading to subsequent formation of microcrystals and single crystals of NiZn-MOF. These bimetallic MOFs and MOGs serve as promising electrocatalysts for oxygen reduction reaction (ORR) with an excellent methanol tolerance property, which can be attributed to the enhanced mass and charge transfer, higher oxygen vacancies, and bimetallic synergistic interactions among the heterometals. This work demonstrates a convenient strategy for producing bimetallic MOGs to MOFs through the introduction of a redox-active metal heterogeneity in the inorganic hybrid functional materials for fundamental and applied research. Our results connect MOGs and MOFs which have been regarded as having opposite physical states, that is, soft vs hard, and provide promising structural correlation between MOGs and MOFs at the molecular level.

In situ conversion of a MOG to a crystalline MOF: a case study on solvent-dependent gelation and crystallization.

Herein, we report in situ transformation of a metal-organic gel (MOG) to a crystalline metal-organic framework (MOF) and solvent-dependent gelation/crystallization via solvothermal reactions of a tetracarboxylic acid, namely 4,4'-dinitro-2,2',6,6'-tetracarboxybiphenyl, and ZnSO4. The results provide structural insights into MOGs at the molecular level and also help in the synthesis of crystalline MOFs that are otherwise difficult to obtain.

In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy.

The design of highly efficient, cost-effective non-noble metal-based electrocatalysts with superior stability for overall water splitting (OWS) reactions is of great importance as well as of immense challenge for the upcoming sustainable and green energy conversion technologies. Herein, a convenient and simple in situ solvothermal method has been adopted to fabricate a self-supported, binder-free 3D electrode (Mn-MOF/NF) by the direct growth of a newly synthesized carboxylate-based pristine Mn(II)-metal-organic framework (Mn-MOF) upon the conducting substrate nickel foam (NF). The binder-free Mn-MOF/NF electrode exhibits excellent performances toward OWS with ultralow overpotentials of 280 mV@20 mA cm-2 for the oxygen evolution reaction (OER) and 125 mV@10 mA cm-2 for the hydrogen evolution reaction (HER) with remarkable durability. Mn-MOF/NF can also attain a current density of 10 mA cm-2 with a low cell voltage of 1.68 V in a 0.1 M KOH solution in a two-electrode system for OWS. The direct growth of nonconducting electroactive Mn-MOF materials upon conducting substrate NF provides an excellent mass transport of the electrolyte with a relatively low contact resistance due to the strong catalyst-substrate contact and enhances the efficient electron transport for OWS. The redox chemical etching of the self-sacrificial substrate NF during solvothermal synthesis introduces redox-active Ni2+ in Mn-MOF/NF. Thus, the excellent OWS electrocatalytic activity can mainly be attributed to the bimetallic synergistic collaboration of the two redox active metal centers (Mn2+ and Ni2+) along with the excellent support surface of NF, which provides a high specific surface area and maximum utilization of the electroactive metal ion sites by preventing the self-aggregation of the active sites. The Mn-MOF/NF electrode also exhibits superb stability and durability for a prolonged time throughout the multiple cycles of full water splitting reactions. Therefore, this work elucidates a convenient and smart approach for constructing MOF-based bifunctional electrocatalysts for OWS.

Molecular Heterogeneity of Cervical Cancer Among Different Ethnic/Racial Populations.

The study aimed to find differential gene mutation profile and gene expression status among different ethnic/racial human populations relevant for cervical cancer pathogenesis. The study was based on freely available datasets of The Cancer Genome Atlas (TCGA) of cervical cancer samples in Genomic Data Commons (GDC) data portal. We identified that choline metabolism in cancer and Ras signaling pathways were significantly associated with the Hispanic and Latino group of cervical cancer patients. In these pathways, mutations in the PIK3CA gene, especially E545K, were significantly associated with the Hispanic and LATINO group. We found that AFF3 gene mutation was associated with downregulation of its expression only among the White racial category of cervical cancer cases. Additionally, hypomethylation of the CpG position in the S shore region of the PM20D1 gene was associated with overexpression among the Asian category of cervical cancer cases. Heterogeneity of the molecular profile of AFF3 and PM20D1 gene among racial groups reflects the potential of differential targeted therapy of cervical cancer.

The influence of IL1RN VNTR polymorphism on HPV infection among some tribal communities.

