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1.
Immunol Rev ; 320(1): 138-146, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37366589

RESUMEN

Chimeric antigen receptor (CAR)-T cell therapy has emerged as a promising approach for cancer treatment. CAR is a synthetic immune receptor that recognizes tumor antigen and activates T cells through multiple signaling pathways. However, the current CAR design is not as robust as T cell receptor (TCR), a natural antigen receptor with high sensitivity and efficiency. TCR signaling relies on specific molecular interactions, and thus electrostatic force, the major force of molecular interactions, play critical roles. Understanding how electrostatic charge regulates TCR/CAR signaling events will facilitate the development of next-generation T cell therapies. This review summarizes recent findings on the roles of electrostatic interactions in both natural and synthetic immune receptor signaling, specifically that in CAR clustering and effector molecule recruitments, and highlights potential strategies for engineering CAR-T cell therapy by leveraging charge-based interactions.


Asunto(s)
Neoplasias , Humanos , Electricidad Estática , Receptores de Antígenos de Linfocitos T/metabolismo , Linfocitos T , Inmunoterapia Adoptiva
2.
RNA ; 29(7): 1007-1019, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37001915

RESUMEN

The multifunctional RNA recognition motif-containing protein Y14/RBM8A participates in mRNA metabolism and is essential for the efficient repair of DNA double-strand breaks (DSBs). Y14 contains highly charged, low-complexity sequences in both the amino- and carboxy-terminal domains. The feature of charge segregation suggests that Y14 may undergo liquid-liquid phase separation (LLPS). Recombinant Y14 formed phase-separated droplets, which were sensitive to pH and salt concentration. Domain mapping suggested that LLPS of Y14 involves multivalent electrostatic interactions and is partly determined by the net charge of its low-complexity regions. Phospho-mimicry of the carboxy-terminal arginine-serine dipeptides of Y14 suppressed phase separation. Moreover, RNA could phase separate into Y14 droplets and modulate Y14 LLPS in a concentration-dependent manner. Finally, the capacity of Y14 in LLPS and coacervation with RNA in vitro correlated with its activity in DSB repair. These results reveal a molecular rule for LLPS of Y14 in vitro and an implication for its co-condensation with RNA in genome stability.


Asunto(s)
Arginina , ARN , ARN/genética , Arginina/química , Dominios Proteicos , Proteínas de Unión al ARN/metabolismo , Reparación del ADN
3.
J Virol ; 98(3): e0000724, 2024 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-38305153

RESUMEN

Pseudorabies virus (PRV) is the causative agent of Aujeszky's disease, which is responsible for enormous economic losses to the global pig industry. Although vaccination has been used to prevent PRV infection, the effectiveness of vaccines has been greatly diminished with the emergence of PRV variants. Therefore, there is an urgent need to develop anti-PRV drugs. Polyethylenimine (PEI) is a cationic polymer and has a wide range of antibacterial and antiviral activities. This study found that a low dose of 1 µg/mL of the 25-kDa linear PEI had significantly specific anti-PRV activity, which became more intense with increasing concentrations. Mechanistic studies revealed that the viral adsorption stage was the major target of PEI without affecting viral entry, replication stages, and direct inactivation effects. Subsequently, we found that cationic polymers PEI and Polybrene interfered with the interaction between viral proteins and cell surface receptors through electrostatic interaction to exert the antiviral function. In conclusion, cationic polymers such as PEI can be a category of options for defense against PRV. Understanding the anti-PRV mechanism also deepens host-virus interactions and reveals new drug targets for anti-PRV.IMPORTANCEPolyethylenimine (PEI) is a cationic polymer that plays an essential role in the host immune response against microbial infections. However, the specific mechanisms of PEI in interfering with pseudorabies virus (PRV) infection remain unclear. Here, we found that 25-kDa linear PEI exerted mechanisms of antiviral activity and the target of its antiviral activity was mainly in the viral adsorption stage. Correspondingly, the study demonstrated that PEI interfered with the virus adsorption stage by electrostatic adsorption. In addition, we found that cationic polymers are a promising novel agent for controlling PRV, and its antiviral mechanism may provide a strategy for the development of antiviral drugs.


