Enhancing ion selectivity by tuning solvation abilities of covalent-organic-framework membranes.

Understanding the molecular-level mechanisms involved in transmembrane ion selectivity is essential for optimizing membrane separation performance. In this study, we reveal our observations regarding the transmembrane behavior of Li+ and Mg2+ ions as a response to the changing pore solvation abilities of the covalent-organic-framework (COF) membranes. These abilities were manipulated by adjusting the lengths of the oligoether segments attached to the pore channels. Through comparative experiments, we were able to unravel the relationships between pore solvation ability and various ion transport properties, such as partitioning, conduction, and selectivity. We also emphasize the significance of the competition between Li+ and Mg2+ with the solvating segments in modulating selectivity. We found that increasing the length of the oligoether chain facilitated ion transport; however, it was the COF membrane with oligoether chains containing two ethylene oxide units that exhibited the most pronounced discrepancy in transmembrane energy barrier between Li+ and Mg2+, resulting in the highest separation factor among all the evaluated membranes. Remarkably, under electro-driven binary-salt conditions, this specific COF membrane achieved an exceptional Li+/Mg2+ selectivity of up to 1352, making it one of the most effective membranes available for Li+/Mg2+ separation. The insights gained from this study significantly contribute to advancing our understanding of selective ion transport within confined nanospaces and provide valuable design principles for developing highly selective COF membranes.

Enhancing Sustainable Energy Conversion Efficiency by Incorporating Photoelectric Responsiveness into Multiporous Ionic Membrane.

The evolution of porous membranes has revitalized their potential application in sustainable osmotic-energy conversion. However, the performance of multiporous membranes deviates significantly from the linear extrapolation of single-pore membranes, primarily due to the occurrence of ion-concentration polarization (ICP). This study proposes a robust strategy to overcome this challenge by incorporating photoelectric responsiveness into permselective membranes. By introducing light-induced electric fields within the membrane, the transport of ions is accelerated, leading to a reduction in the diffusion boundary layer and effectively mitigating the detrimental effects of ICP. The developed photoelectric-responsive covalent-organic-framework membranes exhibit an impressive output power density of 69.6 W m-2 under illumination, surpassing the commercial viability threshold by ≈14-fold. This research uncovers a previously unexplored benefit of integrating optical electric conversion with reverse electrodialysis, thereby enhancing energy conversion efficiency.

Porous Supramolecular Assemblies for Efficient Suzuki Coupling of Aryl Chlorides.

The development of catalytic systems that can activate aryl chlorides for palladium-catalyzed cross-coupling reactions is at the forefront of ongoing efforts to synthesize fine chemicals. In this study, a facile ligand-template approach is adopted to achieve active-site encapsulation by forming supramolecular assemblies; this bestowed the pristine inert counterparts with reactivity, which is further increased upon the construction of a porous framework. Experimental results indicated that the isolation of ligands by the surrounding template units is key to the formation of catalytically active monoligated palladium complexes. Additionally, the construction of porous frameworks using the resulting supramolecular assemblies prevented the decomposition of the Pd complexes into nanoparticles, which drastically increased the catalyst lifetime. These findings, along with the simplicity and generality of the synthesis scheme, suggest that the strategy can be leveraged to achieve unique reactivity and potentially enable fine-chemical synthesis.

Changes in the Microbiota and their Roles in Patients with Type 2 Diabetes Mellitus.

