Ultrafast Removal of Thorium and Uranium from Radioactive Waste and Groundwater Using Highly Efficient and Radiation-Resistant Functionalized Triptycene-Based Porous Organic Polymers.

Thorium (Th) and uranium (U) are important strategic resources in nuclear energy-based heavy industries such as energy and defense sectors that also generate significant radioactive waste in the process. The management of nuclear waste is therefore of paramount importance. Contamination of groundwater/surface water by Th/U is increasing at an alarming rate in certain geographical locations. This necessitates the development of strategic adsorbent materials with improved performance for capturing Th/U species from radioactive waste and groundwater. This report describes the design of a unique, robust, and radiation-resistant porous organic polymer (POP: TP-POP-SO3NH4), which demonstrates ultrafast removal of Th(IV) (<30 s)/U(VI) (<60 s) species present in simulated radioactive wastewater/groundwater samples. Thermal, chemical, and radiation stabilities of these POPs were studied in detail. The synthesized ammoniated POP revealed exceptional capture efficiency for trace-level Th (<4 ppb) and U (<3 ppb) metal ions through the cation-exchange mechanism. TP-POP-SO3NH4 shows a significant sorption capacity [Th (787 mg/g) and U (854 mg/g)] with an exceptionally high distribution coefficient (Kd) of 107 mL/g for Th. This work also demonstrates a facile protocol to convert a nonperforming POP, by simple chemical modifications, into a superfast adsorbent for efficient uptake/removal of U/Th.

A new Eosin Y-based 'turnon' fluorescent sensor for ratiometric sensing of toxic mercury ion (Hg2+) offering unaided eye detection and its antibacterial activity.

A unique fluorescent molecule (ND-S) was obtained from Eosin Y in two simple yet high yielding steps (1). ND-S has special metal ion sensing ability, such that it can selectively detect toxic Hg2+ present in very low concentration in aqueous solutions in the presence of other competing metal ions. The host-guest complexation is ratiometric and is associated with significant increase in fluorescence during the process. Isothermal titration calorimetry (ITC) experiments provided thermodynamic parameters related to interaction between ND-S and Hg2+. Using inductively coupled plasma mass spectrometry (ICP-MS), the Hg2+(aq) removal efficiency of ND-S was estimated to be 99.88%. Appreciable limit of detection (LOD = 7.4 nM) was observed. Other competing ions did not interfere with the sensing of Hg2+ by ND-S. The effects of external stimuli (temperature and pH) were studied. Besides, the complex (ND-M), formed by 1:1 coordination of ND-S and Hg2+ was found to be effective against the survival of Gram-positive bacteria (S. aureus and B. subtilis) with a high selectivity index. Moreover, bacterial cell death mechanism was studied systematically. Overall, we have shown the transformation of a toxic species (Hg2+), extracted from polluted water by a biocompatible sensor (ND-S), into an effective and potent antibacterial agent (ND-M).

Promising CO2 Capture and Effective Iodine Adsorption of Hyper-Cross-Linked Conjugated Porous Organic Polymers Prepared from a Cyclopentannulation Reaction.

Three novel conjugated porous organic polymers, denoted as C-POP1-3 and which consist of alternating pyrene cores with various contorted fluorene surrogates, were successfully synthesized from a versatile one-pot palladium-catalyzed [3+2] cyclocondensation reaction. The resulting polymers were obtained in excellent yields and displayed weight-average molecular weights (Mw) ranging from 12.2 to 20.2 kg/mol with polydispersity indices (Mw/Mn) ranging between 1.8 and 2.4, suggesting that the molecular masses are narrowly distributed and thus implying homogeneous polymer chains. Thermal stability exploration of C-POP1-3 by thermogravimetric analysis (TGA) revealed an impressive robustness with a 10% weight reduction temperature attaining 485 °C. Investigation of the inherent microporosity properties of C-POP1-3 via nitrogen adsorption experiments using Brunauer-Emmett-Teller (BET) theory discloses their surface areas which reach up to 560 m2 g-1 and pore volumes averaging 0.47 cm3 g-1. The target conjugated polymers were explored as adsorbents disclosing a maximum carbon dioxide adsorption of 83.0 mg g-1 at 273 K and low pressure for C-POP1, whereas iodine sorption tests portrayed prominent outcomes, notably for C-POP3 which proved to owe a strong affinity toward the hitherto mentioned halogen by achieving a maximum adsorption of 2220 mg g-1. Additionally, recyclability experiments confirmed the possibility to regenerate the polymers' adsorption capabilities even after seven consecutive cycles of adsorption-desorption cycles, which qualify them as auspicious iodine adsorbents.