Asunto(s)
Antivirales , Herpesvirus Suido 1 , Polietileneimina , Electricidad Estática , Animales , Adsorción/efectos de los fármacos , Antivirales/química , Antivirales/farmacología , Herpesvirus Suido 1/efectos de los fármacos , Herpesvirus Suido 1/metabolismo , Polietileneimina/química , Polietileneimina/farmacología , Seudorrabia/tratamiento farmacológico , Seudorrabia/virología , Porcinos/virología , Enfermedades de los Porcinos/virología
4.
Proc Natl Acad Sci U S A ; 119(42): e2206685119, 2022 10 18.
Artículo en Inglés | MEDLINE | ID: mdl-36215508

RESUMEN

Liquid embolic agents are widely used for the endovascular embolization of vascular conditions. However, embolization based on phase transition is limited by the adhesion of the microcatheter to the embolic agent, use of an organic solvent, unintentional catheter retention, and other complications. By mimicking thrombus formation, a water-soluble polymer that rapidly glues blood into a gel without triggering coagulation was developed. The polymer, which consists of cationic and aromatic residues with adjacent sequences, shows electrostatic adhesion with negatively charged blood substances in a physiological environment, while common polycations cannot. Aqueous polymer solutions are injectable through clinical microcatheters and needles. The formed blood gel neither adhered to the catheter nor blocked the port. Postoperative computed tomography imaging showed that the polymer can block the rat femoral artery in vivo and remain at the injection site without nontarget embolization. This study provides an alternative for the development of waterborne embolic agents.


Asunto(s)
Embolización Terapéutica , Agua , Animales , Embolización Terapéutica/métodos , Polímeros , Ratas , Solventes , Electricidad Estática , Agua/química
5.
Small ; : e2405415, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39225371

RESUMEN

Solvent additives with a high boiling point (BP) and low vapor pressure (VP) have formed a key handle for improving the performance of organic solar cells (OSCs). However, it is not always clear whether they remain in the active-layer film after deposition, which can negatively affect the reproducibility and stability of OSCs. In this study, an easily removable solvent additive (4-chloro-2-fluoroiodobenzene (CFIB)) with a low BP and high VP is introduced, behaving like volatile solid additives that can be completely removed during the device fabrication process. In-depth studies of CFIB addition into the D18-Cl donor and N3 acceptor validate its dominant non-covalent intermolecular interactions with N3 through effective electrostatic interactions. Such phenomena improve charge dynamics and kinetics by optimizing the morphology, leading to enhanced performance of D18-Cl:N3-based devices with a power conversion efficiency of 18.54%. The CFIB-treated device exhibits exceptional thermal stability (T80 lifetime = 120 h) at 85 °C compared with the CFIB-free device, because of its morphological robustness by evolving no residual CFIB in the film. The CFIB features a combination of advantages of solvent (easy application) and solid (high volatility) additives, demonstrating its great potential use in the commercial mass production of OSCs.

6.
Small ; 20(25): e2306543, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38196152

RESUMEN

The fabrication of flexible composites by integrating metal-organic frameworks (MOFs) with flexible substrates is a critical strategy for developing advanced materials with excellent feasibility and processability. These flexible MOF-based composites play a particularly important role in the separation and purification processes. However, several drawbacks remain challenge to overcome such as long processing time, high-cost, complicated processes, or harsh reaction conditions. In this paper, a convenient and efficient method is reported for fabricating MOF/fiber composites using a simple drop-and-drain (D&D) process. By exploiting the electrostatic interactions between the positively charged MOF particles and negatively charged fiber-based flexible substrates, a uniform coating of MOF on flexible fibers are achieved. This is accomplished by allowing the MOF ink to drop and drain through a substrate using a custom-made Teflon cell. Additionally, the D&D method enables the production of multiple layers of composites in a single-step process. UiO-66 and ZIF-8 submicroparticles and various substrates such as cotton-pad, cotton-fabric, nylon-fabric, PET-fabric, and filter-paper are employed to create flexible MOF/fiber composites. These composites demonstrate outstanding capacities for capturing negatively charged organic dyes, including methyl orange and indigo carmine. Furthermore, the MOF/fiber composites can be reused for dye capture after a simple washing process.

