Dual Functional Groups Research Articles

Room-temperature synthesis of covalent organic frameworks with dual functional groups for high-performance adsorption of diclofenac sodium from aqueous solution

Diclofenac sodium (DCF) are commonly found in ambient waterways due to its widespread use, and this poses significant risks to both human health and ecosystems. In this study, we have designed and synthesized a series of imine-linked covalent organic frameworks (COFs) with dual functional groups using a triple assembly strategy. Specifically, the platform molecules 2,5-dimethoxyterephthalaldehyde (DMTP), 2,5-dihydroxyterephthalaldehyde (DHTP), and 1,3,5-tris(4-aminophenyl)benzene (TAPB) were employed for the direct fabrication of COFs through Schiff base condensation reactions. As a proof of concept, three room-temperature synthesized COFs (COF TAPB-DMTP-[OH]n, where n represents the molar mass of DHTP, with n values of 0.02, 0.03, and 0.04) were used for DCF adsorption from water. The adsorption isotherms, kinetics, pH effects, ionic strength, co-existing ions, and COF regeneration for DCF were thoroughly investigated. The incorporation of methoxy (-OMe) and hydroxyl (-OH) groups serves as a functional strategy to facilitate hydrogen bonding interactions with DCF molecules. Consequently, the developed COFs, featuring an ultrahigh surface area and mesoporous structure, demonstrated a maximum adsorption capacity of 413.2 mg/g and a rate constant k2 of 0.0435 g/mg/min, which exceeds the performance of the majority of previously described adsorbents. The adsorption capacity toward DCF remained nearly unchanged after five regeneration cycles of the COF. Furthermore, the self-prepared adsorbent demonstrated efficient adsorption of DCF from real environmental water, indicating its potential for practical DCF removal applications.

Diverse Approaches for the Difunctionalization of PPH Dendrimers, Precise Versus Stochastic: How Does this Influence Catalytic Performance?

Random difunctionalization of dendrimer surfaces, frequently employed in biological applications, provides the advantage of dual functional groups through a synthetic pathway that is simpler compared to precise difunctionalization. However, is the random difunctionalization as efficient as the precise difunctionalization on the surface of dendrimers? This question is unanswered to date because most dendrimer families face challenges in achieving precise functionalization. Polyphosphorhydrazone (PPH) dendrimers present a unique opportunity to obtain precise difunctionalization at each terminal branching point. The work concerning catalysis we report with PPH dendrimers, whether precisely or randomly functionalized, addresses this question. Across PPH dendrimers, from generations 1 to 3, precise functionalization consistently outperforms random functionalization in terms of efficiency. This finding introduces a novel concept in dendrimer science, emphasizing the superiority of precise over random functionalization methodologies. Introducing a groundbreaking concept in the field of dendrimers.

Synthesis of Pyridin-2(1H)-imines via the Transformation of Conjugated Ynones.

Conjugated ynones represent an important class of reactive species, useful synthetic intermediates, and synthons. However, the reactivity and synthetic applications of ynones are usually focused on the transformation of mono- or dual-functional groups. Herein, we developed a straightforward synthesis of pyridin-2(1H)-imines from the transformation of conjugated ynones. This cascade process probably began with a Michael addition of ynones and 2-aminopyridines, further underwent an intramolecular cyclization to generate the N,O-bidentate intermediates, and finally reacted with sulfonyl azides giving the pyridin-2(1H)-imines with accompanying loss of diazo.

