Aqueous Nd3+ capture using a carboxyl-functionalized porous carbon derived from ZIF-8.

A porous graphitic carbon was obtained via the pyrolysis of a zeolite imidazolate framework (ZIF-8) under Ar atmosphere. Then, the carbon was functionalized with carboxylic groups and applied for separation of neodymium ions (Nd3+) from water. The adsorbent (denoted as C-ZDC) was characterized by X-ray diffraction, N2 adsorption-desorption isotherms, infrared spectroscopy, X-ray photoelectron spectroscopy, scanning and transition electron microscopies, thermogravimetric analysis, and Boehm titration. A practical adsorption equilibrium was attained within 4 h, and the adsorption isotherm at 25 °C revealed a maximum adsorption capacity of 175 mg/g, which is one of the highest values reported for different kinds of adsorbents. The adsorption kinetics and equilibrium isotherms were modeled, and the selectivity for Nd3+ over other metal ions was examined. From the effect of solution pH on the adsorption and material characterization results before and after adsorption, the high adsorption capacity of C-ZDC was ascribed to the formation of coordination bonds between Nd3+ ions and the -COOH groups. Further, the material was reusable for at least four adsorption-desorption cycles after a simple step of acid washing.

Aqueous adsorption of sulfamethoxazole on an N-doped zeolite beta-templated carbon.

A zeolite beta-templated carbon (BTC) and its N-doped form (nBTC) were prepared and used for the adsorptive removal of sulfamethoxazole (SMX) antibiotic from water. Both demonstrated excellent adsorption properties, and the maximum adsorption capacity of nBTC (1367 mg/g) was exceptionally high, and surpassed those of other adsorbents reported to date. Adsorption kinetic studies indicated that the adsorption was efficient, and adsorption equilibrium was reached within 10 min. The excellent adsorption performance of nBTC was attributed to the high-surface-area hydrophobic carbons with strong π-π interactions and H-bonding in the uniform microporous geometry of the material. The effect of the solution pH and thermodynamics of the adsorption process were subsequently investigated. nBTC was easily regenerated by washing with acetone, and a recyclability test confirmed that ~88% of the initial SMX adsorption capacity of nBTC was retained after the fifth adsorption-desorption cycle. Moreover, nBTC presented excellent capacity for the adsorptive removal of bisphenol A from water.

Aqueous adsorption of bisphenol A over a porphyrinic porous organic polymer.

A new porphyrinic porous organic polymer (PPOP) with high stability and excellent textural properties (929 m2/g surface area with 0.73 cm3/g pore volume) was made via the Friedel-Crafts reaction and applied for bisphenol A (BPA) adsorption in water. The material was examined by X-ray diffraction, N2 adsorption-desorption isotherms, scanning electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state 13C CP-MAS nuclear magnetic resonance spectroscopy. PPOP was proven highly effective for capturing BPA among the many adsorbent materials investigated. The Langmuir model could closely match the adsorption isotherm data with a high adsorption amount of ca. 653 mg/g at 25 °C. Approximately 95% of BPA was adsorbed in 50 min, and the pseudo-second-order kinetic model satisfactorily described the adsorption behavior. This adsorption process was exothermic (ΔH° = -39.10 kJ/mol), and the capacity gradually decreased with increasing pH. Spectroscopic analyses indicated that the BPA adsorption on PPOP was affected by (1) π-π interaction between BPA and the aromatic constituents of PPOP, (2) hydrogen bonding between the N sites of porphyrin units in PPOP and the hydroxyl group of BPA and, and (3) hydrophobic interactions. PPOP was easily regenerated after acetone washing, and >98% efficiency was observed throughout the five repeated adsorption-desorption cycles.

Highly efficient adsorptive removal of sulfamethoxazole from aqueous solutions by porphyrinic MOF-525 and MOF-545.

