Cancer care continuum at a tertiary care centre in India during the Covid-19 pandemic and nationwide lockdown: Healthcare delivery through telemedicine.

Background The Covid-19 pandemic and subsequent lockdown in India caused disruptions in cancer treatment due to the restriction on movement of patients. We aimed to maintain continuity in cancer treatment during the lockdown through teleconsultations. We tried to reach out to our patients using telephonic consultations by establishing a Teleconsult Centre facility run by a team of doctors and patient navigators. Methods We telephonically contacted all patients who had outpatient appointments from 23 March to 30 April 2020 at our centre through the Teleconsult Centre to understand their current circumstances, feasibility of follow-up, local resources and offered best possible alternatives to continue cancer treatment, if required. Results Of the 2686 patients scheduled for follow-up during this period, we could contact 1783 patients in 9 working days. Through teleconsultations, we could defer follow-ups of 1034 patients (57.99%, 95% confidence interval [CI] 55.6%-60.3%), thus reducing the need for patients to travel to the hospital. Change in systemic therapy was made in 75 patients (4.2%, 95% CI 3.3%-5.2%) as per the requirements and available resources. Symptoms suggestive of disease progression were picked up in 12 patients (0.67%, 95% CI 0.35%-1.17%), who were advised to meet local physicians. Conclusion Our study suggests that the majority of patients on follow-up can be managed with teleconsultation in times of crisis. Teleconsultation has the potential of being one of the standard methods of patient follow-up even during periods of normalcy.

An Ultra-Microporous Metal-Organic Framework with Exceptional Xe Capacity.

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal-organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni-MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO2 . Further 129 Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.

Facile Exfoliation of Single-Crystalline Copper Alkylphosphates to Single-Layer Nanosheets and Enhanced Supercapacitance.

Manipulation of low-dimensional solids through soft chemical routes is an elegant way to realize newer materials. A new family of single-crystalline transition-metal layered organophosphates, with about 185 000 metal phosphate layers in a single crystal, can be exfoliated to a single-layer nanosheet by a facile and rapid solvent assisted method. This exfoliation aids the formation of high-surface-area pyrophosphates with enhanced supercapacitance.

Anthracene-Resorcinol Derived Covalent Organic Framework as Flexible White Light Emitter.

The ordered modular structure of a covalent organic framework (COF) facilitates the selective incorporation of electronically active segments that can be tuned to function cooperatively. This designability inspires developing COF-based single-source white light emitters, required in next-generation solid-state lighting. Here, we present a new anthracene-resorcinol-based COF exhibiting white light emission. The keto-enol tautomers present in the COF give rise to dual emission, which can be tuned by the O-donor and N-donor solvents. Importantly, when suspended in a solid polymer matrix, this dual emission is retained as both tautomers coexist. A mere 0.32 wt % loading of the COF in poly(methyl methacrylate) (PMMA) gives a solvent-free film with intense white light emission (CIE coordinates (0.35, 0.36)). From steady-state and time-resolved studies, the mechanism of the white light emission has been unambiguously assigned to fluorescence, with the blue emission originating from the π-stacked columns of anthracene, and the mixture of red and green from the keto-enol tautomerized resorcinol units. The study introduces the COF as a new class of readily processable, single-source white light emitter.

Highly Stable COF-Supported Co/Co(OH)2 Nanoparticles Heterogeneous Catalyst for Reduction of Nitrile/Nitro Compounds under Mild Conditions.

Ordered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF-Co/Co(OH)2 composite containing about 16 wt% of <6 nm sized Co/Co(OH)2 nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H2 from readily available, safe, and cheap NaBH4 . Furthermore, the released H2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF "by choice" is built from "methoxy" functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP-COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst - a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.

Preferential Adsorption of CO2 in an Ultramicroporous MOF with Cavities Lined by Basic Groups and Open-Metal Sites.