7.
Arch Biochem Biophys ; 754: 109959, 2024 04.
Artículo en Inglés | MEDLINE | ID: mdl-38490311

RESUMEN

Electrical synapses are essential components of neural circuits. Neuronal signal transduction across electrical synapses is primarily mediated by gap junction channels composed of Connexin36 (Cx36), the lack of which causes impaired electrical coupling between certain neurons including cortical interneurons and thalamic reticular nucleus (TRN) neurons. However, the structural basis underlying Cx36 function and assembly remains elusive. Recently, Lee et al. reported cryo-EM structures of Cx36, thus provided first insights of its gating mechanism. Here, we report a consistent cryo-EM structure of Cx36 determined in parallel, and describe unique interactions underpinning its assembly mechanism in complementary to the competing work. In particular, we found non-canonical electrostatic interactions between protomers from opposing hemichannels and a steric complementary site between adjacent protomers within a hemichannel, which together provide a structural explanation for the assembly specificity in homomeric and heteromeric gap junction channels.


Asunto(s)
Sinapsis Eléctricas , Proteína delta-6 de Union Comunicante , Conexinas/química , Conexinas/metabolismo , Microscopía por Crioelectrón , Sinapsis Eléctricas/metabolismo , Uniones Comunicantes/metabolismo , Canales Iónicos , Neuronas/metabolismo , Subunidades de Proteína , Humanos
8.
Biopolymers ; 115(2): e23553, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-37254885

RESUMEN

Before reaching their targets, sequence-specific DNA-binding proteins nonspecifically bind to DNA through electrostatic interactions and stochastically change their locations on DNA. Investigations into the dynamics of DNA-scanning by proteins are nontrivial due to the simultaneous presence of multiple translocation mechanisms and many sites for the protein to nonspecifically bind to DNA. Nuclear magnetic resonance (NMR) spectroscopy can provide information about the target DNA search processes at an atomic level. Paramagnetic relaxation enhancement (PRE) is particularly useful to study how the proteins scan DNA in the search process. Previously, relatively simple two-state or three-state exchange models were used to explain PRE data reflecting the target search process. In this work, using more realistic discrete-state stochastic kinetics models embedded into an NMR master equation, we analyzed the PRE data for the HoxD9 homeodomain interacting with DNA. The kinetic models that incorporate sliding, dissociation, association, and intersegment transfer can reproduce the PRE profiles observed at some different ionic strengths. The analysis confirms the previous interpretation of the PRE data and shows that the protein's probability distribution among nonspecific sites is nonuniform during the target DNA search process.


Asunto(s)
Proteínas de Unión al ADN , ADN , Proteínas de Unión al ADN/química , ADN/química , Espectroscopía de Resonancia por Spin del Electrón/métodos , Espectroscopía de Resonancia Magnética
9.
J Fluoresc ; 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38652358