The metal-organic frameworks MOF-525 and MOF-545 comprised of Zr-oxide clusters and porphyrin moieties in different geometries were synthesized solvothermally and applied for the adsorptive removal of the broadly used organic contaminant sulfamethoxazole (SMX) from water. Both MOFs were found highly efficient for the adsorption of SMX with the maximum adsorption capacities of 585 and 690 mg/g for MOF-525 and MOF-545, respectively. The latter value is the highest adsorption capacity reported so far for the adsorption of SMX molecules on any adsorbent. The adsorption equilibrium could be modeled successfully by the Langmuir model, which showed close to matching with the experimental data. Their adsorption equilibriums were attained within 120 and 30 min for MOF-525 and MOF-545, respectively. MOF-545 with mesopores demonstrated superior adsorption kinetics to MOF-525 with micropores, and the simulation by the pseudo-second-order kinetic model indicated ca. 20 times faster adsorption by MOF-545 than MOF-525. Both showed pH-dependent adsorption of SMX with a gradual reduction at high pH due to the repulsion between negatively charged adsorbent and SMX. The adsorption of SMX conducted over a group of representative MOFs with different physicochemical properties and detailed characterization confirmed that the high adsorption capacity of the porphyrin MOFs is achieved by H-bonding between the SMX molecule and the N-sites of the porphyrin units in the MOFs, π-π interaction, and the high surface area. The adsorbents were easily regenerated by simple washing with acetone and reusable with >95% efficiency during 4 repeated adsorption-desorption cycles.

The effects of continuous- and stop-flow gas streams on adsorptive removal of benzene vapor using type - II covalent organic polymers.

Various materials have been investigated for the adsorptive removal of volatile organic compounds (VOCs, such as benzene). However, most materials proposed for the adsorptive removal of gaseous benzene (and other VOCs) perform relatively poorly (e.g., an impractically low-service 10% breakthrough volume [BTV10] at < 100 ppm). The adsorbent uptake rate (mg g-1 min-1) can also be assessed as a function of the gas-stream flow rate (or space velocity). The main aim of this study is to explore the effect of two different gas-stream supply modes - stopped flow (at a fixed stream flow rate of 330 mL atm min-1) vs. continuous flow (a variable-stream flow rate of 100, 200, or 330 mL atm min-1) on the adsorption metrics of gaseous benzene on 5 mg of two types of - II covalent organic polymers (COPs: CBAP-1 [DETA], CD; or CBAP-1 [EDA], CE). The sorbent tube outlet stream was sampled by two respective sampling methods (i.e., a large-volume injector [LVI] for stopped flow vs. syringe injection [SI] for continuous flow) for sample quantitation by gas chromatography flame-ionization detection (GC-FID). The observed BTV10 values in the two sampling modes were similar when tested using 10 ppm benzene, irrespective of sorbents: 56/60 (CD) vs. 620/624 L atm g-1 (CE). BTV10 values increased systematically with decreasing stream-flow rates to reflect the importance of space velocity in adsorptive removal of benzene. The overall assessment of adsorption performance between stopped flow (LVI) and continuous flow (SI) revealed that the performance of the adsorbent is independent of flow mode (e.g., when performance was compared at flow rate of 330 mL min-1).

Application of Zr-Cluster-Based MOFs for the Adsorptive Removal of Aliphatic Aldehydes (C1 to C5) from an Industrial Solvent.