Crystallization management and defect passivation via additive engineering for efficient and stable carbon-based CsPbI2Br perovskite solar cells

Inorganic CsPbI2Br perovskite solar cells (PSCs) have attracted enormous interest due to their excellent thermal stability and immense potential for application in tandem solar cells. However, the rambunctious crystallization and poor film quality of inorganic CsPbI2Br perovskite are the main factors limiting their performance improvement. Herein, dibenzoylmethane (DBM), containing electron-rich and dual CO functional groups, as an efficient precursor additive, is first introduced to regulate the crystallization of CsPbI2Br perovskite while passivating its associated defects. After DBM modification, nucleation is accelerated and the crystallinity of CsPbI2Br film is improved, thus promoting the phase stability. Additionally, DBM can passivate uncoordinated Pb2+ defects, thereby significantly reducing non-radiative recombination, and can also decrease the energy level difference between CsPbI2Br/Carbon. As a result, when DBM additive is incorporated in the CsPbI2Br, the power conversion efficiency (PCE) of the device with the fluorine doped tin oxide glass (FTO)/SnO2/CsPbI2Br/Carbon structure is significantly improved to 13.46 %, an increase of nearly 13 % compared to the control device (11.72 %). The unpackaged devices exhibit excellent air and thermal stability, still remaining over 90 % of its initial PCE after aging for 500 h under ambient conditions, or continuous heating at 65 °C in glovebox for 500 h, respectively.

Pressure-driven multiple optoelectronic evolution in CsMoO3(IO3) with dual functional [MoO6] and [IO3] groups

Pressure-induced optoelectronic changes were observed in CsMoO3(IO3) by evolutions of dual functional groups, including piezochromism, second harmonic generation transformation, and the enhancement of the photocurrent switching ratio.

Coordination-assembled phosphorescent microstructure from RTP HOF and Eu3+-doping ZGO:Mn phosphors for cancer biomarker amplification detection and information encryption

The ultra-long room temperature phosphorescent hydrogen-bonded organic framework (RTP HOF) materials can achieve long afterglow via ligand hydrogen bond interaction and water implement to suppress the non-radiative decays by matrices rigidification, and its electron donor conjugated structure is first developed as a phosphorescent quencher. The Eu3+/Mn2+ co-doped Zn2GeO4 phosphors (ZGO:Mn, Eu) with abundant metal sites and enhanced phosphorescence were synthesized as response factors and electron acceptors, combined with RTP HOFs to form microstructures featuring multi-color modulation, as an high-level anti-counterfeiting platform and lysophosphatidic acid (LPA) detection unit. LPA is an ideal plasma biomarker for early diagnosis of ovarian and other gynecologic cancers. This detection strategy relies on the differential coordination substitution to restore ZGO:Mn, Eu phosphorescence through synergistic coordination of LPA and the hydrophobic assistance of LPA, and dual functional groups identification of LPA achieve specific detection at the nanomolar level. The anti-counterfeiting platform can fetch specific information by controlling the afterglow distinction and excited light from ZGO:Mn, Eu and RTP HOF. This study not only provides a typical case of the preparation of two phosphors with heterogeneous optical properties, but also expands the application field of combined phosphors as intelligent luminescent materials.

Methyl Oleate-Alkylated Tetralin with Dual-Functional Groups as Base Oil with PAO to Improve the Performance of Lithium-Based Grease

Methyl Oleate-Alkylated Tetralin with Dual-Functional Groups as Base Oil with PAO to Improve the Performance of Lithium-Based Grease

Incorporating Anticoagulant and Antiplatelet Dual Functional Groups into Thermosetting Polymer Chain for Enhancing Antithrombogenicity.

In clinical practice, high-effective antithrombosis remains a challenge for blood-contacting medical devices. Inspired by the enhanced antithrombogenicity of anticoagulant and antiplatelet combination therapy, a strategy is proposed to synthesize dual-pathway antithrombotic polymers by incorporating anticoagulant and antiplatelet dual functional groups into a single thermosetting polymer chain. The synthesized polymer shows increased antithrombogenicity in vitro, with prolonged activated partial thromboplastin time (APTT) and decreased platelet adhesion. Additionally, it downregulates the expression of coagulation- and inflammation-related factors in rabbit plasma after ex vivo arteriovenous shunt assay and maintains patency of small vascular grafts for at least 6 months without thrombosis on the luminal surface after invivoreplacement of rabbit carotid artery. Thiswork provides a new approach to producing novel antithrombotic polymers for blood-contacting medical devices.