RESUMEN

Herein, an aqueous phase synthesis approach was presented for the fabrication of copper nanoclusters (Cu NCs) with aggregation-induced emission (AIE) property, utilizing lipoic acid and NaBH4 as ligands and reducing agent, respectively. The as-synthesized Cu NCs exhibit an average size of 3.0 ± 0.2 nm and demonstrate strong solid-state fluorescence upon excitation with UV light. However, when dissolved in water, no observable fluorescent emission is detected in the aqueous solution of Cu NCs. Remarkably, the addition of Methimazole induced a significant red fluorescence from the aqueous solution of Cu NCs. This unexpected phenomenon can be ascribed to the aggregation of negatively charged Cu NCs caused by electrostatic interaction with positively charged imidazole groups in Methimazole, resulting in enhanced fluorescence through AIE mechanism. Therefore, there exists an excellent linear correlation between the fluorescent intensities of Cu NCs aqueous solution and the concentration of Methimazole within a range of 0.1-1.5 mM with a low limit of detection of 82.2 µM. Importantly, the designed enhanced-fluorescent nanoprobe based on Cu NCs exhibits satisfactory performance in assaying commercially available Methimazole tablets, demonstrating its exceptional sensitivity, reliability, and accuracy.

10.
Macromol Rapid Commun ; : e2400532, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-39090528

RESUMEN

A dual zwitterionic diblock copolymer (M100C100) consisting of poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC, M) and poly(3-((2-(methacryloyloxy)ethyl) dimethylammonio) propionate) (PCBMA, C) is synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. A double hydrophilic diblock copolymer (M100S100) consist of PMPC and anionic poly(3-sulfopropyl methacrylate potassium salt) (PMPS, S) is synthesized via RAFT. The degrees of polymerization of each block are 100. The charges of PMPC are neutralized intramolecularly. At neutral pH, the charges in PCBMA are also neutralized intramolecularly due to its carboxybetaine structure. Under acidic conditions, PCBMA exhibits polycation behavior as the pendant carboxy groups become protonated, forming cationic tertiary amine groups. PMPS shows permanent anionic nature independent of pH. Charge neutralized mixture of cationic M100C100 and anionic M100S100 in acidic aqueous solution forms water-soluble polyion complex (PIC) micelle owing to electrostatic attractive interactions. The core is composed of the cationic PCBMA and anionic PMPS blocks, with the PMPC blocks serving as shells that covered the core surface, forming spherical core-shell PIC micelles. Above pH 4 the pendant carboxy groups in PCBMA undergo deprotonation, transitioning to a zwitterionic state, thereby eliminating the cationic charge in PCBMA. Therefore, above pH 4 the PIC micelles are dissociated due to the disappearance of the charge interactions.

11.
Nanomedicine ; 62: 102781, 2024 Aug 18.
Artículo en Inglés | MEDLINE | ID: mdl-39163902

RESUMEN

Gold nanorods (GNR) produce heat upon irradiation with near-infrared light, enabling a tumor-targeted photothermal therapy. In this study, we prepared GNR coated with sulfated hyaluronic acid (sHA) with a binding affinity for CD44 via electrostatic interactions to deliver GNR to tumors efficiently and stably, and evaluated their usefulness for photothermal therapy. Cationic GNR modified with trimethylammonium groups electrostatically interacted with native HA or sHA with varying degrees of sulfation to form complexes. While GNR/HA was unstable in saline, GNR/sHA maintained the absorbance peak in the near-infrared region, particularly for GNR/sHA with higher degrees of sulfation. GNR/sHA exhibited an intense photothermal effect upon irradiation with near-infrared light. Furthermore, in vitro and in vivo studies revealed that GNR coated with sHA containing approximately 1.2 sulfated groups per HA unit could accumulate in CD44-positive tumors via an HA-specific pathway. These findings indicate the effectiveness of GNR/sHA as a tumor-targeted photothermal therapeutic agent.