Metal-organic frameworks (MOFs) are recognized as advanced sorbents for the effective removal and recovery of various hazardous pollutants in liquid and gaseous environments. In this research, the potential applicability of two Zr-based MOFs (UiO-66 (U6) and its amine counterpart UiO-66-NH2 (U6N)) was investigated relative to activated carbon (AC, tested as a reference adsorbent) for the purification of industrial organic solvents (e.g., methanol) from six different carbonyl impurities (CCs (C1 to C5): formaldehyde (FA, CH2O), acetaldehyde (AA, CH3CHO), propionaldehyde (PA, C3H6O), butyraldehyde (BA, C4H8O), isovaleraldehyde (IA, C5H10O), and valeraldehyde (VA, C5H10O)). In the sorptive removal of these CCs (both individually and in binary mixtures with FA), U6N showed higher efficacy in capturing all of the target CCs than U6 and AC. The adsorption selectivity of U6N toward single CC compounds was in the order of PA (165.1 mg g-1) > BA (158.9 mg g-1) > IA (154 mg g-1) > AA (136 mg g-1) > VA (131.5 mg g-1) > FA (120 mg g-1). In all binary mixtures, U6N selectively captured FA over the heavier CCs (C2-C5) by 1.5-3.3 times due to the steric hindrance of the C2-C5 aliphatic tails in the pore diffusion mechanism. The preferential adsorption of FA onto U6N can also be accounted for by the contribution of chemical bonding (Schiff base interaction) between the -NH2 groups in U6N and the C═O functionalities (aldehyde molecules) and physisorption, as confirmed by density functional theory (DFT) calculations. Theoretical DFT simulations also revealed that the competition between aldehyde molecules for Brønsted acidic sites (µ3-OH of Zr-clusters) created minor distortions in the U6/U6N frameworks.

Adsorption properties of advanced functional materials against gaseous formaldehyde.

Intense efforts have been made to eliminate toxic volatile organic compounds (VOCs) in indoor environments, especially formaldehyde (FA). In this study, the removal performances of gaseous FA using two metal-organic frameworks, MOF-5 and UiO-66-NH2, and two covalent-organic polymers, CBAP-1 (EDA) and CBAP-1 (DETA), along with activated carbon as a conventional reference material, were evaluated. To assess the removal capacity of FA under near-ambient conditions, a series of adsorption experiments were conducted at its concentrations/partial pressures of both low (0.1-0.5 ppm/0.01-0.05 Pa) and high ranges (5-25 ppm/0.5-2.5 Pa). Among all tested materials at the high-pressure region ㅐ (e.g., at 2.5 ppm FA), a maximum adsorption capacity of 69.7 mg g-1 was recorded by UiO-66-NH2. Moreover, UiO-66-NH2 also displayed the best 10% breakthrough volume (BTV10) of 534 L g-1 (0.5 ppm FA) to 2963 L g-1 (0.1 ppm FA). In contrast, at the high concentration test (at 5, 10, and 25 ppm FA), the maximum BTV10 values were observed as: 137 (UiO-66-NH2), 144 (CBAP-1 (DETA)), and 36.8 L g-1 (CBAP-1 (EDA)), respectively. The Langmuir isotherm model was observed to be a better fit of the adsorption data than the Freundlich model under most of the tested conditions. The superiority of UiO-66-NH2 was attributed to the van der Waals interactions between the linkers (framework) and the hydrocarbon "tail" (FA) coupled with interactions between its open metal sites and the FA carbonyl groups. This study demonstrated the good potential of these advanced functional materials toward the practical removal of gaseous FA in indoor environments.

Recent Progress in Direct Conversion of Methane to Methanol Over Copper-Exchanged Zeolites.

The conversion of methane into an easily transportable liquid fuel or chemicals has become a highly sought-after goal spurred by the increasing availability of cheap and abundant natural gas. While utilization of methane for the production of syngas and its subsequent conversion via an indirect route is typical, it is cost-intensive, and alternative direct conversion routes have been investigated actively. One of the most promising directions among these is the low-temperature partial oxidation of methane to methanol over a metal-loaded zeolite, which mimics facile enzymatic chemistry of methane oxidation. Thus mono-, bi-, and trinuclear oxide compounds of iron and copper stabilized on ZSM-5 or mordenite, which are structurally analogous to those found in methane monooxygenases, have demonstrated promising catalytic performances. The two major problems of theses metal-loaded zeolites are low yield to methanol and batch-like non-catalytic reaction systems challenging to extend to an industrial scale. In this mini-review, attention was given to the direct methane oxidation to methanol over copper-loaded zeolite systems. A brief introduction on the catalytic methane direct oxidation routes and current status of the applied metal-containing zeolites including the ones with copper ions are given. Next, by analyzing the extensive experimental and theoretical data available, the consensus among the researchers to achieve the target of high methanol yield is discussed in terms of zeolite topology, active species, and reaction parameters. Finally, the recent efforts on continuous methanol production from the direct methane oxidation aiming for an industrial process are summarized.