An association between type 2 diabetes mellitus (T2DM) and gut microbiota is well established, but the results of related studies are inconsistent. The purpose of this investigation is to elucidate the characteristics of the gut microbiota in T2DM and non-diabetic subjects. Forty-five subjects were recruited for this study, including 29 T2DM patients and 16 non-diabetic subjects. Biochemical parameters, including body mass index (BMI), fasting plasma glucose (FPG), serum total cholesterol (TC), triglycerides (TG), high-density lipoprotein (HDL), and hemoglobin A1c (HbA1c), were analyzed and correlated with the gut microbiota. Bacterial community composition and diversity were detected in fecal samples using direct smear, sequencing, and real-time polymerase chain reaction (PCR). In this study, it was observed that indicators such as BMI, FPG, HbA1c, TC, and TG in T2DM patients were on the rise, concurrent with dysbiosis of the microbiota. We observed an increase in Enterococci and a decrease in Bacteroides, Bifidobacteria, and Lactobacilli in patients with T2DM. Meanwhile, total short-chain fatty acids (SCFAs) and D-lactate concentrations were decreased in the T2DM group. In addition, FPG was positively correlated with Enterococcus and negatively correlated with Bifidobacteria, Bacteroides, and Lactobacilli. This study reveals that microbiota dysbiosis is associated with disease severity in patients with T2DM. The limitation of this study is that only common bacteria were noted in this study, and more in-depth related studies are urgently needed.

Up/Down Tuning of Poly(ionic liquid)s in Aqueous Two-Phase Systems.

Thermally induced reversible up/down migration of poly(ionic liquid)s (PILs) in aqueous two-phase systems (ATPSs) was achieved for the first time in this study. Novel ATPSs were fabricated using azobenzene (Azo)- and benzyl (Bn)-modified PILs, and their upper and lower phases could be easily tuned using the grafting degree (GD) of the Azo and Bn groups. Bn-PIL with higher GDBn could go up into the upper phase and Azo-PIL come down to the lower phase when the temperature increased (>65 °C); this behavior was reversed at lower temperatures. Moreover, a reversible two-phase/single-phase transition was realized under UV irradiation. Experimental and simulation results revealed that the difference in the hydration capacity between Bn-PIL and Azo-PIL accounted for their unique phase-separation behavior. A versatile platform for fabricating ATPSs with tunable stimuli-responsive behavior can be realized based on our findings, which can broaden their applications in the fields of smart separation systems and functional material development.

Impact factors of the degradation of bisphenol A by nitrocellulose membrane under illumination.

Nitrocellulose membrane (NCM) can produce hydroxyl radicals under illumination, which promotes the oxidative degradation of organic pollutants. In this paper, NCM was used to oxidize bisphenol A (BPA) under simulated sunlight. The effects of pH, temperature, light intensity, anion and cation on the degradation of BPA were analyzed. The photodegradation process of BPA was discussed. The optimal photolysis rate was 0.031 min-1 when the temperature was 30°C, the light intensity was 2.67 × 104 Lux, and the pH value was 9.0. The alkaline environment, temperature and light intensity can promote the photodegradation of BPA. Except for nitrate ions, anions and cations can inhibit the photodegradation of BPA. Compared with cations, anions have a greater inhibitory effect on BPA degradation. The degradation products of BPA by NCM were analyzed by gas chromatographic/mass. This study may provide useful information for the BPA degradation by NCM in complex water samples.

Porous polymer catalysts with hierarchical structures.

The emergence of porous organic polymers (POPs) has provided great opportunities for new applications in heterogeneous catalysis owing to their unprecedented intrinsic structural features such as high surface areas, extraordinary framework stabilities and chemically adjustable compositions. In this tutorial review, representative recent developments in the POPs-based catalysts with hierarchically porous structures are presented. Various strategies for the syntheses of hierarchically porous polymers including hard-templating, soft-templating and template-free approaches and the design of catalytically active porous polymers including post-modification, co-polymerization and self-polymerization have been discussed. In addition, their catalytic properties are compared. Finally, we emphasize the importance of the synthesis of hierarchically porous polymer based heterogeneous catalysts using sustainable routes under template-free and metal-free conditions.

Highly Efficient Heterogeneous Hydroformylation over Rh-Metalated Porous Organic Polymers: Synergistic Effect of High Ligand Concentration and Flexible Framework.

