One-pot Construction of Metal Nanoparticles Loaded COF Catalysts for Aqueous Hydrogenation Reactions.

The catalysis performance of metal nanoparticles (NPs) will be significantly deteriorated because of their spontaneous agglomeration during practical applications. Covalent-organic frameworks (COFs) materials with functional groups and well-defined channels benefit for the dispersion and anchor of metal ions and the confined growth of metal NPs, working as an ideal platform to compose catalytic systems. In this article, we report a one-pot strategy for the preparation of metal NPs loaded COFs without the need of post-modification. During the polymerization process, the pre-added metal ions were stabilized by the rapidly formed COF oligomers and hardly disturb the construction of COFs. After reduction, metal NPs are uniformly anchored on the COF matrix. Eventually, a wide spectrum of metal NPs, including Au, Pd, Pt, AuPd, CuPd, CuPt and CuPdPt, loaded COFs are successfully prepared. The versatility and metal ions anchoring mechanism are verified with four different COF matrixes. Taking AuPd NPs as example, the resultant AuPd NPs loaded COF materials can selectively decompose ammonium formate and produce hydrogen in-situ, exhibiting over 99 % conversion of hydrodechlorination for chlorobenzenes and nitro-reduction reaction for nitroaromatic compounds under ambient temperature in aqueous solution.

UV Light-Driven Nitric Oxide Release from Porous Nitrogen Heterocyclic Polymers.

In this study, porous polymers with nitrogen heterocyclic core structures are synthesized through the condensation of enaminonitrile and terephthalaldehyde monomers. These polymers are used as a platform to store bioactive nitric oxide (NO) and control its release. NO loading is achieved by nitrosating the polymers with acidified nitrite, a process that also imparts photoresponsivity to the polymers. Polymer composition and porosity affect NO storage and release. It is observed that under UV light at 365 nm in a PBS solution, the polymers (NO@DHP-POP) can release NO in a manner fully controlled by UV lighting. Under experimental conditions, these porous polymers release NO at a rate of ≈10.0-50.0 µmol g-1 over 60 min. These findings demonstrate the potential of these polymers for integrating NO delivery into phototherapy applications.

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators.

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g-1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Oxoporphyrinogen (OxP) is a unique chromophore compound in that it is intrinsically de-aggregated allowing large quantum yields of singlet oxygen generation. Due to its structure, OxP is also an ideal building block for porous systems. In this work, we describe the first incorporation of OxP in highly stable microporous polymers strongly enhanced singlet oxygen generation for selective oxidation of organic sulfides to sulfoxides (as a model reaction) under heterogeneous conditions. The novelty of this work lies in the high stability and easy recovery of the materials, the synergetic enhancement of singlet oxygen generation in the polymers over the starting OxP, and the excellent selectivity for the oxidation reaction.

Simple Functionalization of a Donor Monomer to Enhance Charge Transfer in Porous Polymer Networks for Photocatalytic Hydrogen Evolution.

Porous polymer networks (PPNs) are promising candidates as photocatalysts for hydrogen production. Constructing a donor-acceptor structure is known to be an effective approach for improving photocatalytic activity. However, the process of how a functional group of a monomer can ensure photoexcited charges transfer and improve the hydrogen evolution rate (HER) has not yet been studied on the molecular level. Herein, we design and synthesize two kinds of triazatruxene (TAT)-based PPNs: TATR-PPN with a hexyl (R) group and TAT-PPN without the hexyl group, to understand the relationship between the presence of the functional group and charge transfer. The hexyl group on the TAT unit was found to ensure the transfer of photoexcited electrons from a donor unit to an acceptor unit and endowed the TATR-PPN with stable hydrogen production.

Self-assembled porous polymer films for improved oxygen sensing.

Absolute oxygen sensors based on quenching of phosphorescence have been the subject of numerous studies for the monitoring of biological environments. Here, we used simple fabrication techniques with readily available polymers to obtain high performance phosphorescent films. Specifically, evaporation-based phase separation and the breath figure technique were used to induce porosity. The pore sizes ranged from ∼37 nm to ∼141 µm while the maximum average porosity achieved was ∼74%. The oxygen sensing properties were evaluated via a standarised calibration procedure with an optoelectronic setup in both transmission and reflection based configurations. When comparing non-porous and porous films, the highest improvements achieved were a factor of ∼7.9 in dynamic range and ∼7.3 in maximum sensitivity, followed by an improved linearity with a half-sensitivity point at 43% O2 V/V. Also, the recovery time was reduced by an order of magnitude in the high porosity film and all samples prepared were not affected by variations in the humidity of the surrounding environment. Despite the use of common polymers, the fabrication techniques employed led to the significant enhancement of oxygen sensing properties and elucidated the relation between porous film morphologies and sensing performance.