12.
Int J Mol Sci ; 25(19)2024 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-39409188

RESUMEN

The chemokine receptors CCR1 and CCR5 display overlapping expression patterns and ligand dependency. Here we find that ligand activation of CCR5, not CCR1, is dependent on N-terminal receptor O-glycosylation. Release from O-glycosylation dependency is obtained by increasing CCR5 N-terminus acidity to the level of CCR1. Ligand activation of CCR5, not CCR1, drastically improves in the absence of glycosaminoglycans (GAGs). Ligand activity at both CCR1 and CCR5 is boosted by positively charged/basic peptides shown to interact with acidic chemokine receptor N-termini. We propose that receptors with an inherent low N-terminus acidity rely on post-translational modifications (PTMs) to efficiently compete with acidic entities in the local environment for ligand capture. Although crucial for initial ligand binding, strong electrostatic interactions between the ligand and the receptor N-terminus may counteract following insertion of the ligand into the receptor binding pocket and activation, a process that seems to be aided in the presence of basic peptides. Basic peptides bind to the naked CCR1 N-terminus, not the CCR5 N-terminus, explaining the loss of boosting of ligand-induced signaling via CCR5 in cells incapable of glycosylation.


Asunto(s)
Péptidos , Procesamiento Proteico-Postraduccional , Receptores CCR1 , Receptores CCR5 , Receptores CCR5/metabolismo , Receptores CCR5/química , Humanos , Glicosilación , Ligandos , Péptidos/química , Péptidos/metabolismo , Receptores CCR1/metabolismo , Receptores CCR1/química , Glicosaminoglicanos/metabolismo , Glicosaminoglicanos/química , Unión Proteica , Animales
13.
Molecules ; 29(14)2024 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-39064981

RESUMEN

In this study, a new polyionic polymer inhibitor, TIL-NH2, was developed to address the instability of shale gas horizontal wells caused by water-based drilling fluids. The structural characteristics and inhibition effects of TIL-NH2 on mud shale were comprehensively analyzed using infrared spectroscopy, NMR spectroscopy, contact angle measurements, particle size distribution, zeta potential, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy. The results demonstrated that TIL-NH2 significantly enhances the thermal stability of shale, with a decomposition temperature exceeding 300 °C, indicating excellent high-temperature resistance. At a concentration of 0.9%, TIL-NH2 increased the median particle size of shale powder from 5.2871 µm to over 320 µm, effectively inhibiting hydration expansion and dispersion. The zeta potential measurements showed a reduction in the absolute value of illite's zeta potential from -38.2 mV to 22.1 mV at 0.6% concentration, highlighting a significant decrease in surface charge density. Infrared spectroscopy and X-ray diffraction confirmed the formation of a close adsorption layer between TIL-NH2 and the illite surface through electrostatic and hydrogen bonding, which reduced the weakly bound water content to 0.0951% and maintained layer spacing of 1.032 nm and 1.354 nm in dry and wet states, respectively. Thermogravimetric analysis indicated a marked reduction in heat loss, particularly in the strongly bound water content. Scanning electron microscopy revealed that shale powder treated with TIL-NH2 exhibited an irregular bulk shape with strong inter-particle bonding and low hydration degree. These findings suggest that TIL-NH2 effectively inhibits hydration swelling and dispersion of shale through the synergistic effects of cationic imidazole rings and primary amine groups, offering excellent temperature and salt resistance. This provides a technical foundation for the low-cost and efficient extraction of shale gas in horizontal wells.

14.
Angew Chem Int Ed Engl ; 63(12): e202317203, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38286752

RESUMEN

The two-dimensional (2D) MXenes with sufficient interlayer spacing are promising cathode materials for aluminum-ion batteries (AIBs), yet the electrostatic repulsion effect between the surface negative charges and the active anions (AlCl4 - ) hinders the intercalation of AlCl4 - and is usually ignored. Here, we propose a charge regulation strategy for MXene cathodes to overcome this challenge. By doping N and Co, the zeta potential is gradually transformed from negative (Ti3 C2 Tx ) to near-neutral (Ti3 CNTx ), and finally positive (Ti3 CNTx @Co). Therefore, the electrostatic repulsion force can be greatly weakened between Ti3 CNTx and AlCl4 - , or even formed a strong electrostatic attraction between Ti3 CNTx @Co and AlCl4 - , which can not only accommodate more AlCl4 - ions in the Ti3 CNTx @Co interlayers to increase the capacity, but also solve the stacking and expansion problems. As a result, the optimized Al-MXene battery exhibits an ultrahigh capacity of up to 240 mAh g-1 (2-4 times the capacity of graphite cathode, 60-120 mAh g-1 ) and a potential ultrahigh energy density (432 Wh kg-1 , 2-4 times the value of graphite, 110-220 Wh kg-1 ) based on the mass of cathode materials, comparable to LiFePO4 -based lithium-ion batteries (350-450 Wh kg-1 , based on the mass of LiFePO4 ).