A series of diphosphine ligand constructed porous polymers with stable and flexible frameworks have been successfully synthesized under the solvothermal conditions from polymerizing the corresponding vinyl-functionalized diphosphine monomers. These insoluble porous polymers can be swollen by a wide range of organic solvents, showing similar behavior to those of soluble analogues. Rather than just as immobilizing homogeneous catalysts, these porous polymers supported with Rh species demonstrate even better catalytic performance in the hydroformylations than the analogue homogeneous catalysts. The sample extraordinary performance could be attributed to the combination of high ligand concentration and flexible framework of the porous polymers. Meanwhile, they can be easily separated and recycled from the reaction systems without losing any activity and selectivity. This excellent catalytic performance and easy recycling heterogeneous catalyst property make them be very attractive. These diphosphine ligand constructed porous polymers may provide new platforms for the hydroformylation of olefins in the future.

SLoN: a spiking looming perception network exploiting neural encoding and processing in ON/OFF channels.

Looming perception, the ability to sense approaching objects, is crucial for the survival of humans and animals. After hundreds of millions of years of evolutionary development, biological entities have evolved efficient and robust looming perception visual systems. However, current artificial vision systems fall short of such capabilities. In this study, we propose a novel spiking neural network for looming perception that mimics biological vision to communicate motion information through action potentials or spikes, providing a more realistic approach than previous artificial neural networks based on sum-then-activate operations. The proposed spiking looming perception network (SLoN) comprises three core components. Neural encoding, known as phase coding, transforms video signals into spike trains, introducing the concept of phase delay to depict the spatial-temporal competition between phasic excitatory and inhibitory signals shaping looming selectivity. To align with biological substrates where visual signals are bifurcated into parallel ON/OFF channels encoding brightness increments and decrements separately to achieve specific selectivity to ON/OFF-contrast stimuli, we implement eccentric down-sampling at the entrance of ON/OFF channels, mimicking the foveal region of the mammalian receptive field with higher acuity to motion, computationally modeled with a leaky integrate-and-fire (LIF) neuronal network. The SLoN model is deliberately tested under various visual collision scenarios, ranging from synthetic to real-world stimuli. A notable achievement is that the SLoN selectively spikes for looming features concealed in visual streams against other categories of movements, including translating, receding, grating, and near misses, demonstrating robust selectivity in line with biological principles. Additionally, the efficacy of the ON/OFF channels, the phase coding with delay, and the eccentric visual processing are further investigated to demonstrate their effectiveness in looming perception. The cornerstone of this study rests upon showcasing a new paradigm for looming perception that is more biologically plausible in light of biological motion perception.

Accessing ladder-shape azetidine-fused indoline pentacycles through intermolecular regiodivergent aza-Paternò-Büchi reactions.

Small molecules with conformationally rigid, three-dimensional geometry are highly desirable in drug development, toward which a direct, simple-to-complexity synthetic logic is still of considerable challenges. Here, we report intermolecular aza-[2 + 2] photocycloaddition (the aza-Paternò-Büchi reaction) of indole that facilely assembles planar building blocks into ladder-shape azetidine-fused indoline pentacycles with contiguous quaternary carbons, divergent head-to-head/head-to-tail regioselectivity, and absolute exo stereoselectivity. These products exhibit marked three-dimensionality, many of which possess 3D score values distributed in the highest 0.5% region with reference to structures from DrugBank database. Mechanistic studies elucidated the origin of the observed regio- and stereoselectivities, which arise from distortion-controlled C-N coupling scenarios. This study expands the synthetic repertoire of energy transfer catalysis for accessing structurally intriguing architectures with high molecular complexity and underexplored topological chemical space.

Ionic liquids with reversible photo-induced conductivity regulation in aqueous solution.

Stimulus-responsive ionic liquids have gained significant attention for their applications in various areas. Herein, three kinds of azobenzimidazole ionic liquids with reversible photo-induced conductivity regulation were designed and synthesized. The change of electrical conductivity under UV/visible light irradiation in aqueous solution was studied, and the effect of chemical structure and concentration of ionic liquids containing azobenzene to the regulation of photoresponse conductivity were discussed. The results showed that exposing the ionic liquid aqueous solution to ultraviolet light significantly increased its conductivity. Ionic liquids with longer alkyl chains exhibited an even greater increase in conductivity, up to 75.5%. Then under the irradiation of visible light, the electrical conductivity of the solution returned to its initial value. Further exploration of the mechanism of the reversible photo-induced conductivity regulation of azobenzene ionic liquids aqueous solution indicated that this may attributed to the formation/dissociation of ionic liquids aggregates in aqueous solution induced by the isomerization of azobenzene under UV/visible light irradiation and resulted the reversible conductivity regulation. This work provides a way for the molecular designing and performance regulation of photo-responsive ionic liquid and were expected to be applied in devices with photoconductive switching and micro photocontrol properties.