Palladium(II)-immobilized Triptycene based Hypercrosslinked Polymers: An Efficient, Green, and Reusable Heterogenous Catalyst for Suzuki-Miyaura Cross-coupling Reaction.

The Suzuki-Miyaura cross-coupling (SMCC) involves the coupling of organohalides and organoboron molecules in the presence of Pd(II)-based catalysts. Often SMCC reactions employ homogenous catalysts. However, such homogenous SMCC reactions are associated with certain limitations which has motivated design of effective and sustainable Pd(II)-based heterogeneous catalytic systems. Herein, we report a systematic development of a Pd(II)-immobilized and triptycene based ionic hyper crosslinked polymer (Pd@TP-iHCP) and explored its application as a heterogeneous catalyst for SMCC reaction. Pd@TP-iHCP has ample N-heterocyclic carbene (NHC) pendants that anchor Pd(II) centres on the polymeric matrix. Pd@TP-iHCP was characterized satisfactorily using FT-IR, 13 C CP-MAS NMR, BET surface area analysis, SEM, EDX and HRTEM. The performance of Pd@TP-iHCP as a heterogeneous catalyst for SMCC reactions was explored using various combinations of aryl boronic acids and aryl halides. Experimental results show that Pd@TP-iHCP is associated with a moderately high surface area. It is an efficient catalyst for SMCC (in aqueous media) with a modest loading of 0.8 mol % Pd(II)-catalyst since high yields of the expected products were obtained in shorter time intervals. Pd@TP-iHCP also features excellent stability and catalyst recyclability since it could be re-used for several cycles without any significant decrease in catalytic efficiency.

Synthesis of flaxseed gum/melanin-based scaffold: A novel approach for nano-encapsulation of doxorubicin with enhanced anticancer activity.

Doxorubicin is a powerful chemotherapy medicine that is frequently used to treat cancer, but because of its extremely destructive side effects on other healthy cells, its applications have been severely constrained. With the aim of using lower therapeutic doses of doxorubicin while maintaining the same anti-cancerous activity as those of higher doses, the present study designs nano-encapsulation of doxorubicin by acrylamide grafted melanin as core and acrylic acid grafted flax seed gum as shell (DOX@AAM-g-ML/AA-g-FSG-NPs) for studies in-vivo and in-vitro anticancer activity. For biological studies, the cytotoxicity of DOX@AAM-g-ML/AA-g-FSG-NPs was examined on a cancerous human cell line (HCT-15) and it was observed that DOX@AAM-g-ML/AA-g-FSG-NPs exhibited very high toxicity towards HCT-15. In-vivo investigation in colon cancer-inflicted rat model also showed that DOX@AAM-g-ML/AA-g-FSG-NPs showed better anticancer activity against cancerous cells as compared to free doxorubicin. The drug release behavior of DOX@GML-GFS-NPs was studied at several pH and maximum drug release (95 %) was recorded at pH -7.2, and kinetic data of drug release was follows the Higuchi (R2 = 0.9706) kinetic model. Our study is focussed on reducing the side effects of doxorubicin by its nano-encapsulation in acrylamide grafted melanin as core and acrylic acid grafted flax seed gum that will also enhance its efficiency.

Iodine and Nickel Ions Adsorption by Conjugated Copolymers Bearing Repeating Units of Dicyclopentapyrenyl and Various Thiophene Derivatives.

The synthesis of three conjugated copolymers TPP1-3 was carried out using a palladium-catalyzed [3+2] cycloaddition polymerization of 1,6-dibromopyrene with various dialkynyl thiophene derivatives 3a-c. The target copolymers were obtained in excellent yields and high purity, as confirmed by instrumental analyses. TPP1-3 were found to divulge a conspicuous iodine adsorption capacity up to 3900 mg g-1, whereas the adsorption mechanism studies revealed a pseudo-second-order kinetic model. Furthermore, recyclability tests of TPP3, the copolymer which revealed the maximum iodine uptake, disclosed its efficient regeneration even after numerous adsorption-desorption cycles. Interestingly, the target copolymers proved promising nickel ions capture efficiencies from water with a maximum equilibrium adsorption capacity (qe) of 48.5 mg g-1.

Carbon dot-based superhydrophobic modification of a covalent organic framework for oil-in-water emulsion separation.

A super hydrophobic composite is developed for the first time through the non-covalent self-assembly of a hydrophilic covalent organic framework (COF) and amphoteric CDs to achieve highly selective separation of dispersed micro droplets of oil from an oil/water mixture.