Porous Covalent Organic Polymers Comprising a Phosphite Skeleton for Aqueous Nd(III) Capture.

In order to meet the ever-increasing industrial demand for rare-earth elements (REEs), it is desirable to separate and recycle them at low concentrations from various sources including industrial and urban wastes. Here, we introduced phosphorus binding sites on the hydrophobic surface of a robust and high-surface area porous polymer backbone for environmentally benign and selective recovery of REEs via adsorption. For this purpose, two porous covalent organic polymer (COP) materials incorporated with in-built phosphite functionality (P-COP-1 and P-COP-2) were synthesized and applied for the adsorptive separation of Nd(III) ions from aqueous solution. A strategy to develop a series of P-COPs via a simple Friedel-Crafts reaction was introduced, and their application to the selective adsorption of REEs was explored for the first time. The newly synthesized P-COPs were amorphous and/or weakly crystalline and showed excellent chemical stability and large specific surface area with sufficient mesoporosity for enhanced diffusion of REE ions. P-COP-1 exhibited an exceptionally high Nd(III) adsorption capacity of 321.0 mg/g, corresponding to the stoichiometric ratio of P/Nd(III) = 1:0.7 and high selectivity of >86% over other competing transition and alkaline earth metal ions, whereas P-COP-2 gave a Nd(III) adsorption capacity of 175.6 mg/g at 25 °C and pH 5. Moreover, P-COP-1 showed a distribution coefficient value of 5.45 × 105 mL/g, which is superior to other benchmark adsorbent materials reported so far. Finally, the P-COPs were reusable for a minimum of 10 cycles without deterioration in adsorption capacities.

Competitive adsorption of gaseous aromatic hydrocarbons in a binary mixture on nanoporous covalent organic polymers at various partial pressures.

Covalent-organic polymers (COPs) are recognized for their great potential for treating diverse pollutants via adsorption. In this study, the sorption behavior of benzene and toluene was investigated both individually and in a binary mixture against two types of COPs possessing different -NH2 functionalities. Namely, the potential of COPs was tested against benzene and toluene in a low inlet partial pressure range (0.5-20 Pa) using carbonyl-incorporated aromatic polymer (CBAP)-1-based diethylenediamine (EDA) [CD] and ethylenetriamine (DETA) [CE]. The maximum adsorption capacity and breakthrough values of both COPs showed dynamic changes with increases in the partial pressures of benzene and toluene. The maximum adsorption capacities (Amax) of benzene (as the sole component in N2 under atmospheric conditions) on CD and CE were in the range of 24-36 and 33-75 mg g-1, respectively. In contrast, with benzene and toluene in a binary mixture, the benzene Amax decreased more than two-fold (range of 2.7-15 and 6-39 mg g-1, respectively) due to competition with toluene for sorption sites. In contrast, the toluene Amax values remained consistent, reflecting its competitive dominance over benzene. The adsorption behavior of the targeted compounds (i.e., benzene and toluene) was explained by fitting the adsorption data by diverse isotherm models (e.g., Langmuir, Freundlich, Elovich, and Dubinin-Radushkevich). The current research would be helpful for acquiring a better understanding of the factors affecting competitive adsorption between different VOCs in relation to a given sorbent and across varying partial pressures.

Amine-Functionalized Metal-Organic Frameworks and Covalent Organic Polymers as Potential Sorbents for Removal of Formaldehyde in Aqueous Phase: Experimental Versus Theoretical Study.