Super hydrophilic-electrons acceptor regulated rutile TiO2 nanorods for promoting photocatalytic H2 evolution

Photocatalytic H2 evolution from water splitting in liquid–solid two-phase requires an efficient photocatalyst with excellent ability of charge separation and reactant molecular diffusion.In this study, the super hydrophilic-electrons acceptor with abundant –C=O and –OH functional groups were evenly grafted onto rutile TiO2 nanorods surface to speed up the charge separation and water molecular diffusion, respectively. The photocatalytic results showed that the TiO2-CA grafted by citric acid (with three –C=O, three carboxy-(–OH) and one alcohol-(–OH)) presented a 1.48° contact angle and a distinct increased H2-production activity (48.5 mmol·h−1·g−1), whereas the TiO2-PA grafted by propane-1,2,3-tricarboxylicacid (Just lack of one alcohol-(–OH) compared with TiO2-CA) showed a 30.95° contact angle and a decreased H2-production activity (19.3 mmol·h−1·g−1) compared to the unmodified TiO2 (25.8 mmol·h−1·g−1), indicating that the super hydrophilic-electrons acceptor is vitally important to the photocatalytic activity of TiO2. Based on the present results, the carbonyl group (–C=O) possess a stronger reducing capability and act as “electrons acceptor”, while the only alcohol-hydroxyl group (–OH) in TiO2-CA can decrease the mass transfer resistance and serve as “super hydrophilic absorber”. Considering its mild preparation, inexpensive cost, and admirable efficiency, the super hydrophilic-electrons acceptor with dual functional groups regulated TiO2 can become a promising way for potential application in photocatalytic field.

Post-synthesis introduction of dual functional groups in metal–organic framework for enhanced adsorption of moxifloxacin antibiotic

Highly effective removal of antibiotics from aqueous solution is of importance while still faces challenge. Herein, we report a novel metal–organic framework (MOF) adsorbent, MOF-808-SIPA (SIPA, 5-sulfoisophthalic acid), constructed via post-synthesis exchange strategy. On the basis, dual active groups including sulfonic acid and carboxyl groups are successfully introduced. The novel MOF-808-SIPA exhibits a high adsorption capacity of 287.1 mg g−1 for moxifloxacin hydrochloride (MOX·HCl), superior to that (174.6 mg g−1) of the pristine MOF-808-AA (AA, acetic acid). Besides, MOF-808-SIPA shows rapid adsorption equilibrium of ∼ 30 min, strong anti-interference ability from pH and inorganic ions, and feasible regeneration. The superiority renders MOF-808-SIPA a potential adsorbent for MOX removal. Density function theory (DFT) calculation and experiment confirm that H-bond interaction contributes largely to the excellent adsorption in MOF-808-SIPA. Our work provides a guideline for designing high-efficiency MOF-based adsorbent.

Theoretical Study of the Electrochemical Properties for Solid Electrolytes Containing Ethoxy and Carbonate Groups

The density functional theory calculations are performed to investigate the redox properties of dual functional groups polymer (polycarbonate possessing ethoxy side groups (PEtGEC), poly(diethylene glycol carbonate) (PDEC), poly(triethylene glycol carbonate) (PTEC)) electrolytes containing carbonate and ethoxy groups, and coordination structures and interactions of Li+ ions with polymers. The oxidation and reduction processes of dual functional groups polymers occur on the ethoxy and carbonate groups, respectively. The electrochemical windows of PEtGEC (4.08 V) and PDEC (4.42 V) electrolytes are predicted by calculations. The oxidation potentials of electrolytes are defined by the polymers, and the electrolytes without branched chains have better oxidation stability. The reduction potentials are controlled by the salt anion, and the structure of lithium salt changes during the reduction process. The simulated infrared spectra show that Li+ ions interact with the carbonyl and ether oxygen atoms of polymers. The number of oxygen atoms that coordinate with the Li+ ion in these electrolytes is 4–5. The PEtGEC electrolyte has favorable transport ability due to its loose coordination environment and easy formation, the transformation between configurations, the dual-path of Li+ ions transport and good long range transport ability. These findings provide theoretical guidance for designing solid electrolytes in the future.