Porous Cyclodextrin Polymer Enables Dendrite-Free and Ultra-Long Life Solid-State Zn-I2 Batteries.

Zn-I2 batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of ß-cyclodextrin with SiCl4 , and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10-3  S cm-1 at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm-2 and 1200 h at 20 mA cm-2 ). The solid-state Zn-I2 battery shows an ultra-long life of over 35,000 cycles at 2 A g-1 . Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I2 batteries.

Covalent Organic Frameworks for Extracting Water from Air.

Water scarcity is becoming an increasingly pressing issue due to global population growth and industrialization. One effective approach to addressing this issue is sorption-based atmospheric water harvesting (SAWH). Covalent organic frameworks (COFs) are a type of porous crystalline material that have emerged as promising sorbents for water harvesting due to their high surface area, tunable pore size, and customizable pore chemistry. In this mini-review, we provide an overview of the different types of COFs, their structural characteristics, and the diverse linkage chemistries used to construct them. Then, we summarize recent advances in using COF-based sorbents for atmospheric water harvesting, including strategies for controlling sorption properties and optimizing performance in terms of thermodynamics and dynamics. Finally, we discuss prospects and challenges associated with improving the efficiency of COF-based SAWH systems.

"Activated Borane" - A Porous Borane Cluster Network as an Effective Adsorbent for Removing Organic Pollutants.

The unprecedented co-thermolysis of decaborane(14) (nido-B10 H14 ) and toluene results in a novel porous material (that we have named "activated borane") containing micropores between 1.0 and 1.5 nm in diameter and a specific surface area of 774 m2 g-1 (Ar, 87 K) that is thermally stable up to 1000 °C. Solid state 1 H, 11 B and 13 C MAS NMR, UV-vis and IR spectroscopies suggest an amorphous structure of borane clusters interconnected by toluene moieties in a ratio of about three toluene molecules for every borane cluster. In addition, the structure contains Lewis-acidic tri-coordinated boron sites giving it some unique properties. Activated borane displays high sorption capacity for pollutants such as sulfamethoxazole, tramadol, diclofenac and bisphenol A that exceed the capacity of commercially-available activated carbon. The consistency in properties for each batch made, and the ease of its synthesis, make activated borane a promising porous material worthy of broad attention.

Designing Mesoporous Photonic Structures for High-Performance Passive Daytime Radiative Cooling.

Passive daytime radiative cooling (PDRC) has drawn significant attention recently for electricity-free cooling. Porous polymers are attractive for PDRC since they have excellent performance and scalability. A fundamental question remaining is how PDRC performance depends on pore properties (e.g., radius, porosity), which is critical to guiding future structure designs. In this work, optical simulations are carried out to answer this question, and effects of pore size, porosity, and thickness are studied. We find that mixed nanopores (e.g., radii of 100 and 200 nm) have a much higher solar reflectance R̅solar (0.951) than the single-sized pores (0.811) at a thickness of 300 µm. With an Al substrate underneath, R̅solar, thermal emittance ε̅LWIR, and net cooling power Pcool reach 0.980, 0.984, and 72 W/m2, respectively, under a semihumid atmospheric condition. These simulation results provide a guide for designing high-performance porous coating for PDRC applications.

N-Rich, Polyphenolic Porous Organic Polymer and Its In Vitro Anticancer Activity on Colorectal Cancer.

N-rich organic materials bearing polyphenolic moieties in their building networks and nanoscale porosities are very demanding in the context of designing efficient biomaterials or drug carriers for the cancer treatment. Here, we report the synthesis of a new triazine-based secondary-amine- and imine-linked polyphenolic porous organic polymer material TrzTFPPOP and explored its potential for in vitro anticancer activity on the human colorectal carcinoma (HCT 116) cell line. This functionalized (-OH, -NH-, -C=N-) organic material displayed an exceptionally high BET surface area of 2140 m2 g-1 along with hierarchical porosity (micropores and mesopores), and it induced apoptotic changes leading to high efficiency in colon cancer cell destruction via p53-regulated DNA damage pathway. The IC30, IC50, and IC70 values obtained from the MTT assay are 1.24, 3.25, and 5.25 µg/mL, respectively.

A Novel Nanocomposite Based on Triazine Based Covalent Organic Polymer Blended with Porous g-C3N4 for Photo Catalytic Dye Degradation of Rose Bengal and Fast Green.