Photoelectric responsive ionic channel for sustainable energy harvesting.

Access to sustainable energy is paramount in today's world, with a significant emphasis on solar and water-based energy sources. Herein, we develop photo-responsive ionic dye-sensitized covalent organic framework membranes. These innovative membranes are designed to significantly enhance selective ion transport by exploiting the intricate interplay between photons, electrons, and ions. The nanofluidic devices engineered in our study showcase exceptional cation conductivity. Additionally, they can adeptly convert light into electrical signals due to photoexcitation-triggered ion movement. Combining the effects of salinity gradients with photo-induced ion movement, the efficiency of these devices is notably amplified. Specifically, under a salinity differential of 0.5/0.01 M NaCl and light exposure, the device reaches a peak power density of 129 W m-2, outperforming the current market standard by approximately 26-fold. Beyond introducing the idea of photoelectric activity in ionic membranes, our research highlights a potential pathway to cater to the escalating global energy needs.

Functional Porous Ionic Polymers as Efficient Heterogeneous Catalysts for the Chemical Fixation of CO2 under Mild Conditions.

The development of efficient and metal-free heterogeneous catalysts for the chemical fixation of CO2 into value-added products is still a challenge. Herein, we reported two kinds of polar group (-COOH, -OH)-functionalized porous ionic polymers (PIPs) that were constructed from the corresponding phosphonium salt monomers (v-PBC and v-PBH) using a solvothermal radical polymerization method. The resulting PIPs (POP-PBC and POP-PBH) can be used as efficient bifunctional heterogeneous catalysts in the cycloaddition reaction of CO2 with epoxides under relatively low temperature, ambient pressure, and metal-free conditions without any additives. It was found that the catalytic activities of the POP-PBC and POP-PBH were comparable with the homogeneous catalysts of Me-PBC and PBH and were higher than that of the POP-PPh3-COOH that was synthesized through a post-modification method, indicating the importance of the high concentration catalytic active sites in the heterogeneous catalysts. Reaction under low CO2 concentration conditions showed that the activity of the POP-PBC (with a conversion of 53.8% and a selectivity of 99.0%) was higher than that of the POP-PBH (with a conversion of 32.3% and a selectivity of 99.0%), verifying the promoting effect of the polar group (-COOH group) in the porous framework. The POP-PBC can also be recycled at least five times without a significant loss of catalytic activity, indicating the high stability and robustness of the PIPs-based heterogeneous catalysts.

Stable Porous Organic Polymers Used for Reversible Adsorption and Efficient Separation of Trace SO2.

The development of porous solid adsorbents for selective adsorption and separation of SO2 has attracted much attention recently. Herein, we design porous organic polymers (POPs) decorated with pyridine ligands as building units (POP-Py) through a radical polymerization of the 2,5-divinylpyridine (v-Py) monomer. Due to its high BET surface area, nanoporosity, and excellent stability, the prepared POP-Py can be used for reversible adsorption and efficient separation of SO2. The POP-Py possesses a SO2 capacity of 10.8 mmol g-1 at 298 K and 1.0 bar, which can be well retained after 6 recycles, showing an excellent reversible adsorption capacity. The POP-Py also shows superior separation performance for SO2 from a ternary SO2/CO2/N2 mixture (0.17/15/84.83v%), giving a breakthrough time and a saturated SO2 capacity at 178 min g-1 and 0.4 mmol g-1. The retention time was well maintained even under high moisture conditions, confirming its superior water resistance. Furthermore, when other vinyl-functionalized organic ligand monomers (bipyridine, pyrimidine, and pyrazine) were employed for radical polymerization, all of the resultant porous organic ligand polymers (POP-BPy, POP-PyI, and POP-PyA) exhibited superior performance for reversible adsorption and efficient separation of SO2. The combined features of reversible adsorption, efficient separation, and water resistance are important for the industrial applications of these materials as SO2 adsorbents.