Regio- and Stereoselective Addition to gem-Difluorinated Ene-Ynamides: Access to Stereodefined Fluorinated Dienes.

The first synthesis of gem-difluorinated ene-ynamides is presented via deprotonation of trifluoromethylated N-allenamides and δ extrusion of fluorine. These highly reactive building blocks, owing to their dual functional groups, offer a unique entry to difluorinated dienes and to stereodefined, monofluoro-substituted dienes. Stereoselective addition to the ynamide moiety led to difluorinated dienes. A stereocontrolled domino δ elimination reaction followed by an addition/elimination sequence from trifluoromethylated N-allenamides provided exclusively stereodefined monofluorinated ene-ynamides.

Facile Li-ion conduction and synergistic electrochemical performance via dual functionalization of flexible solid electrolyte for Li metal batteries

Herein, a novel polymer electrolyte membrane based on poly(arylene ether sulfone)-g- poly(vinylethylene carbonate)/poly(ethylene glycol) (PAES-g-PVEC/PEG) combined with 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide was prepared to achieve the superior electrochemical performance with good thermal and mechanical stability. The synergistic effect was provided for the lithium ion transport and electrochemical performance by the dual functional groups of polyether and polycarbonate grafted on the rigid PAES backbones. The membrane containing 30 mol% PVEC and 70 mol% PEG exhibited the ionic conductivity of 0.81 × 10 − 3 S cm −1 and Li + transference number of 0.65 at room temperature, maintaining the thermal and mechanical stability in the flexible solid state. As this membrane illustrated a good interfacial compatibility with Li metal electrode, the LiFePO 4 ||Li cell demonstrated an outstanding cycling discharge capacity of ∼151 mA h g −1 and the coulomb efficiency 99% after 100 cycles under 0.1C. Based on this excellency, the PAES-g-PVEC/PEG electrolyte herein synthesized is considered to be a promising candidate for the application of all-solid-state lithium metal batteries with high power and energy density. • PAES-g-PVEC/PEG was synthesized to prepare flexible solid electrolyte membranes. • Enhanced single Li + conduction was realized by dual functional grafts. • It exhibited Li + conductivity of 0.81 × 10 −3 S cm −1 and transference number of 0.65. • It showed quite low interfacial resistance with Li metal anode.

Simple carbonaceous-material-loaded mesoporous SiO2 composite catalyst for epoxide-CO2 cycloaddition reaction

In this paper, a novel arginine-glucose derived carbonaceous-material-loaded SiO2 composite catalyst (Ar-G-CM/SiO2) was synthesized from non-toxic and harmless reagents (arginine, glucose and tetraethylorthosilicate) by simple hydrothermal process. Mesoporous SiO2 with high specific area served as support for carbonaceous material and provided extra hydrogen bond donor (HBD) groups. Ar-G-CM/SiO2 with acid-base dual functional groups (COOH, NH2) and HBD group (OH) presented 62% yield and 99% selectivity to product of propylene carbonate in CO2 cycloaddition reaction with propylene oxide even at 40 °C, 2 MPa under metal-absent and solvent-free conditions. For some less active epoxides with steric hindrance, Ar-G-CM/SiO2 also showed good yield and selectivity over 90% by raising temperature to 120 °C. Furthermore, the Ar-G-CM/SiO2 catalyst could be reused for six successive cycles without significant decrease in catalytic activity or structural deterioration, because the carbon deposition was restrained owing to the mesoporous structure of the catalyst.

