Spacer Length Research Articles

Enhancing the Elasticity of Conjugated Polymers through Precise Control of the Spacing between the Backbone and Siloxane Side-Chains.

Intrinsically stretchable conjugated polymers (CPs) have extensively been studied for the development of novel flexible electronic devices. In this work, a method to control the elastic properties of CPs has been proposed via regulation of spacer length between the siloxane side-chain and the backbone. The target polymers were CP films with the structure P(mC-Si) for four different numbers of the spacer methylene groups, namely, m = 5, 6, 7, and 8. The effect of spacer length on the aggregation state as well as on electrical and elastic properties of the prepared films was then investigated. An adjustable lamellar spacing (dL-L), in addition to improved elastic properties, was achieved as the spacer length was changed in the prepared polymer films. Moreover, P(7C-Si) has a sufficient dL-L value of 35.77 Å, which provides enough space for inter-chain sliding to dissipate stress. This facilitated the dissipation of stress during the straining process. At a strain value of 100% in the vertical direction, the mobility of the P(7C-Si) film was 0.79 cm2 V-1 s-1 and reduced to 84.0% of the initial value without any applied strain. The study provides clear evidence that tuning the spacer length between the silicone endgroup and backbone is an effective way to improve the intrinsic stretchability of CPs with siloxane side chains.

Power Output Optimisation via Arranging Gas Flow Channels for Low-Temperature Polymer Electrolyte Membrane Fuel Cell (PEMFC) for Hydrogen-Powered Vehicles

As we move away from internal combustion engines to tackle climate change, the importance of hydrogen-powered vehicles and polymer electrolyte membrane fuel cell (PEMFC) technology has dramatically increased. In the present study, we aimed to determine the optimal configuration for the power output of a PEMFC system using computational fluid dynamics (CFD) modelling to analyse variations of the primary serpentine design of gas flow channels. This helps improve efficiency and save on valuable materials used, reducing potential carbon emissions from the production of hydrogen vehicles. Different numbers of serpentine gas channels were represented with various spacing between them, within the defined CFD model, to optimise the gas channel geometry. The results show that the optimum configuration was found to have 11 serpentine channels with a spacing of 3.25 mm. In this optimum configuration, the ratio between the channel width, channel spacing, and serpentine channel length was found to be 1:2.6:38 for PEMFCs. Furthermore, the inclusion of fillets to the bends of the serpentine gas channels was found to have a negative effect on the overall power output of the fuel cell. Moreover, the optimisation procedures with respect to the number of gas channels and the spacing revealed an optimal power density exceeding 0.65 W/cm2.

Strong Exciton–Exciton Scattering of Exfoliated van der Waals InSe toward Efficient Continuous-Wave Near-Infrared P-Band Emission

P-band emission is a superlinear low-coherence emission through exciton-exciton (X-X) scattering into photon-like states. It occurs without the prerequisites of population inversion or macroscopical coherence, rendering lower power consumption than the widely explored superlinear low-coherence emissions including superfluorescence, amplified spontaneous emission, and random lasing, and holds great potential for speckle-free imaging and interferometric sensing. However, competition processes including exciton dissociation and annihilation undermine its operation at room temperature and/or low excitation conditions. Here we report room-temperature P-band emission from InSe microflakes with excitation density of 1010 cm-2, offering 2-orders-of-magnitude lower operation density compared to the state-of-the-art superlinear low-coherence emissions. The efficient P-band emission is attributed to a large X-X scattering strength of 0.25 μeV μm2 due to enhanced spatial confinement along with intrinsic material metrics of 3D/2D exciton complex and asymmetric electron/hole mass. These findings open an avenue toward strong low-coherence near-infrared light sources based on van der Waals semiconductors.

A Novel Program Scheme for Z-Interference Improvement in 3D NAND Flash Memory.

With gate length (Lg) and gate spacing length (Ls) shrinkage, the cell-to-cell z-interference phenomenon is increasingly severe in 3D NAND charge-trap memory. It has become one of the key reliability concerns for 3D NAND cell scaling. In this work, z-interference mechanisms were investigated in the programming operation with the aid of Technology Computer-Aided Design (TCAD) and silicon data verification. It was found that the inter-cell trapped charges are one of the factors causing z-interference after cell programming, and these trapped charges can be modulated during programming. Thus, a novel program scheme is proposed to suppress the z-interference by reducing the pass voltage (Vpass) of the adjacent cells during programming. As a result, the proposed scheme suppresses the Vth shift of 40.1% for erased cells with Lg/Ls = 31/20 nm. In addition, this work further analyzes the optimization and balance of program disturbance and z-interference with the scaling of cell Lg-Ls based on the proposed scheme.

Chemico-Physical Properties of Some 1,1'-Bis-alkyl-2,2'-hexane-1,6-diyl-bispyridinium Chlorides Hydrogenated and Partially Fluorinated for Gene Delivery.