Here, we present a new ultramicroporous Cu2 paddlewheel based MOF. This ultramicroporous MOF has most of the features such as porosity (BET surface area = 945 m2/g), CO2 capacity (3.5 mmol/g at ambient temperature and pressure), CO2/N2 selectivity (sCO2/N2 = 250), and fast CO2 diffusion kinetics ( Dc = 2.25 × 10-9 m2/s), comparable to some of the other high-performing ultramicroporous MOFs, with strong binding sites. Typically, such MOFs exhibit strong CO2-framework interactions (evidenced from a heat of adsorption ≥ 38 kJ/mol). However, the MOF explained here, despite having channels lined by the amine and the open-metal sites, possesses only a moderate CO2-framework interaction (HOA = 26 kJ/mol). Using periodic DFT, we have probed this counterintuitive observation.

Ultralow Parasitic Energy for Postcombustion CO2 Capture Realized in a Nickel Isonicotinate Metal-Organic Framework with Excellent Moisture Stability.

Metal-organic frameworks (MOFs) have attracted significant attention as solid sorbents in gas separation processes for low-energy postcombustion CO2 capture. The parasitic energy (PE) has been put forward as a holistic parameter that measures how energy efficient (and therefore cost-effective) the CO2 capture process will be using the material. In this work, we present a nickel isonicotinate based ultramicroporous MOF, 1 [Ni-(4PyC)2·DMF], that has the lowest PE for postcombustion CO2 capture reported to date. We calculate a PE of 655 kJ/kg CO2, which is lower than that of the best performing material previously reported, Mg-MOF-74. Further, 1 exhibits exceptional hydrolytic stability with the CO2 adsorption isotherm being unchanged following 7 days of steam-treatment (>85% RH) or 6 months of exposure to the atmosphere. The diffusion coefficient of CO2 in 1 is also 2 orders of magnitude higher than in zeolites currently used in industrial scrubbers. Breakthrough experiments show that 1 only loses 7% of its maximum CO2 capacity under humid conditions.

Translation and pilot validation of Hindi, Marathi, and Bangla translation of quality of life EORTC module (QLQ-SH-22) for assessing sexual health-related quality of life.

AIM: To translate and validate the European Organization for Research and Treatment for Cancer (EORTC) module for assessing the sexual health-related quality of life in cancer patients (QLQ-SH22), in Hindi, Marathi, and Bangla languages for clinical use. METHODS AND RESULTS: The EORTC QLQ-SH-22 was translated into Hindi, Marathi, and Bangla by adopting standard guidelines given by EORTC. Initially, the original questionnaire was forward translated by two separate translators, followed by the reconciliation of the forward translations by a third person. This was followed by two back translations of the reconciled version into English by two other translators. These back-translated questions were then compared with the original EORTC questions for accuracy, and once acceptable, a preliminary questionnaire was prepared in all three languages. These questionnaires were then pilot tested with 30 patients (10 for each language) diagnosed with any of the cancers in the pelvic region who are expected to be at risk of sexual quality of life due to tumor or treatment like pelvic radiotherapy. Participated patients had never seen or filled the questionnaire before, each patient was interviewed after filling the questionnaire for difficulty in answering, confusion, difficulty understanding, or if any of the questions were upsetting and if patients would have asked the question differently. RESULTS: None of the patients reported any changes or suggestions for all the three translations. All the translated questionnaires were well understood by all the patients. Pilot testing reports were sent to EORTC. After reviewing the entire report of Hindi, Marathi, and Bangla translations, these questionnaires were approved by the EORTC translation unit. The questionnaires are reliable with Cronbach's α for Hindi, Marathi, and Bangla being 0.69, 0.66, and 0.86, respectively. CONCLUSION: The final Hindi, Marathi, and Bangla translations of SH 22 have been approved by the EORTC and can be used to assess the sexual health of cancer patients in routine oncology practices and/or clinical studies.

Translation and Pilot Validation of Hindi, Marathi, and Bangla Translation of Quality-of-Life EORTC Radiation Proctitis Module (PRT-20) for Routine Clinical Use.