Porous materials have been identified as efficient sorbent media to remove volatile organic compounds. To evaluate their potential as adsorbents, the adsorptive removal of formaldehyde (FA) in aqueous environments was investigated using four materials, two water-stable metal-organic frameworks (MOFs) of UiO-66 (U6) and U6-NH2 (U6N) and two covalent organic polymers (COPs) with amine-functionality, CBAP-1-EDA (CE) and CBAP-1-DETA (CD). U6N exhibited the highest removal capacity of 93% (0.56 mg g-1) of the tested materials [e.g., CE (81.1%, 0.53 mg g-1) > CD (67.2%, 0.43 mg g-1) > U6 (66.9%, 0.42 mg g-1)], which was 2 times higher than that of the reference sorbent, activated carbon (AC: 50%, 0.30 mg g-1). The results of Fourier transform infrared and powder X-ray diffraction analyses confirmed the interactions between FA molecules and the amine components of the materials (U6N, CD, and CE). According to density functional theory calculations, the formation of hydrogen bonds between FA molecules and amine components was apparent and was further verified by FA/amine distance (CD: 2.83, CE: 2.88, and U6N: 2.66 Å) along with enthalpy values (CD: -32.4, CE: -45.5, and U6N: -272 kJ mol-1). In case of U6, the major interactions occurred in the metal-clusters (-19.3 kJ mol-1) via electrostatic interactions (distance: 5.49 Å). Furthermore, the sorption by amine-functionalized materials such as U6N is suggested to be dominated by hydrogen bonding which ultimately led to the formation of imine. If the performance of the tested materials is evaluated in terms of partition coefficient, U6N (1153 mg g-1 mM-1) is found as the outperformer in all tested subjects. Regeneration of spent MOFs/COPs was also plausible in the presence of ethanol to maintain their structural integrity even after 10 adsorption-desorption cycles. Overall, the selected MOFs/COPs were seen to have very high removal capacity for hazardous FA molecules in aqueous phase.

Selective Adsorption of Rare Earth Elements over Functionalized Cr-MIL-101.

Efficient rare earth elements (REEs) separation and recovery are crucial to meet the ever-increasing demand for REEs extensively used in various high technology devices. Herein, we synthesized a highly stable chromium-based metal-organic framework (MOF) structure, Cr-MIL-101, and its derivatives with different organic functional groups (MIL-101-NH2, MIL-101-ED (ED: ethylenediamine), MIL-101-DETA (DETA: diethylenetriamine), and MIL-101-PMIDA (PMIDA: N-(phosphonomethyl)iminodiacetic acid)) and explored their effectiveness in the separation and recovery of La3+, Ce3+, Nd3+, Sm3+, and Gd3+ in aqueous solutions. The prepared materials were characterized using various analytical instrumentation. These MOFs showed increasing REE adsorption capacities in the sequence MIL-101 < MIL-101-NH2 < MIL-101-ED < MIL-101-DETA < MIL-101-PMIDA. MIL-101-PMIDA showed superior REE adsorption capacities compared to other MOFs, with Gd3+ being the element most efficiently adsorbed by the material. The adsorption of Gd3+ onto MIL-101-PMIDA was examined in detail as a function of the solution pH, initial REE concentration, and contact time. The obtained adsorption equilibrium data were well represented by the Langmuir model, and the kinetics were treated with a pseudo-second-order model. A plausible mechanism for the adsorption of Gd3+ on MIL-101-PMIDA was proposed by considering the surface complexation and electrostatic interaction between the functional groups and Gd3+ ions under different pH conditions. Finally, recycling tests were carried out and demonstrated the higher structural stability of MIL-101-PMIDA during the five adsorption-regeneration runs.

Electroresponsive Polymer-Inorganic Semiconducting Composite (MCTP-Fe3O4) Particles and Their Electrorheology.