Persistent infection of human Papillomavirus is the main etiological factor for cervical cancer. Austro-Asiatic tribes are early settlers in India and they have unique genetic variations compared to other people. The immunological response is crucial for the prevention of viral associated diseases. Interleukin-1 receptor antagonist (IL-1RN) is considered being an important regulator of host immune surveillance. A total of 45 Santali tribal women and 10 Kora tribal women were enrolled in the present study and demographic variables were recorded during collection. Genomic DNA was extracted from cervical/vaginal swab samples. IL1RN variable number of tandem repeats (VNTR) polymorphisms and HPV types were determined by PCR-based assay. Association between IL1RN VNTR polymorphisms with the HPV infections among the tribal communities was determined by logistic regression analysis. HPV18 prevalence was significantly higher among tribal women. We observed that the polymorphism A2*A2 (p = 0.022; odds ratio [OR] (95% confidence interval [CI]) = 0.16 (0.03-0.86)] were more resistant to oncogenic HPV infection. Use of oral contraceptives was associated with higher relative risk (p = 0.008; OR [95% CI] = 5.39 [1.47-19.8]) for oncogenic HPV18 positivity among the tribal women. The A2 allele homozygosity of IL1RN VNTR was identified to be associated with the protection from oncogenic HPV infection among various tribal communities of West Bengal and therefore may be a useful marker of host immune response among them.

Metal-organic frameworks as proton conductors: strategies for improved proton conductivity.

Recent studies on proton conductivity using pristine MOFs and their composite materials have established an outstanding area of research owing to their potential applications for the development of high performance solid state proton conductors (SSPCs) and proton exchange membranes (PEMs) in fuel cells (FCs). MOFs, as crystalline organic and inorganic hybrid materials, provide a large number of degrees of freedom in their framework composition, coordination environment, and chemically functionalized pores for the targeted design of improved proton carriers, functioning over a wide range of temperature and humidity conditions. Herein, our efforts have been emphasized on fundamental principles and different design strategies to achieve enhanced proton conductivity with appropriate examples. We also have discussed the modification mechanism of MOF-composite materials and mixed matrix membranes for commercial applications in FCs. Thus, this review aims to direct readers' attention towards the design strategies and structure-property relationship for proton transport in MOFs.

Coordination polymers as heterogeneous catalysts in hydrogen evolution and oxygen evolution reactions.

The efficiency of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in the process of electrochemical water oxidation will determine the competence for mass distributions of sustainable energy conversion technologies in the future. Recently, coordination polymers (CPs)/metal-organic frameworks (MOFs) have emerged as desirable hybrid materials for catalysing electrochemical energy conversion processes due to their unique advantages, such as crystalline porous structure, high surface area, and diverse and tunable chemical components. This feature article briefly summarizes the recent part of the fast growing literature on electrocatalysis by pristine MOF/CPs, MOF composites, as well as post-synthetically modified materials for HER, OER and overall water splitting reactions. The article highlights the contributions of various authors in this area and aims to provide a consolidated idea regarding the engineering strategies and composition-structure-activity relationships of these pristine CP based materials for such electrocatalytic applications.

2D MOFs with Ni(II), Cu(II), and Co(II) as Efficient Oxygen Evolution Electrocatalysts: Rationalization of Catalytic Performance vs Structure of the MOFs and Potential of the Redox Couples.

Earth-abundant transition-metal-based metal-organic frameworks (MOFs) are of immense interest for the development of efficient and durable heterogeneous water splitting electrocatalysts. This repot explores the design of two-dimensional (2D) MOFs with redox-active metal centers (Ni(II), Co(II), and Cu(II)) containing two types of electron-rich linkers such as bis(5-azabenzimidazole), linear L1 and angular L2, and aromatic dicarboxylates. The electron-rich linkers are considered to stabilize the higher oxidation state of the redox-active metal centers in the course of the electrocatalytic oxygen evolution reaction (OER) process. The 2D MOFs of L1 and L2 with Co(II) (1 and 3) and Ni(II) (2 and 4) have been produced via the conventional hydrothermal synthesis, while the MOFs of Cu(II) (Cu@1 and Cu@3) are obtained by the postsynthetic transmetallation reaction of MOFs 1 and 3. The electrocatalytic OER activities of the six MOFs have been studied to explore the influence of the redox potential of the transition-metal quasi-reversible couples and the coordination environment around the redox-active metal centers in the electrocatalytic activity. The lowest overpotential of 370 mV exhibited by MOF 2 with the highest current density and TOF value indicates the importance of the presence of coordinated water molecules and the lowest redox potential value of the most favorable quasi-reversible couple Ni+2/Ni+3. These catalysts exhibit a remarkable stability up to 1000 OER cycles. These studies pave the way for the design of MOF materials toward the development of a promising heterogeneous OER electrocatalyst.