Rationally Designed Ionic Covalent Organic Networks (iCONs) with Efficient Antimicrobial Activities.

Two unique ionic covalent organic networks (iCONs) incorporated with guanidinium motifs were obtained and characterized by various techniques. Upon 8 h of treatment with iCON-HCCP (250 µg/mL), >97% killing of Staphylococcus aureus, Candida albicans, and Candida glabrata strains was observed. Antimicrobial efficacies against bacteria and fungi were also evident from FE-SEM studies. High antifungal efficacies also correlated well with >60% reduction of ergosterol content, high lipid peroxidation, and membrane damage leading to necrosis.

Meropenem loaded 4-arm-polyethylene-succinimidyl-carboxymethyl ester and hyaluronic acid based bacterial resistant hydrogel.

Developing an ideal vitreous substitute/implant is a current challenge. Moreover, implants (e.g., heart valves and vitreous substitutes), are associated with a high risk of bacterial infection when it comes in contact with cells at implant site. Due to infection, many implants fail, and the patient requires immediate surgery and suffers from post-operative problems. To overcome these problems in vitreous implants, we developed a bacterial resistant vitreous implant, where meropenem (Mer), an antibiotic, has been incorporated in a hydrogel prepared by crosslinking HA (deacetylated sodium hyaluronate) with 4-arm-polyethylene-succinimidyl-carboxymethyl-ester (PESCE). The HA-PESCE hydrogel may serve as a suitable artificial vitreous substitute (AVS). The pre-gel solutions of HA-PESCE without drug and with the drug are injectable through a 22 G needle, and the gel formation occurred in approx. 3 min: it indicates its suitability for in-situ gelation through vitrectomy surgery. The HA-PESCE hydrogel depicted desired biocompatibility, transparency (>90 %), water content (96 %) and sufficient viscoelasticity (G' >100 Pa) calculated after 1 month in-vitro, which are suitable for vitreous substitute. The HA-Mer-PESCE hydrogel showed improved biocompatibility, suitable transparency (>90 %), high water content (96 %), and suitable viscoelasticity (G' >100 Pa) calculated after 1 month in-vitro, which are suitable for vitreous substitute. Further, hydrogel strongly inhibits the growth of bacteria E.coli and S.aureus. The drug loaded hydrogel showed sustained in-vitro drug release by the Fickian diffusion-mediated process (by Korsmeyer-Peppas and Peppas Sahlin model). Thus, the developed hydrogel may be used as a potential bacterial resistant AVS.

Ordered Macro/Microporous Ionic Organic Framework for Efficient Separation of Toxic Pollutants from Water.

In case of pollutant segregation, fast mass diffusion is a fundamental criterion in order to achieve improved performance. The rapid mass transport through porous materials can be achieved by availing large open pores followed by easy and complete accessibility of functional sites. Inducing macroporosity into such materials could serve as ideal solution providing access to large macropores that offer unhindered transport of analyte and full exposure to interactive sites. Moreover, the challenge to configure the ionic-functionality with macroporosity could emerge as an unparalleled avenue toward pollutants separation. Herein, we strategized a synthetic protocol for construction of a positively charged hierarchically-porous ordered interconnected macro-structure of organic framework where the size and number of macropores can easily be tuned. The ordered macropores with strong electrostatic interaction synergistically exhibited ultrafast removal efficiency towards various toxic pollutants.

Pterostilbene-isothiocyanate inhibits breast cancer metastasis by selectively blocking IKK-ß/NEMO interaction in cancer cells.

Metastasis, the main cause of breast cancer-associated fatalities, relies on many regular pathways involved in normal cell physiology and metabolism, thus, making it challenging to identify disease-specific therapeutic target(s). Chemically synthesized anti-metastatic agents are preferred for their fast and robust actions. However, these agents have adverse side effects, thus, increasingly favouring the identification of phytocompounds as suitable alternatives. Resveratrol and pterostilbene have long been established as potent anti-cancer agents. Earlier studies from our laboratory documented the anti-cancer activities associated with pterostilbene-isothiocyanate (PTER-ITC), a derivative of pterostilbene. The current study focuses on evaluating the anti-metastatic property of PTER-ITC and the underlying mechanism, by employing in silico, in vitro, and in vivo approaches. The significant anti-metastatic activity of PTER-ITC was observed in vitro against breast cancer metastatic cell line (MDA-MB-231) and in vivo in the 4T1 cell-induced metastatic mice model. Epithelial-mesenchymal transition (EMT), a hallmark of metastasis regulated by the transcription factors, Snail1 and Twist, was found to be reverted in vitro by PTER-ITC treatment. PTER-ITC blocked the activation of NF-κB/p65 and its concomitant nuclear translocation, resulting in the transcriptional repression of its target genes, Snail1 and Twist. PTER-ITC prevented the formation of IKK complex, central to NF-κB activation, by binding to the NEMO-binding domain (NBD) of IKK-ß and inhibiting its interaction with NEMO (NF-κB essential modulator). According to our observations, PTER-ITC attenuated NF-κB activation selectively in cancerous cells. In conclusion, this study demonstrated that PTER-ITC is a potent anti-metastatic agent capable of targeting physiologically important pathways in a cancer-specific manner.