Metal free visible light active photocatalysts of covalent organic polymers (COPs) and polymeric graphitic carbon nitride (g-C3N4) are interesting porous catalysts that have enormous potential for application in organic pollutant degradation. Imine condensation for COPs, and thermal condensation for g-C3N4 were used to produce the catalysts. FT-IR, Raman, NMR, UV-Vis Spectroscopy, X-ray diffraction, and scanning electron microscopy studies were used to investigate the structural, optical, and morphological features of the metal free catalysts. We have constructed COPs with a π-electron deficient (Lewis acidic) triazine core and π -electron rich (Lewis basic) naphthalene and anthraquinone rings coupled by -O and -N donors in this study. Furthermore, the prepared Bulk-g-C3N4 (B-GCN) was converted to porous g-C3N4 (P-GCN) using a chemical oxidation process, and the generated P-GCN was efficiently mixed with the COP to create a novel nanocomposite for photocatalytic application. Using the anthraquinone-based COP and P-GCN (1:1 ratio, PA-GCN) catalyst, the highest photodegradation efficiencies for the polymeric graphitic carbon nitride of 88.2% and 82.3% were achieved using the Fast green (FG) and Rose bengal (RB) dyes, respectively. The rate constant values of 0.032 and 0.024/min were determined for FG and RB degradation, respectively. Higher activity may be related to the incorporation of COP and PA-GCN, which act significantly well in higher visible light absorption, have superior reactive oxygen generation (ROS), and demonstrate an excellent pollutant-catalyst interaction.

Comparison of the CytoSorb® 300 mL and Jafron HA380 hemoadsorption devices: an in vitro study.

INTRODUCTION: We performed an analysis of two blood purification systems to determine their performance for removing interleukins (ILs)-6 and 10, tumor necrosis factor (TNF)-α and monocyte chemoattractant protein (MCP)-1 from blood. MATERIAL AND METHODS: An in vitro hemoperfusion blood recirculation circuit was used to compare the CytoSorb® 300 mL (CytoSorbents Inc., Princeton, NJ) and Jafron HA 380 (Jafron Biomedical Co., Ltd., Zhuhai City, China) devices. The removal of purified recombinant human IL-6, IL-10, TNFα and MCP-1 by the adsorbers was compared at various timepoints. Three runs were completed and removal was evaluated as the mean area under the curve (AUC). RESULTS: Both devices showed effective removal of the tested cytokines. IL-6, IL-10, TNFα and MCP-1 were removed faster and to a higher extent by the CytoSorb® 300 mL device. At maximal time of 12 h, overall removal according to AUC of remaining concentrations was significantly lower with CytoSorb® 300 mL compared with HA 380 (IL-6: 1075.5 ± 665.9 vs. 4345.1 ± 1499.3 (p = 0.01), IL-10: 5065.7 ± 882.5 vs. 11,939.7 ± 4523.1 (p = 0.03), TNF-α: 6519.9 ± 997.6 vs. 10,303.7 ± 2347.0 (p = 0.03) and MCP-1: 278.9 ± 40.7 vs. 607.3 ± 84.4 (p = 0.001)). CONCLUSIONS: Both the CytoSorb® and the Jafron HA 380 devices are capable of removing cytokines from blood in a benchtop model. The CytoSorb® 300 device was significantly more efficient achieving the bulk of the removal in the first 120 min.

Self-Driven Pretreatment and Room-Temperature Storage of Water Samples for Virus Detection Using Enhanced Porous Superabsorbent Polymer Beads.

The continuous emergence of infectious viral diseases has become a major threat to public health. To quantify viruses, proper handling of water samples is required to ensure the accuracy and reliability of the testing results. In this study, we develop enhanced porous superabsorbent polymer (PSAP) beads to pretreat and store water samples for virus detection. By applying PSAP beads to collect water samples, the viruses are captured and encapsulated inside the beads while undesired components are excluded. We have successfully demonstrated that the shelf life of the model virus can be effectively extended at room temperature (22 °C) and an elevated temperature (35 °C). Both the infectivity level and genome abundance of the viruses are preserved even in a complex medium such as untreated wastewater. Under the tested conditions, the viral degradation rate constant can be reduced to more than 10 times using the PSAP beads. Therefore, the enhanced PSAP beads provide a low-cost and efficient sample pretreatment and storage method that is feasible and practical for large-scale surveillance of viral pathogens in water samples.

Rapid and simple pressure-sensitive adhesive microdevice fabrication for sequence-specific capture and fluorescence detection of sepsis-related bacterial plasmid gene sequences.