Different functional groups modified porous organic polymers used for low concentration CO2 fixation.

Through a facile post-synthetic method, different kinds of polar group-functionalized ionic liquid porous organic polymers (POP-PA-COOH, POP-PA-OH, and POP-PA-NH2) were obtained. The materials can be used as efficient heterogeneous catalysts in the cycloaddition reaction of CO2 with epoxides under mild and co-catalyst-free conditions. It is demonstrated that POP-PA-NH2 possesses much higher catalytic activity than POP-PA-OH and POP-PA-COOH. Interestingly, this activity difference can further be amplified when the reaction is carried out under low CO2 concentration, and POP-PA-NH2 possesses a conversion of 84.7% with a selectivity of 99.0% in 96 h. It is noteworthy to mention that research focusing on the transformation of CO2 under low concentration using heterogeneous catalysts is rare and still a challenge. The excellent activities of POP-PA-NH2 under low CO2 concentration make this material a good candidate for CO2 elimination under mild conditions.

Metalated Porous Phenanthroline-Based Polymers as Efficient Heterogeneous Catalysts for Regioselective C-H Activation of Heteroarenes.

Direct C-H bond activation of heterocycles as a step-economical and environmentally friendly approach to build the heterobiaryls motifs is highly attractive, but it still has a challenge to design and prepare a cheap and regioselective heterogeneous catalyst. To tackle this challenge, we have introduced Ni species into a porous phenanthroline-based organic polymer donated as POP-Phen@Ni. This heterogeneous catalyst shows excellent catalytic performances in regioselective C-H activation of heterocycles, even better than those of the corresponding homogenous catalyst. H/D exchange experiments show that the lithium bis(trimethylsilyl)amide (LiHMDS), a base added in the reaction, play a very important role during the reaction processes. We believe that this heterogeneous catalyst would open a new door for design of heterogeneous catalysts to efficiently catalyze the regioselective C-H activation of heterocycles.

Effects of O-1602 and CBD on TNBS-induced colonic disturbances.

BACKGROUND: This study attempted to provide the effects and mechanisms of two cannabinoids, O-1602 and cannabidiol (CBD), on colonic motility of 2,4,6-trinitro-benzene sulfonic acid (TNBS) colitis. METHODS: TNBS was used to induce the model of motility disorder. G protein-coupled receptor 55 (GPR55) expression was detected using real-time PCR and immunohistochemistry in colon. Pro-inflammatory cytokines and myeloperoxidase were also measured. The colonic motility was measured by upper GI transit in vivo and recorded using electrical stimulation organ bath technique in vitro. Freshly isolated smooth muscle from the rat colon were applied to determine the membrane potential and Ca2+ -ATPase activity, respectively. KEY RESULTS: CBD or O-1602 separately improved inflammatory conditions significantly in TNBS-induced colitis rats. However, sole CBD pretreatment reduced GPR55 expression, which was up-regulated in TNBS colitis. O-1602 and CBD each lowered MPO and IL-6 levels remarkably in TNBS colitis, while TNF-α levels experienced no change. CBD rescued the downward colonic motility in TNBS colitis in vivo; however, it decreased the upward contraction of the smooth muscle strip under electrical stimulation in vitro. Pretreatment with CBD prevented against TNBS-induced changes of Ca2+ -ATPase activity of smooth muscle cells. However, membrane potential of the smooth muscle cells decreased by TNBS experienced no change after O-1602 or CBD import. CONCLUSIONS & INFERENCES: The present study suggested that CBD participated in the regulation of colonic motility in rats, and the mechanisms may be involved in the regulation of inlammatory factors and Ca2+ -ATPase activity through GPR55.

Chiral induction, memory, and amplification in porphyrin homoaggregates based on electrostatic interactions.