A novel poly (amic-acid) modified single-walled carbon nanohorns adsorbent for efficient removal of uranium (VI) from aqueous solutions and DFT study

Poly(amic-acid) modified single-walled carbon nanohorns (PAA/SWCNH-COOH) contained dual-functional groups (amide and carboxyl) were synthesized by in-situ polymerization and used for the elimination of uranium (VI). It was found that the adsorption capacity of SWCNH-COOH increased significantly after grafting PAA chains, and the theoretical monolayer adsorption capacity of PAA/SWCNH-COOH could reach 216.0 mg/g. The adsorption capacity of this material could remain up to 90% of the initial value after 5 times of reuse. Moreover, PAA/SWCNH-COOH has an excellent adsorption selectivity, which could be attributed to the synergistic adsorption effects between amide and carboxyl groups. To further study the interaction mechanism between uranium ions and the adsorbents, the quantum chemical calculations were performed using DFT method. The simulation results show that both amide and carboxyl groups have a strong interaction with uranium ions, which ensures the high adsorption capacity of this material. This research proved that the PAA/SWCNH-COOH is a promising adsorption material for removing uranium from wastewater and it also sheds a light on the interaction mechanism between bifunctional adsorbents and uranium ions.

Anion Exchange Ionomers: Impact of Chemistry on Thin‐Film Properties

AbstractIonomer thin‐films (i.e., 20–100 nm) on supports serve as model systems to understand ionomer‐catalyst interfacial behavior as well as the confinement‐driven deviation in properties from bulk membranes. While ionomer thin‐films have been examined for proton exchange ionomers, the thin‐film properties of anion exchange ionomers (AEIs) remain largely unexplored. More importantly, delineating the convoluted impact of chemistry and confinement on thin‐film morphology and hydration is of interest to advancing the field on functional ionic interfaces. In this work, these aspects are studied by using AEIs of different backbones (perfluorinated, aliphatic, and aromatic) and side chains (various lengths, and single versus dual functional groups). Quartz‐crystal microbalance and spectroscopic ellipsometry are used to analyze density and coupled with calculated free volume fraction of thin‐films to provide insights on their gas transport properties. AEI side‐chain's chemical character plays a key role in how confinement modulates hydration (in thin‐film versus bulk). The results elucidate the effects of backbone, side‐chain chemistry versus anion/cation type in the confinement‐driven changes in thin‐film morphology and swelling. This study also provides new insights for tuning AEI transport functionalities at interfaces via chemistry, which can benefit the design and development of electrode‐ionomers for alkaline membrane‐based energy systems.

Synergistic Engineering of Natural Carnitine Molecules Allowing for Efficient and Stable Inverted Perovskite Solar Cells

Efficient control of the perovskite crystallization and passivation of the defects at the surface and grain boundaries of perovskite films have turned into the most important strategies to restrain charge recombination toward high-performance and long-term stability of perovskite solar cells (PSCs). In this paper, we employed a small amount of natural vitamin B (carnitine) with dual functional groups in the MAPbI3 precursor solution to simultaneously passivate the positive- and negative-charged ionic defects, which would be beneficial for charge transport in the PSCs. In addition, such methodology can efficiently ameliorate crystallinity with texture, better film morphology, high surface coverage, and longer charge carrier lifetime, as well as induce preferable energy level alignment. Benefiting from these advantages, the power conversion efficiency of PSCs significantly increases from 16.43 to 20.12% along with not only a higher open-circuit voltage of 1.12 V but also an outstanding fill factor of 82.78%.

A porous nano-adsorbent with dual functional groups for selective binding proteins with a low detection limit.