Microbial resistance to currently available antibiotics poses a great threat in the global fight against infections. An important step in determining bacterial antibiotic resistance can be selective DNA sequence capture and fluorescence labeling. In this paper, we demonstrate the fabrication of simple, robust, inexpensive microfluidic devices for DNA capture and fluorescence detection of a model antibiotic resistance gene sequence. We laser micromachined polymethyl methacrylate microchannels and enclosed them using pressure-sensitive adhesive tapes. We then formed porous polymer monoliths with DNA capture probes in these microchannels and used them for sequence-specific capture, fluorescent labeling, and laser-induced fluorescence detection of picomolar (pM) concentrations of synthetic and plasmid antibiotic resistance gene targets. The relative fluorescence for the elution peaks increased with loaded target DNA concentration. We observed higher fluorescence signal and percent recovery for synthetic target DNA compared to plasmid DNA at the same loaded target concentration. A non-target gene was used for control experiments and produced < 3% capture relative to the same concentration of target. The full analysis process including device fabrication was completed in less than 90 min with a limit of detection of 30 pM. The simplicity of device fabrication and good DNA capture selectivity demonstrated herein have potential for application with processes for bacterial plasmid DNA extraction and single-particle counting to facilitate determination of antibiotic susceptibility. Graphical abstract.

Application of nitrogen-rich porous organic polymer for the solid-phase synthesis of 2-amino-4H-benzo[b]pyran scaffolds using ball milling process.

This paper presents the efficient synthesis of 2-amino-4H-benzo[b]pyrans using mesoporous poly-melamine-formaldehyde as a polymeric heterogeneous catalyst. According to the principals of green chemistry, the reaction was performed by the planetary ball milling process at ambient and neat conditions. The heterogeneous catalyst could be reused up to five runs with no reducing of catalytic efficiency. A variety of substituted 2-amino-4H-benzo[b]pyrans were obtained in good to excellent yields under eco-friendly conditions. Other advantages of the current methodology include short reaction time, wide substrate-scope, and use of a metal-free polymeric catalyst. Also, the current method avoids the use of hazardous reagents and solvents, tedious workup and multi-step purification. This work revealed that porous organic polymers containing Lewis base sites having acceptor-donner hydrogen bonding functional groups, and high porosity could play a vital role in the promotion of the one-pot multicomponent reactions in the solid-phase synthesis.

Dual-stimuli-responsive porous polymer enzyme reactor for tuning enzymolysis efficiency.

A strategy for preparing a dual-stimuli-responsive porous polymer membrane enzyme reactor (D-PPMER) is described, consisting of poly (styrene-maleic anhydride-N-isopropylacrylamide-acrylate-3',3'-dimethyl-6-nitro-spiro[2H-1-benzopyran-2,2'-indoline]-1'-esterspiropyran ester) [P(S-M-N-SP)] and D-amino acid oxidase. Tunable control via "on/off" 365 nm UV light irradiation and temperature variation was used to change the membrane surface configuration and adjust the enzymolysis efficiency of the D-PPMER. A chiral capillary electrophoresis technique was developed for evaluation of the enzymatic efficiency of D-PPMER with a Zn(II)-dipeptide complex as the chiral selector and D,L-serine as the substrate. Interestingly, the enzymatic kinetic reaction rate of D-PPMER under UV irradiation at 36 °C (9.2 × 10-2 mM·min-1) was 3.2-fold greater than that of the free enzyme (2.9 × 10-2 mM·min-1). This was because upon UV irradiation at high temperature, the P(SP) and P(N) moieties altered from a "stretched" to a "curled" state to encapsulate the enzyme in smaller cavities. The confinement effect of the cavities further improved the enzymatic efficiency of the D-PPMER. This protocol highlights the outstanding potential of smart polymers, enables tunable control over the kinetic rates of stimuli-responsive enzyme reactors, and establishes a platform for adjusting enzymolysis efficiency using two different stimuli.

Sensitivities of Rheological Properties of Magnetoactive Foam for Soft Sensor Technology.