Rahul Krishnatry The aim of this study was to translate and validate the European Organization for Research and Treatment for Cancer (EORTC) "Radiation Proctitis" (PRT-20) module in Hindi, Marathi, and Bangla languages. The EORTC PRT-20 was translated into Hindi, Marathi, and Bangla using EORTC guidelines. Two separate translators first translated the original questionnaire into the three regional languages, following which a reconciled forward translation was compiled. This reconciled version in each language was then back-translated into English by two other translators. This back-translated version was then compared with the original the EORTC questionnaire for correctness, and the preliminary questionnaires were formed in all three languages. The EORTC translation unit approved the questionnaires. The preliminary questionnaires were administered to 30 patients (10 for each language) diagnosed with rectal or anal canal cancer who had received pelvic radiotherapy and were at risk of developing PRT. None of the patients had seen the questionnaire before. After filling out the questionnaire, each patient was interviewed for difficulty in answering, confusion, understanding, or if any of the questions were upsetting and if patients would have asked the question differently. No changes were suggested for Marathi and Bangla translations. Two modifications were suggested in the Hindi translation, which was then retested in five patients and finalized. All the suggestions were incorporated into the preliminary questionnaires, which were sent back to the EORTC for final approval. After reviewing the entire report of pilot testing for the translated quality-of-life questionaire-PRT-20 in three languages, it was approved by the EORTC translation unit. The translated questionnaires were reliable, with Cronbach α values of 0.767, 0.799, and 0.898 for Hindi, Marathi, and Bangla, respectively. The Hindi, Marathi, and Bangla translations of PRT-20 have been approved by the EORTC and can be used in routine clinical practice.

A Scalable Robust Microporous Al-MOF for Post-Combustion Carbon Capture.

Herein, a robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, (MIL, AP: Institute Lavoisier and Ambient Pressure synthesis, respectively) is reported, which exhibits high CO2 uptake (1.9 mmol g-1 at 0.1 bar, 298 K). In situ Synchrotron X-ray diffraction measurements together with Monte Carlo simulations reveal that this structure offers a favorable CO2 capture configuration with the pores being decorated with a high density of µ2-OH groups and accessible aromatic rings. Meanwhile, based on calculations and experimental evidence, moderate host-guest interactions Qst (CO2) value of MIL-120(Al)-AP (-40 kJ mol-1) is deduced, suggesting a relatively low energy penalty for full regeneration. Moreover, an environmentally friendly ambient pressure green route, relying on inexpensive raw materials, is developed to prepare MIL-120(Al)-AP at the kilogram scale with a high yield while the Metal- Organic Framework (MOF) is further shaped with inorganic binders as millimeter-sized mechanically stable beads. First evidences of its efficient CO2/N2 separation ability are validated by breakthrough experiments while operando IR experiments indicate a kinetically favorable CO2 adsorption over water. Finally, a techno-economic analysis gives an estimated production cost of ≈ 13 $ kg-1, significantly lower than for other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate as an adsorbent for industrial-scale CO2 capture processes.

Exploring Texture Analysis to Optimize Bladder Preservation in Muscle Invasive Bladder Cancer.

PURPOSE: To explore if texture analysis of Muscle Invasive Bladder Cancer (MIBC) can aid in better patient selection for bladder preservation. METHODS: Pretreatment noncontrast CT images of 41 patients of MIBC treated with bladder preservation were included. The visible tumor was contoured on all slices by a single observer. The primary endpoint was to identify texture parameters associated with disease recurrence posttreatment. The secondary endpoints included intra and interobserver variability, single and multislice analysis, and differentiating the texture features of normal bladder and tumor. For interobserver variability of bladder tumor texture features, 3 observers contoured the visible tumor on all slices independently. Observer 1 contoured again at an interval of 1 month for intraobserver variability. RESULTS: The median follow-up was 30 months with 12 patients having a recurrence. In the primary endpoint analysis, the mean of the pixels at Spatial Scaling Filter (SSF) 2 for the no recurrence group and recurrence group was 6.44 v 13.73 respectively (P = .031) and the same at SSF-3 was 11.95 and 22.32 respectively (P = .034). The texture features that could significantly differentiate tumor and normal bladder were mean, standard deviation and kurtosis of the pixels at SSF-2 and entropy and kurtosis of the pixels at SSF-3. Overall, there was an excellent intra and interobserver concordance in texture features. Only multislice analysis and not single-slice could differentiate recurrence and no recurrence posttreatment. CONCLUSIONS: Texture analysis can be explored as a modality for patient selection for bladder preservation along with the established clinical parameters to improve outcomes.

Hydroxide ion-conducting viologen-bakelite organic frameworks for flexible solid-state zinc-air battery applications.