15.
Angew Chem Int Ed Engl ; 63(41): e202407909, 2024 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-38993054

RESUMEN

In situ construction of solid electrolyte interfaces (SEI) is an effective strategy to enhance the reversibility of zinc (Zn) anodes. However, in situ SEI to afford high reversibility under high current density conditions (≥20 mA cm-2) is highly desired yet extremely challenging. Herein, we propose a dual reaction strategy of spontaneous electrostatic reaction and electrochemical decomposition for the in situ construction of SEI, which is composed of organic-rich upper layer and inorganic-rich inner layer. Particularly, in situ SEI performs as "growth binder" at small current density and "orientation regulator" at high current density, which significantly suppresses side reactions and dendrite growth. The in situ SEI affords the record-breaking reversibility of Zn anode under practical conditions, Zn//Zn symmetric cells can stably cycle for over 1300 h and 400 h at current densities of 50 mA cm-2 and 100 mA cm-2, respectively, showcasing an exceptional cumulative capacity of 67.5 Ah cm-2. Furthermore, the practicality of this in situ SEI is verified in Zn//PANI pouch cells with high mass loading of 25.48 mg cm-2. This work provides a universal strategy to design advanced SEI for practical Zn-ion batteries.

16.
Small ; 19(26): e2208052, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36942697

RESUMEN

The formation of nanoaggregates makes a great difference to the improvement of photodynamic therapy (PDT) performance to some extent, but constructing stable aggregates with a clear structure is simultaneously a big challenge for us. Herein, just by electrostatic interaction, cationic 2PAHs and anionic FBA351, regarded as acceptor (A) and donor (D), respectively, are utilized to prepare stable aggregate of ionic-bonds coupled polymer (ICP) with repeated "D-A" structure, which is fully characterized by nuclear magnetic resonance (NMR), time-of-flight mass spectrometry, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Remarkably, aggregate ICP with multiple "D-A" structures showed enhanced photosensitization efficiency over its precursor 2PAHs and FBA351, which is in accord with the image-guided photodynamic anticancer therapy. Such results not only offer a simple way to obtain stable aggregate but also give us a guideline to design efficient photosensitizers.

17.
Small ; 19(35): e2302060, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-37096933

RESUMEN

2D materials that can provide long-range ordered channels in thin-film form are highly desirable for proton exchange membranes (PEMs). Covalent organic framework nanosheets (CONs) are promising 2D materials possessing intrinsic porosity and high processability. However, the potential of CONs in PEMs is limited by loose sheet stacking and interfacial grain boundary, which lead to unsatisfied mechanical property and discontinuous conduction pathway. Herein, chitosan (CS), a natural polymer with rich NH2 groups, is designed as the linker of dual-sulfonate CONs (CON-2(SO3 H)) to obtain CON-2(SO3 H)-based membrane. Ultrathin CON-2(SO3 H) with high crystallinity and large lateral size is synthesized at water-octanoic acid interface. The high flexibility of CS chains and their electrostatic interactions with SO3 H groups of CON-2(SO3 H) enable effective connection of CON-2(SO3 H), thus endowing membrane dense structure and exceptional stability. The stacked CON-2(SO3 H) constructs regular hydrophilic nanochannels containing high-density SO3 H groups, and the electrostatic interactions between CON-2(SO3 H) and CS form interfacial acid-base pairs transfer channels. Consequently, CON-2(SO3 H)@CS membrane simultaneously achieves superior proton conductivity of 353 mS cm-1 (under 80 °C hydrated condition) and tensile strength of 95 MPa. This work highlights the advantages of proton-conducting porous CON-2(SO3 H) in advanced PEMs and paves a way in fabricating robust CON-based membranes for various applications.