Fluorinated Iron(ii) clathrochelate units in metalorganic based copolymers: improved porosity, iodine uptake, and dye adsorption properties.

We report the synthesis of metalorganic copolymers made from the palladium catalyzed Sonogashira cross-coupling reaction between various iron(ii) clathrochelate building blocks with diethynyl-triptycene and fluorene derivatives. The target copolymers CCP1-5 were isolated in excellent yield and characterized by various instrumental analysis techniques. Interestingly, investigation of the copolymers' porosity properties discloses BET surface areas up to 337 m2 g-1 for the target compounds bearing fluorinated iron(ii) clathrochelate units CCP2,5. Moreover, the fluorinated copolymers display an outstanding uptake capacity of iodine with a maximum adsorption of 200 wt%. The target metalorganic copolymers CCP1-5 reveal very good adsorption of organic dyes, namely, methyl blue and methylene blue, from aqueous media.

Triptycene-Based and Schiff-Base-Linked Porous Networks: Efficient Gas Uptake, High CO2/N2 Selectivity, and Excellent Antiproliferative Activity.

A set of unique triptycene-based and organic Schiff-base-linked polymers (TBOSBLs) are conveniently synthesized in which triptycene motifs are connected with 1,3,5-triformylphloroglucinol units via Schiff-base linkages. TBOSBLs are amorphous, thermally stable with a reasonable surface area (SABET up to 649 m2/g), and have abundant nanopores (pore size < 100 nm). TBOSBLs are good sorbents for small gas molecules (such as CO2, H2, and N2) and they can selectively capture CO2 over N2. Additionally, TBOSBLs show superior antiproliferative activity against human colorectal cancer cells relative to previously reported covalent organic frameworks (COFs). The mechanism of cell death is also studied elaborately.

Chitosan-based zeolite-Y and ZSM-5 porous biocomposites for H2 and CO2 storage.

Sustainable energy is the most valuable clean and renewable energy for the future. A simple, robust, and inexpensive ecofriendly method has been developed here to prepare chitosan-based zeolite porous biocomposites via solvent exchange followed by calcination. The resulting chitosan-based zeolite biocomposites were characterized using advanced technologies including attenuated total reflection-infrared (ATR-IR) spectroscopy, X-ray powder diffraction (XRD) analysis, thermogravimetric analysis (TGA), high-resolution field-emission scanning electron microscopy (HR-FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and nitrogen adsorption-desorption isotherms. The Brunauer-Emmett-Teller (BET) surface area of the ZeY@CS composite (795 m2 g-1) was greater than those of ZSM-5@CS (444 m2 g-1), pure chitosan, pure zeolite Y, and ZSM-5. The chitosan-based zeolite biocomposites show enhanced gas storage for small molecule like CO2 and hydrogen. Therefore, chitosan-based zeolite biocomposites should be suitable for energy storage, carbon capture, and sequestration (CCS) applications.

Triptycene-Derived Photoresponsive Fluorescent Azo-Polymer as Chemosensor for Picric Acid Detection.

Two new triptycene-based azobenzene-functionalized polymers (TBAFPs) have been synthesized using the well-known Pd-catalyzed Sonogashira cross-coupling polycondensation reaction between 2,6-diethynyltriptycene and (meta or para) dibromo-azobenzenes. Enhancement of the fluorescent emission intensity was observed upon trans → cis isomerization of -N=N- linkage in TBAFPs. The cis-lifetime of TBAFP1 is rather long (greater than 2 days). The resulting materials were tested as a potential chemosensor for the detection of picric acid (PA)-a water pollutant as well as chemical constituent of explosives used in warfare. PA was found to interact strongly with TBAFPs, which led to significant quenching of the latter's fluorescence emission intensities. The binding constants are in the order of 105 M-1. TBAFPs were also able to detect PA in nanomolar concentrations.