Supramolecular chirality in two configurational homoaggregates of anionic meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) can be induced by D- and L-alanine in acidic water (see picture). The chirality can be further memorized and enforced through strong electrostatic interactions between TPPS aggregates and achiral poly(allylamine) [PAA].Supramolecular chirality in two configurational homoaggregates of anionic meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) can be induced by D- and L-alanine (Ala) in acidic water, respectively. The induced supramolecular chirality can be further memorized and enforced, even after complete removal of Ala or in the presence of excess Ala with the opposite configuration, through strong electrostatic interactions with achiral poly(allylamine) [PAA]. The ionic chiral interactions between TPPS and Ala or PAA are characterized by means of UV/Vis absorption and circular dichroism spectrometry. Fluorescence spectroscopy and atomic force microscopy are used as complementary techniques. On the basis of the comprehensive experimental results, a possible mechanism for chiral induction, memory, and amplification of TPPS homoaggregates by chiral amino acids and achiral PAA is proposed. Thus, we demonstrate a novel strategy to realize chiral memory in supramolecular systems by polyelectrolytes through hierarchical electrostatic self-assembly.

Optimal synthesis of a direct Z-scheme photocatalyst with ultrathin W18O49 nanowires on g-C3N4 nanosheets for solar-driven oxidation reactions.

Constructing Z-scheme photocatalysts is an effective approach to enhance the conversion efficiency of solar to chemical energy. Herein, W18O49/g-C3N4 heterostructures have been synthesized by growing W18O49 ultrathin nanowires on g-C3N4 nanosheets via a convenient solvothermal process. Various characterizations were performed on the materials to understand the structure-performance relationship. The photocatalytic properties of the W18O49/g-C3N4 heterostructures were evaluated by the two oxidation reactions, phenol degradation and oxidative NC coupling of benzylamines, under a simulated sunlight (360 ≤  λ  ≤ 780 nm). With tuning the W18O49/g-C3N4 mass ratio, the optimal photocatalyst of W18O49(30)/g-C3N4 containing 30 wt% W18O49 nanowires exhibited the highest activity in both the photocatalytic reactions. The generations and contributions of the active species in the photocatalytic reactions were identified by electron spin resonance (ESR) spectra and active-species-eliminating experiments. Accordingly, the photocatalytic mechanism of W18O49/g-C3N4 heterostructures has been expounded based on the direct Z-scheme electron transfer between the two semiconductors as well as the synergistic actions of active sites on W18O49 nanowires and g-C3N4 nanosheets. This work demonstrates a rational paradigm to construct 1D/2D semiconductor heterostructures and provides further insights into Z-scheme photocatalytic mechanism for boosting solar-driven pollutant degradation and organic transformation.

[Photolysis Mechanism of p-Nitrophenol by Nitrocellulose Membrane in Aqueous Solution].

To investigate the potential application of nitrocellulose membrane (NCM) in water treatment, this study examined the photolysis of p-nitrophenol, with NCM as the source of reactive oxygen species. Effects of solution pH, light conditions, and water dissolved substances on p-nitrophenol photolysis were investigated, and possible mechanisms were discussed. The results demonstrated that the quantum yield for hydroxyl radicals from the NCM was 1.30×10-4, which is approximately 1.86 times higher than that from TiO2. The photolysis rate of p-nitrophenol in the presence of NCM was 0.0055 min-1, which is much higher than that in pure water (9.52×10-4 min-1). This promotion was mainly caused by photo-induced generation of ·OH on NCM surface under light, in which UVA plays an important role in photolysis. The photolysis rate of p-nitrophenol increased with the increase of light intensity and membrane area. Acidic solution (pH=2.0) was preferred for the degradation of p-nitrophenol, with a photolysis rate of 0.0165 min-1; the corresponding degradation of p-nitrophenol exceeded 90% in 120 min. The effects of dissolved substances on photolysis were significantly different. NO3- promoted photolysis by generation of ·OH, and dissolved organic matter decreased photolysis through light attenuation. The intermediate products of gas chromatography-mass spectrometry analysis mainly included phenol, hydroquinone, malonic acid, and oxalic acid, and the possible photolysis pathway was given accordingly.