Adaptable polymer-based solid-state electrolytes can be a game-changer toward safe, lightweight flexible batteries. We present a robust Bakelite-type organic polymer covalently decked with viologen, triazine, and phenolic moieties. Its flexible structure with cationic viologen centers incorporates counter-balancing free hydroxide ions into the polymeric framework. By design, the aromatic groups and heteroatoms in the framework can be activated under an applied potential to prompt a push-pull drive, setting off the towing of hydroxide ions via weak electrostatic, van der Waals, and hydrogen-bond interactions. The frontier orbitals from a DFT-modeled structure certify this. The hydroxyl-polymer requires minimal KOH wetting to maintain a humid environment for Grotthuss-type transport. The hydroxide ion conductivity reaches a value of 1.4 × 10-2 S cm-1 at 80 °C and 95% RH, which is retained for over 15 h. We enhanced its practical utility by coating it as a thin solid-state separator-cum-electrolyte on readily available filter paper. The composite exhibits a conductivity of 4.5 × 10-3 S cm-1 at 80 °C and 95% RH. A zinc-air battery (ZAB) constructed using this polymer-coated paper as electrolyte yields a maximum power density of 115 mW cm-2 and high specific capacitance of 435 mA h g-1. The power density recorded for our ZAB is among the best reported for polymer electrolyte-based batteries. Subsequently, the flexible battery fabricated with IISERP-POF11_OH@FilterPaper exhibits an OCV of 1.44 V, and three batteries in series power a demo traffic signal. To underscore the efficiency of hydroxide ion transport through the complex multifunctional backbone of the polymer, we calculated the diffusion coefficient for OH- (Exp: 2.9 × 10-5 cm2 s-1; Comp. 5.2 × 10-6 cm2 s-1) using electrochemical methods and MD simulations. Climbing-edge NEB calculations reveal a large energy barrier of 2.11 eV for Zn2+ to penetrate the polymer and identify hydroxide ions within the polymer, suggesting no undesirable Zn2+ crossover. Our findings assert the readily accessible C-C-linked cationic polymer's capacity as a solid-state electrolyte for ZABs and any anion-conducting membrane.

Nanopores of a Covalent Organic Framework: A Customizable Vessel for Organocatalysis.

Covalent organic frameworks (COFs) as crystalline polymers possess ordered nanochannels. When their channels are adorned with catalytically active functional groups, their highly insoluble and fluffy powder texture makes them apt heterogeneous catalysts that can be dispersed in a range of solvents and heated to high temperatures (80-180 °C). This would mean very high catalyst density, facile active-site access, and easy separation leading to high isolated yields. Different approaches have been devised to anchor or disperse the catalytic sites into the nanospaces offered by the COF pores. Such engineered COFs have been investigated as catalysts for many organic transformation reactions. These range from Suzuki-Miyaura coupling, Heck coupling, Knoevenagel condensation, Michael addition, alkene epoxidation, CO2 utilization, and more complex biomimetic catalysis. Such catalysts employ COF as a "passive" support that merely docks catalytically active inorganic clusters, or in other cases, the COF itself participates as an "active" support by altering the electronics of the inorganic catalytic sites through the redox activity of its framework. Even more, catalytic organic pockets or metal complexes have been directly tethered to COF walls to make them behave like single-site organocatalysts. Here, we have listed most COF-based organic transformations by categorizing them as metal-free non-noble-metal@COF and noble-metal@COF. The initial part of this review highlights the advantages of COFs as a component of a heterogeneous catalyst, while the latter part discusses all of the current literature on this topic.

Coordination Flexibility Aided CO2 -specific Gating in an Iron Isonicotinate MOF.

Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal-organic framework (MOF), (Fe(4-PyC)2 ⋅ (OH). The framework showed CO2 -specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF's physisorptive porosity towards CO2 , CH4 , and N2 was investigated; it adsorbed only CO2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO2 pressure opening the gate for a sharp increase in CO2 uptake at 333 mmHg (At 298 K, the CO2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF's potential for CO2 /N2 and CO2 /CH4 gas separation aided by this gating. IAST model reveals that the CO2 /N2 selectivity jumps from 325 to 3131 when the gate opens, while the CO2 /CH4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M2+ -isonicotinate MOFs (M=Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.