Polymer-inorganic semiconducting composite (MCTP-Fe3O4) particles were fabricated by loading nanosized Fe3O4 on the microporous covalent triazine-based polymer (MCTP) through a chemical coprecipitation method and then applied to an electrorheological (ER) material. The structural and morphological images of MCTP-Fe3O4 composite were examined by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Their magnetic property was also investigated by vibrating sample magnetometry. The chain structure formation of MCTP-Fe3O4 dispersed in silicone oil under an external electric field was confirmed using an optical microscope. The ER fluid based on MCTP-Fe3O4 was processed by dispersing the composite particles in an oil medium, and for comparison, an ER fluid based on pure MCTP was also prepared by the same process. The ER performance of two different ER fluids was scrutinized by a rotational rheometer, which demonstrated that MCTP-Fe3O4 showed better ER characteristics than MCTP-based ER suspension.

Preparation and Application of Porous Materials based on Deep Eutectic Solvents.

Deep eutectic solvents (DESs) are a common successor to ionic liquids (ILs) with similar physicochemical properties. DESs have attracted considerable interest in related chemical research based on the superiority of DESs over ILs and in the preparation of porous materials. In addition, DESs-based materials have been applied widely in chemical research. This review highlights the preparation and properties of DESs. The application of DES in the preparation of silica and polymers is also discussed. The available data and references in this field are reviewed to summarize the applications and developments of DESs. Based on the development of DESs, the exploitation of new DES-based materials is expected to diversify into chemical research.

Porous NH2-MIL-125 as an efficient nano-platform for drug delivery, imaging, and ROS therapy utilized Low-Intensity Visible light exposure system.

Metal-organic frameworks are a novel class of organic-inorganic hybrid polymer with potential applications in bioimaging, drug delivery, and ROS therapy. NH2-MIL-125, which is a titanium-based metal organic framework with a large surface area of 1540m2/g, was synthesized using a hydrothermal method. The material was characterized by powder X-ray diffreaction (PXRD), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM), and N2 isotherm analyses. The size of the polymer was reduced to the nanoscale using a high-frequency sonication process. PEGylation was carried out to improve the stability and bioavailability of the NMOF. The as-synthesized nano-NH2-MIL-125/PEG (NMOF/PEG) exhibited good biocompatibility over the (Cancer) MCF-7 and (Normal) COS-7 cell line. The interaction of NMOF/PEG with the breast cancer cell line (MCF-7) was examined by BIO-TEM analysis and laser confocal imaging. 2',7'-dichlorofluorescin diacetate (DCFDA) analysis confirmed that NMOF/PEG produced free radicals inside the cancer cell line (MCF-7) upon visible light irradiation. NMOF/PEG absorbed a large amount of DOX (20wt.% of DOX) and showed pH, and photosensitive release. This controlled drug delivery was attributed to the presence of NH2, Ti group in MOF and a hydroxyl group in PEG. This combination of chemo- and ROS-therapy showed excellent efficiency in killing cancer MCF-7 cells.

Hybrid molecularly imprinted polymers modified by deep eutectic solvents and ionic liquids with three templates for the rapid simultaneous purification of rutin, scoparone, and quercetin from Herba Artemisiae Scopariae.

Different kinds of deep eutectic solvents based on choline chloride and ionic liquids based on 1-methylimidazole were used to modify hybrid molecularly imprinted polymers with the monomer γ-aminopropyltriethoxysilane-methacrylic and three templates (rutin, scoparone, and quercetin). The materials were adopted as solid-phase extraction packing agents, and were characterized by FTIR spectroscopy and field emission scanning electron microscopy. The hybrid molecularly imprinted polymers modified by deep eutectic solvents had high recoveries and a strong recognition of rutin, scoparone, and quercetin in Herba Artemisiae Scopariae than those modified by ionic liquids. In the procedure of solid-phase extraction, deep eutectic solvents-2-hybrid molecularly imprinted polymers were obtained with the best recoveries with rutin (92.27%), scoparone (87.51%), and quercetin (80.02%), and the actual extraction yields of rutin (5.6 mg/g), scoparone (2.3 mg/g), and quercetin (3.4 mg/g). Overall, the proposed approach with the high affinity of hybrid molecularly imprinted polymers might offer a novel method for the purification of complex samples.