18.
Small ; 19(11): e2205857, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36623935

RESUMEN

To increase chemical reaction rates, general solutions include increasing the concentration/temperature and introducing catalysts. In this study, the rate constant of an electrophilic metal coordination reaction is accelerated 23-fold on the surface of layered aluminosilicate (LAS), where the reaction substrate (ligand molecule) induces dielectric polarization owing to the polar and anionic surface. According to the Arrhenius plot, the frequency factor (A) is increased by almost three orders of magnitude on the surface. This leads to the conclusion that the collision efficiency between the ligands and metal ions is enhanced on the surface due to the dielectric polarization. This is surprising because one side of the ligand is obscured by the surface, so the collision efficiency is expected to be decreased. This unique method to accelerate the chemical reaction is expected to expand the range of utilization of LASs, which are chemically inert, abundant, and environmentally friendly. The concept is also applicable to other metal oxides which have polar surfaces, which will be useful for various chemical reactions in the future.

19.
J Mol Recognit ; 36(7): e3024, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37158286

RESUMEN

Based on the synergistic action of hydrogen bond and electrostatic interaction, provided by methacrylic acid and 2-aminoethyl ester hydrochloride (FM2), respectively, novel molecularly imprinted polymers (SA-MIPs) were designed to improve its selective recognition ability. Diclofenac sodium (DFC) was chosen as the template molecule of this study. The interaction and their recognition sites between two functional monomers and templates were confirmed by nuclear magnetic resonance hydrogen spectroscopy. Because of the synergistic action of hydrogen bond and electrostatic interaction, the imprinting factor (IF) of SA-MIPs (IF = 2.26) is superior to the corresponding monofunctional monomer imprinting materials (IF = 1.52, 1.20) and the materials using two functional monomers with an only single type of interaction (IF = 1.54, 1.75). The results of selective adsorption experiments indicate that the selective recognition ability of SA-MIPs is significantly better than that of the other four MIPs, and the difference in selectivity coefficient for methyl orange is the largest between SA-MIPs and the MIPs only using FM2, which is about 70 times. In addition, x-ray photoelectron spectroscopy was used to verify the interaction between SA-MIPs and the template. This work and its explanation of the interaction mechanism at the molecular level will be helpful for the rational design of novel MIPs with higher selectivity. Besides, SA-MIPs have good adsorption performance (37.75 mg/g) for DFC in aqueous solutions, which could be used as potential adsorption materials for the effective removal of DFC in the aquatic environment.


Asunto(s)
Impresión Molecular , Polímeros Impresos Molecularmente , Impresión Molecular/métodos , Polímeros/química , Enlace de Hidrógeno , Electricidad Estática , Adsorción
20.
Chemistry ; 29(44): e202300877, 2023 Aug 04.
Artículo en Inglés | MEDLINE | ID: mdl-37183972

RESUMEN

We employ a molecular torsion balance displaying bifurcated conformational isomerism to quantitatively evaluate the non-covalent interactions between the fullerene surface and substituted arene moieties containing elements with high atomic numbers, as well as the thermodynamic processes involved in the folding equilibrium using nuclear magnetic resonance spectroscopy. The interaction between fullerene and haloaryl groups was stronger in cases where the introduced halogen had a higher atomic number, indicating that dispersion forces play a significant role in the interaction between fullerenes and 4-haloaryl groups. The dispersion term also significantly contributed to the interaction between fullerene and the 4-mercaptophenyl group. Moreover, the addition of an appropriate base to the 4-mercaptophenyl-appended torsion balance formed the corresponding thiophenolate anion, resulting in a large negative change in the folding free energy in CDCl3 . Detailed analysis suggested that the observed attractive anionic arene-fullerene interactions predominantly originated from solvation effects.

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