Deciphering the Weak CO2···Framework Interactions in Microporous MOFs Functionalized with Strong Adsorption Sites-A Ubiquitous Observation.

Carbon capture from industrial effluents such as flue gas or natural gas mixture (cf. landfill gas), the primary sources of CO2 emission, greatly aids in balancing the environmental carbon cycle. In this context, the most energy-efficient physisorptive CO2 separation process can benefit immensely from improved porous sorbents. Metal organic frameworks (MOFs), especially the ultramicroporous MOFs, built from readily available small and rigid ligands, are highly promising because of their high selectivity (CO2/N2) and easy scalability. Here, we report two new ultramicroporous Co-adeninato isophthalate MOFs. They concomitantly carry basic functional groups (-NH2) and Lewis acidic sites (coordinatively unsaturated Co centers). They show good CO2 capacity (3.3 mmol/g at 303 K and 1 bar) along with high CO2/N2 (∼600 at 313 K and 1 bar and ∼340 at 303 K and 1 bar) selectivity, working capacity, and smooth diffusion kinetics (Dc = 7.5 × 10-9 m2 s-1). The MOFs exhibit good CO2/N2 kinetic separation under both dry and wet conditions with a smooth breakthrough profile. Despite their well-defined CO2 adsorption sites, these MOFs exhibit only a moderately strong interaction with CO2 as evidenced from their HOA values. This counterintuitive observation is ubiquitous among many MOFs adorned with strong CO2 adsorption sites. To gain insights, we have identified the binding sites for CO2 using simulation and MD studies. The radial distribution function analysis reveals that despite the amine and bare-metal sites, the pore size and the pore structure determine the positions for the CO2 molecules. The most favorable sites become the confined spaces lined by aromatic rings. A plausible explanation for the lack of strong adsorption in these MOFs is premised from these collective studies, which could aid in the future design of superior CO2 sorbents.

Ag Nanoparticles Supported on a Resorcinol-Phenylenediamine-Based Covalent Organic Framework for Chemical Fixation of CO2.

Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host-guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 Å). The heat of adsorption value (32 kJ mol-1 ) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (≈4-5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.

Water-stable Adenine-based MOFs with Polar Pores for Selective CO2 Capture.

Here, we report two novel water-stable amine-functionalized MOFs, namely IISERP-MOF26 ([NH2 (CH3 )2 ][Cu2 O(Ad)(BDC)]⋅(H2 O)2 (DMA), 1) and IISERP-MOF27 ([NH2 (CH3 )2 ]1/2 [Zn4 O(Ad)3 (BDC)2 ]⋅(H2 O)2 (DMF)1/2 , 2), which show selective CO2 capture capabilities. They are made by combining inexpensive and readily available terephthalic acid and N-rich adenine with Cu and Zn, respectively. They possess 1D channels decorated by the free amine group from the adenine and the polarizing oxygen atoms from the terephthalate units. Even more, there are dimethyl ammonium (DMA+ ) cations in the pore rendering an electrostatic environment within the channels. The activated Cu- and Zn-MOFs physisorb about 2.7 and 2.2 mmol g-1 of CO2 , respectively, with high CO2 /N2 and moderate CO2 /CH4 selectivity. The calculated heat of adsorption (HOA=21-23 kJ mol-1 ) for the CO2 in both MOFs suggest optimal physical interactions which corroborate well with their facile on-off cycling of CO2 . Notably, both MOFs retain their crystallinity and porosity even after soaking in water for 24 hours as well as upon exposure to steam over 24 hours. The exceptional thermal and chemical stability, favorable CO2 uptakes and selectivity and low HOA make these MOFs promising sorbents for selective CO2 capture applications. However, the MOF's low heat of adsorption despite having a highly CO2 -loving groups lined walls is quite intriguing.

Cu/Cu2O Nanoparticles Supported on a Phenol-Pyridyl COF as a Heterogeneous Catalyst for the Synthesis of Unsymmetrical Diynes via Glaser-Hay Coupling.