Polymorphic self-assembly of pyrazine-based tectons at the solution-solid interface.

Exploring the surface self-assembly of small molecules that act as building blocks (tectons) for complex supramolecular structures is crucial for realizing surface-supported functional molecular devices. Here, we report on the synthesis and surface self-assembly of a new pyrazine-derived molecule with pyridine pendants. Ambient scanning tunneling microscopy investigation at the solution-solid interface reveals polymorphic self-assembly of these molecules on a HOPG substrate. Two different molecular packing structures with equal distribution are observed. Detailed analysis of the STM images emphasizes the crucial role of weak intermolecular hydrogen bonding, and molecule-substrate interactions in the formation of the observed polymorphs. Such weak hydrogen bonding interactions are highly desirable for the formation of modular supramolecular architectures since they can provide sufficiently robust molecular structures and also facilitate error correction.

Heterobimetallic (FeII/PtII)-Based Supramolecular Coordination Complexes Using 1,1'-Ferrocene Dicarboxylate: Self-Assembly and Interaction with Carbon Dots.

The synthesis and characterization of a new pyrazine-based ditopic organoplatinum(II) complex having a bite angle of 180° is reported. The facile and efficient syntheses are described of three discrete neutral Fe(II)/Pt(II) heterobimetallic SCCs with Pt(II) acceptor clips of different binding angles, 0, 120, and 180°. These new SCCs were characterized by multinuclear NMR and mass spectrometry. Electrochemical response of these ferrocene containing self-assembled ensembles was studied using cyclic voltammetry. The diplatinum acceptor organometallic clips significantly quench the fluorescence of highly emitting carbon quantum dots (CD), while the self-assembled macrocycles tend to nullify the quenching effect of the organometallic clips. Interestingly, the inefficient quenching of CD fluorescence by these SCCs was found to be directly related to the angular disposition of the binding sites in the Pt(II) based organometallic clips.

Chitosan grafted graphene oxide aerogel: Synthesis, characterization and carbon dioxide capture study.

We have demonstrated a superficial, environmentally friendly and sustainable development of chitosan (CS) grafted graphene oxide aerogels for adsorption of CO2 gas. The CS is grafted into the carbonaceous materials like graphene oxide, multi-walled carbon nanotubes etc. to provide the large surface area, high porosity and a large number of amine group which facilitates the adsorption of CO2 gas. CS and carbonaceous materials undergo crosslinking by using cross-linker reagents, and freeze-drying technique to yield CS based aerogels with ordered porous structures. Crosslinking between CS and carbonaceous materials was confirmed by FT-IR. Physical properties of the CS-based aerogels were studied using SEM, TGA, XRD, BET isotherm analysis. The adsorption capacity of CO2 gas by CS grafted graphene oxide aerogels is around 0.257 mmol g-1 at 1 bar, that is significantly higher in comparison to the adsorption capacity of pure CS. We believe that this study helps to reduce the cost of adsorbents due to the large availability of marine waste (CS) and thus aims to reduce the anthropogenic CO2 gas at low cost, favourable temperature and pressure as compared to previously reported.

Self-Assembly of a [1 + 1] Ionic Hexagonal Macrocycle and Its Antiproliferative Activity.

A unique irregular hexagon was self-assembled using an organic donor clip (bearing terminal pyridyl units) and a complementary organometallic acceptor clip. The resulting metallamacrocycle was characterized by multinuclear NMR, mass spectrometry, and elemental analyses. Molecular modeling confirmed hexagonal shaped cavity for this metallamacrocycle which is a unique example of a discrete hexagonal framework self-assembled from only two building blocks. Cytotoxicity of the Pt-based acceptor tecton and the self-assembled PtII-based macrocycle was evaluated using three cancer cell lines and results were compared with cisplatin. Results confirmed a positive effect of the metallamacrocycle formation on cell growth inhibition.

Concentration dependent supramolecular interconversions of triptycene-based cubic, prismatic, and tetrahedral structures.

The quantitative, single step, self-assembly of a shape-persistent, three-dimensional C3v-symmetric, triptycene-based tris-terpyridinyl ligand initially gives a platonic-based cubic architecture, which was unequivocally characterized by 1D and 2D NMR spectroscopy, mass spectrometry, and single crystal X-ray structural analysis. The unique metal-ligand binding properties of the Cd2+ analogue of this construct give rise to a concentration-dependent dynamic equilibrium between cube, prism, and tetrahedron-shaped architectures. Dilution transforms this cube into two identical tetrahedra through a stable prism-shaped intermediate; increasing the concentration reverses the process.