In this study, porous silica nanoparticles functionalized with a thiol group (SiO2–SH NPs) were synthesized via a one-pot method. Subsequently, iminodiacetic acid was modified, and further adsorption of Ni2+ ions was conducted to obtain a SiO2–S/NH–Ni nano-adsorbent. Then, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TG) and X-ray diffraction (XRD) were employed to characterize its morphology and composition. The results indicate that the SiO2–S/NH–Ni nano-adsorbent is porous, has an average diameter of 77.1 nm and has a small porous structure of about 3.7 nm in the silica skeleton. The Brunauer–Emmett–Teller (BET) surface area and total pore volume were 537.2 m2 g−1 and 3.3 cm3 g−1, respectively, indicating a large BET surface area. The results indicate that the as-prepared SiO2–S/NH–Ni nano-adsorbent would be suitable to selectively and efficiently bind His-tagged proteins from an E. coli cell lysate. The SDS-PAGE results show that the as-prepared nano-adsorbent presents specifically to both His-tagged CPK4 and His-tagged TRX proteins, indicating the nano-adsorbent can be used to effectively separate His-tagged proteins and is universal to all His-tagged fusion proteins. We also found that the as-prepared nano-adsorbent exhibits a low detection limit (1.0 × 10−7 mol L−1) and a strong regeneration ability based on four regeneration experiments that were particularly suited to the separation of His-tagged proteins.

Polymer electrolyte with dual functional groups designed via theoretical calculation for all-solid-state lithium batteries

Solid polymer electrolytes (SPEs) have great potential to solve the safety issue of lithium batteries, nevertheless, the design of SPE with well comprehensive performance has always been a formidable challenge. As we know, in the polymer different groups have different functions, and there are complex interactions between them. Hence, the roles of various functional groups in electrolytes is too complex to be clearly understood, which restricts the structural design of SPE by experience. Herein, theoretical calculations are conducted in designing polymer electrolyte with dual functional groups of ethylene carbonate (EC) and ethyoxyl (EO) group, revealing the interaction between lithium ions and different groups as well as the lithium ions migration mechanism. Designed SPE demonstrates high conductivity of 1.84 × 10−4 S cm−1 (30 °C), and wide electrochemical window of 4.75 V. Combining with in-situ interface modification technology, the SPE not only prolongs solid-state LiFePO4 (LFP)/Li battery cycle life to 600 cycles (110 mA h g−1 retained), but also shows potential application in high energy density LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode and Si anode batteries. In this work, theoretical calculation is demonstrated to be a high effective method for constructing the functional groups of polymer electrolyte matrix.

Synthesis optimization of hybrid anion exchanger containing triethylamine functional groups and hydrated Fe(III) oxide nanoparticles for simultaneous nitrate and phosphate removal

The excessive discharge of nutrient into natural water can cause detrimental eutrophication effect to the ecological system. For the nutrient removal, there is quite challenging to simultaneously remove trace phosphate usually exists at level <2.0 mg/L and high concentration of nitrate exists at level 100 mg/L under the presence of competing background ions. In this study, the novel hybrid polymeric anion exchanger impregnated with hydrated Fe(III) oxide (HFO) nanoparticles (HA520E-Fe) was synthesized, characterized, and evaluated preliminary performance for co-removal of trace nitrate and phosphate. HA520E-Fe composes of dual functional groups; triethylamine that selective for nitrate ions through the ion exchange mechanism and HFO nanoparticles that selective for phosphate adsorption through Lewis acid based (LAB) interactions. During the HFO loading process, low dielectric constant solution preferred ethanol was used as aqueous medium to reduce the Donnan exclusion effect (i.e., repulsion between Fe3+ ions and triethylamine functional groups) and thus enhances HFO formation inside the parent anion exchange resin. Upto 5 loading cycles can enhance the phosphate removal capacity without sacrifice the nitrate take up capacity. HA520E-Fe was further characterized by SEM-EDX, HR-TEM, XRD, and EXAFS. The HFO nanoparticles were uniformly dispersed throughout the pore structure at approximately 12.45 %w/w with size well below 50 nm. From XRD diffractograms, the HFO inside the material retains high surface area of amorphous phase even after 5th cyclic sorption-desorption runs. Preliminary performance studies using equilibrium batch tests including effect of feed pH, pHPZC, and sorption isotherms, and fixed-bed column runs were also evaluated. The novel HA520E-Fe exhibits high removal capacity for simultaneous sorption of nitrate and phosphate and can be applied in various applications such as secondary effluent, including aquacultures wastewater.