Magnetoactive (MA) foam, with its tunable mechanical properties and magnetostriction, has the potential to be used for the development of soft sensor technology. However, researchers have found that its mechanical properties and magnetostriction are morphologically dependent, thereby limiting its capabilities for dexterous manipulation. Thus, in this work, MA foam was developed with additional capabilities for controlling its magnetostriction, normal force, storage modulus, shear stress and torque by manipulating the concentration of carbonyl iron particles (CIPs) and the magnetic field with regard to morphological changes. MA foams were prepared with three weight percentages of CIPs, namely, 35 wt.%, 55 wt.% and 75 wt.%, and three different modes, namely, zero shear, constant shear and various shears. The results showed that the MA foam with 75 wt.% of CIPs enhanced the normal force sensitivity and positive magnetostriction sensitivity by up to 97% and 85%, respectively. Moreover, the sensitivities of the storage modulus, torque and shear stress were 8.97 Pa/mT, 0.021 µN/mT, and 0.0096 Pa/mT, respectively. Meanwhile, the magnetic dipolar interaction between the CIPs was capable of changing the property of MA foam from a positive to a negative magnetostriction under various shear strains with a low loss of energy. Therefore, it is believed that this kind of highly sensitive MA foam can potentially be implemented in future soft sensor systems.

Metal-Coordinated Supramolecular Polymers from the Minimalistic Hybrid Peptide Foldamers.

Availing the peptide folded architectures to design metal-coordinated frameworks and cages is restricted due to the scarcity of readily accessible short and stable secondary structures. The secondary structures, α-helix and ß-sheets, play significant roles in stabilizing tertiary folds of proteins. Designing such helical structures from the short sequences of peptides without having any steric restrictions is exceptionally challenging. Here we reveal the short α,γ-hybrid tripeptide sequences that manifest stable helical structures without having any sterically constrained amino acids. These short hybrid tripeptides fold into helices even in the presence of two typically ß-sheet favoring Val residues. The hybrid helix consisting of terminal pyridine units coordinates with the metal ions and drives the helical polymerization. Depending on the sequence and the position of N in pyridine moieties, these peptides form selective metallogels with Ag+ and Cu2+ ions. The X-ray diffracted analysis of the peptide single crystals obtained from the gel matrix reveals that the helical structure is maintained during the self-assembly process. Further, by varying the counter anion, a 3D helical crystalline coordination polymer with permanent porosity is generated. The findings reported here can be used to design new functional metal-foldamer coordinated polymers.

Porous silica and polymer monolith architectures as solid-state optical chemosensors for Hg2+ ions.

We demonstrate a simple strategy to concoct a competent solid-state opto-chemosensor for the selective and sensitive visual detection of Hg2+ ions. The sensor fabrication involves the utilization of indigenously prepared mesoporous silica and polymer monoliths as probe anchoring templates and 8-hydroxy-7-(4-n-butylphenylazo) quinoline (HBPQ) as the chromo-ionophoric probe for Hg2+ sensing. Both the monoliths are designed with discrete structural and morphological features to serve as efficient host templates. The structural and surface features of the monoliths are characterized using p-XRD, TEM, SEM, SAED, EDAX, XPS, and N2 isotherm analysis. The synergetic features of monolith structural hierarchy along with the probe's selective chelating ability enable rapid signal response and remarkable ion selectivity for Hg2+. The solid-state sensors evince a linear signal response from 0.6 to 150 µg/L for Hg2+ recognition, with superior data authenticity and replication that is preceded by an RSD value of ≤ 2.25% when tested with real water samples.Graphical abstract Mesoporous silica and polymer monolith architects hosting HBPQ probe molecules demonstrate an excellent visual sensing of ultra-trace (µg/L) Hg2+ in various water samples with a striking color transition from light orange to dark red upon complexation of probe with Hg2+. The solid-state sensors are Hg2+ ion selective, super-responsive, real-time applicable, and also reusable.

Green synthesis of a magnetic ß-cyclodextrin polymer for rapid removal of organic micro-pollutants and heavy metals from dyeing wastewater.

Adsorption is one of the most preferred techniques in the advanced treatment of dyeing wastewater. Magnetic porous materials with good adsorption performance, excellent reusability, and a green synthesis route are highly desirable adsorbents in commerce. In this study, we synthesized a magnetic ß-cyclodextrin polymer (MNP-CM-CDP) containing many macro- and ultramicropores in aqueous phase. CO2 adsorption-desorption isotherms and a dye adsorption method provided Langmuir specific surface areas for the MNP-CM-CDP of 114.4 m2 g-1 and 153 m2 g-1, respectively. Model pollutants (BPA, MB, BO2, RhB, Cr(III), Pb(II), Zn(II), and Cu(II)) were rapidly and efficiently removed from the aqueous solution by the MNP-CM-CDP. In addition, the polymer could be easily separated from the solution under an external magnetic field. The adsorption of the contaminants was dependent on pH, while the effects of ionic strength and humic acid were slight in the concentration range studied. The polymer could be easily regenerated at room temperature and retained good adsorption performance. Moreover, the MNP-CM-CDP showed good feasibility for the removal of pollutants from actual dyeing wastewater samples.