Covalent organic frameworks (COFs) are a new class of porous crystalline polymers with a modular construct that favors functionalization. COF pores can be used to grow nanoparticles (nPs) with dramatic size reduction, stabilize them as dispersions, and provide excellent nP access. Embedding substrate binding sites in COFs can generate host-guest synergy, leading to enhanced catalytic activity. In this report, Cu/Cu2O nPs (2-3 nm) are grown on a COF, which is built by linking a phenolic trialdehyde and a triamine through Schiff bonds. Their micropores restrict the nP to exceptionally small sizes (∼2-3 nm), and the pore walls decorated with strategically positioned hydrogen-bonding phenolic groups anchor the substrates via hydrogen-bonding, whereas the basic pyridyl sites serve as cationic species to stabilize the [CuclusterCl2]2- type reactive intermediates. This composite catalyst shows high activity for Glaser-Hay heterocoupling reactions, an essential 1,3-diyne yielding reaction with widespread applicability in organic synthesis and material science. Despite their broad successes in homocoupled products, preparation of unsymmetrical 1,3-diynes is challenging due to poor selectivity. Here, our COF-based Cu catalyst shows elevated selectivity toward heterocoupling product(s) (Cu nP loading 0.0992 mol %; turn over frequency: ∼45-50; turn over number: ∼175-190). The reversible redox activity at the Cu centers has been demonstrated by carrying out X-ray photoelectron spectroscopy on the frozen reactions, whereas the crucial interactions between the substrates and the binding sites in their optimized configurations have been modeled using density functional theory methods. This report emphasizes the utility of COFs in developing a heterogeneous catalyst for a truly challenging organic heterocoupling reaction.

Hyper-Cross-linked Porous Organic Frameworks with Ultramicropores for Selective Xenon Capture.

Exceptionally stable ultramicroporous C-C-bonded porous organic frameworks (IISERP-POF6, 7, 8) have been prepared using simple Friedel-Crafts reaction. These polymers exhibit permanent porosity with a Brunauer-Emmett-Teller surface area of 645-800 m2/g. Xe/Kr adsorptive separation has been carried out with these polymers, and they display selective Xe capture ( s(Xe/Kr) = 6.7, 6.3, and 6.3) at 298 K and 1 bar pressure. Interestingly, these polymers also show remarkable Xe/N2 ( s(Xe/N2) = 200, 180, and 160 at 298 K and 1 bar) and Xe/CO2 selectivity ( s(Xe/CO2) = 5.6, 7.4, and 5.6) for a 1:99 composition of Xe-N2/Xe-CO2. Selective removal of Xe at such low concentrations is extremely challenging; the observed selectivities are higher compared to those observed in porous carbons and metal-organic frameworks. Breakthrough studies were performed using the composition relevant to the nuclear off-gas mixture with the polymers, and we find that the polymers hold Xe for a longer time in the column, which illustrates the Xe/Kr separation performance under dynamic conditions.

Carbon Derived from Soft Pyrolysis of a Covalent Organic Framework as a Support for Small-Sized RuO2 Showing Exceptionally Low Overpotential for Oxygen Evolution Reaction.

Electrochemical water splitting is the most energy-efficient technique for producing hydrogen and oxygen, the two valuable gases. However, it is limited by the slow kinetics of the anodic oxygen evolution reaction (OER), which can be improved using catalysts. Covalent organic framework (COF)-derived porous carbon can serve as an excellent catalyst support. Here, we report high electrocatalytic activity of two composites, formed by supporting RuO2 on carbon derived from two COFs with closely related structures. These composites catalyze oxygen evolution from alkaline media with overpotentials as low as 210 and 217 mV at 10 mA/cm2, respectively. The Tafel slopes of these catalysts (65 and 67 mV/dec) indicate fast kinetics compared to commercial RuO2. The observed activity is the highest among all RuO2-based heterogeneous OER catalysts-a touted benchmark OER catalyst. The high catalytic activity arises from the extremely small-sized (∼3-4 nm) RuO2 nanoparticles homogeneously dispersed in a micro-mesoporous (BET = 517 m2/g) COF-derived carbon. The porous graphenic carbon favors mass transfer, while its N-rich framework anchors the catalytic nanoparticles, making it highly stable and recyclable. Crucially, the soft pyrolysis of the COF enables the formation of porous carbon and simultaneous growth of small RuO2 particles without aggregation.