CO2 Adsorption Over Metal-Organic Frameworks: A Mini Review.

Metal-organic frameworks (MOFs) are a class of porous materials that are comprised of metal ion-containing nodes linked by multi-dentate organic ligand bridges principally through coordination bonding. Over the last few decades, MOFs have been studied widely as CO2 adsorbents. CO2 adsorption in MOFs can be enhanced by tuning their physicochemical properties. This short review discusses CO2 adsorption over MOFs with particular focus on the contributory effects of (1) inherent textural properties, (2) coordinatively unsaturated open metal sites, (3) surface functionalization, (4) structural interpenetration (catenation), and (5) ion-exchange.

Fabrication of Palladium Nanoparticles on Porous Aromatic Frameworks as a Sensing Platform to Detect Vanillin.

Here, we report the fabrication of palladium nanoparticles on porous aromatic frameworks (Pd/PAF-6) using a facile chemical approach, which was characterized by various spectro- and electrochemical techniques. The differential pulse voltammetry (DPV) response of Pd/PAF-6 toward the vanillin (VA) sensor shows a linear relationship over concentrations (10-820 pM) and a low detection limit (2 pM). Pd/PAF-6 also exhibited good anti-interference performance toward 2-fold excess of ascorbic acid, nitrophenol, glutathione, glucose, uric acid, dopamine, ascorbic acid, 4-nitrophenol, glutathione, glucose, uric acid, dopamine, and 100-fold excess of Na(+), Mg(2+), and K(+) during the detection of VA. The developed electrochemical sensor based on Pd/PAF-6 had good reproducibility, as well as high selectivity and stability. The established sensor revealed that Pd/PAF-6 could be used to detect VA in biscuit and ice cream samples with satisfactory results.

Porous Covalent Triazine Polymer as a Potential Nanocargo for Cancer Therapy and Imaging.

A microporous covalent triazine polymer (CTP) network with a high surface area was synthesized via the Friedel-Crafts reaction and employed as a potential transport system for drug delivery and controlled release. The CTP was transformed to the nanoscale region by intense ultrasonication followed by filtration to yield nanoscale CTP (NCTP). This product showed excellent dispersibility in physiological solution while maintaining its chemical structure and porosity. An anticancer drug, doxorubicin (DOX), was loaded onto the NCTP through hydrophobic and π-π interactions, and its release was controlled at pH 4.8 and 7.4. The NCTP showed no toxicity toward cancer or normal cells, but the NCTP-DOX complex showed high efficacy against both types of cells in vitro. In-vitro cell imaging revealed that NCTP is a potential material for bioimaging. The potency of NCTP on cellular senescence was confirmed by the expression of senescence associated marker proteins p53 and p21. These results suggest that NCTP can be used as a new platform for drug delivery and imaging with potential applications in diagnosis and therapy.

Palladium Nanoparticles Supported on MIL-101 as a Recyclable Catalyst in Water-Mediated Heck Reaction.

Pd nanoparticles supported on the chromium terephthalate metal organic framework, Pd0.9/MIL-101, was prepared by simple Pd-acetate adsorption on MIL-101 followed by reduction in acetone. The material was characterized by XRD, N2 adsorption-desorption isotherm, TEM and ICP analysis. Pd0.9/MIL-101 was found to be an effective heterogeneous catalyst for the water-mediated Heck cross-coupling reaction of various aryl iodides and alkenes under mild reaction conditions with product yields of 81 to 97%. The electron-withdrawing group attached to aryl iodide reacted faster than the electron-donating one, and the activity increased in the sequence of 4-methoxy-1- iodobenzene << iodobenzene < 1-iodo-4-nitrobenzene. The catalyst could be reused several times without losing its initial catalytic activity, and XRD and TEM confirmed that the crystallinity of Pd0.9/MIL-101 had been retained during the reaction with no metal leaching or agglomeration observed.