The development of very efficient and safe non-viral vectors, constituted mainly by cationic lipids bearing multiple charges, is a landmark for in vivo gene-based medicine. To understand the effect of the hydrophobic chain's length, we here report the synthesis, and the chemico-physical and biological characterization, of a new term of the homologous series of hydrogenated gemini bispyridinium surfactants, the 1,1'-bis-dodecyl-2,2'-hexane-1,6-diyl-bispyridinium chloride (GP12_6). Moreover, we have collected and compared the thermodynamic micellization parameters (cmc, changes in enthalpy, free energy, and entropy of micellization) obtained by isothermal titration calorimetry (ITC) experiments for hydrogenated surfactants GP12_6 and GP16_6, and for the partially fluorinated ones, FGPn (where n is the spacer length). The data obtained for GP12_6 by EMSA, MTT, transient transfection assays, and AFM imaging show that in this class of compounds, the gene delivery ability strictly depends on the spacer length but barely on the hydrophobic tail length. CD spectra have been shown to be a useful tool to verify the formation of lipoplexes due to the presence of a "tail" in the 288-320 nm region attributed to a chiroptical feature named ψ-phase. Ellipsometric measurements suggest that FGP6 and FGP8 (showing a very interesting gene delivery activity, when formulated with DOPE) act in a very similar way, and dissimilar from FGP4, exactly as in the case of transfection, and confirm the hypothesis suggested by previously obtained thermodynamic data about the requirement of a proper length of the spacer to allow the molecule to form a sort of molecular tong able to intercalate DNA.

Organic nanoparticles with tunable AIE derived from amino acids appended naphthalenediimide based amphiphiles

Fluorescent organic nanoparticles (FONPs) are unique cooperative manifestations of supramolecular self-aggregates and luminescent nanoparticles. In this work, we developed naphthalenediimide (NDI) based amphiphiles (NDI-1-9) having amino acids substitution from L-alanine to L-phenyl alanine to 3-(2-naphthyl)-L-alanine in absence and presence of alkyl spacer (C-6, C-11). Formation of self-aggregated spherical organic nanoparticles of ∼50 nm took place at and above 50 vol% water or methyl cyclohexane (MCH) in different binary solvent systems (DMSO/DMF-water, CHCl3-MCH) via J-aggregation. In case of NDI-1-3 (amino acids are directly connected to the NDI) self-assembled FONPs (MCH in CHCl3) exhibited aggregation-induced emission (AIE) through excimer formation. Red shift in the emission maxima were observed from 484 nm to 495 nm, and 590 nm, respectively with increasing π electron cloud at substituted donor from NDI-1 to NDI-3. Alongside, in case of aromatic amino acids substitution, FONPs of 6-amino caproic acid spacer containing NDI derivatives (NDI-5 and NDI-6) showed AIE at 505 nm and 545 nm (water in DMF/DMSO). Corresponding 11-amino undecanoic acid containing analogues (NDI-8 and NDI-9) showed AIE at 480 nm and 585 nm in CHCl3-MCH and DMF/DMSO-water. The multi colour emission from blue-green to yellow-orange with enrichment of π-electron cloud density in the side chain substitution of NDI was observed possibly due to the facilitated electron transfer at a lesser energy to the electron deficient NDI core that resulted in red shifted emission maxima. This was further clarified by regulating the availability of π-electrons of phenyl ring of NDI-2 by including electron withdrawing –NO2 and donating -OMe groups at the molecular backbone (NDI-2a and NDI-2b) that showed blue shifted (475 nm) and red shifted (570 nm) emission maxima with respect to NDI-2 (495 nm). However, increase in alkyl spacer length between side chain substitution and NDI core yielded relatively lower quantum yield presumably due to the impeded electron transfer.

Towards a Rational Design of Antibody-Recruiting Molecules through a Computational Microscopy View of their Interactions with the Target Antibody.

Antibody recruiting molecules (ARMs) are an innovative class of chimeric molecules, consisting of an antibody-binding ligand (ABL) and a target-binding ligand (TBL). ARMs mediate ternary complex formation between a target cell of interest for elimination and endogenous antibodies that are present in human serum. Clustering of fragment crystallizable (Fc) domains on the surface of antibody-bound cells mediate destruction of the target cell by innate immune effector mechanisms. ARMs are typically designed by conjugating small molecule haptens to a (macro)molecular scaffold, without considering the structure of the respective anti-hapten antibody. Here we report on a computational molecular modeling methodology that allows for studying the close contacts between ARMs and the anti-hapten antibody, considering (1) the spacer length between ABL and TBL; (2) the number of ABL and TBL, and (3) the molecular scaffold onto which these are positioned. Our model predicts the difference in binding modes of the ternary complex and predicts which ARMs are optimal recruiters. Avidity measurements of the ARM-antibody complex and ARM-mediated antibody recruitment to cell surfaces in vitro confirmed these computational modeling predictions. This kind of multiscale molecular modelling holds potential for design of drug molecules that rely on antibody binding for their mechanism of action.

Approach to Evaluation of Electrocatalytic Water Splitting Parameters, Reflecting Intrinsic Activity: Toward the Right Pathway.

The development of transition metal-based non-precious-metal electrocatalysts for energy storage and conversion systems has received a lot of interest recently. To further this subject in the proper way given the development of electrocatalysts, a fair comparison of their respective performance is necessary. This Review investigates the parameters used for the comparison of electrocatalyst activity. Significant evaluation criteria employed in electrochemical water splitting studies are the overpotential at defined current density usually at 10 mA per geometric surface area, Tafel slope, exchange current density, mass activity, specific activity and turnover frequency (TOF). This Review will discuss how to identify the specific activity and TOF by electrochemical and non-electrochemical methods to represent intrinsic activity as well as the benefits and uncertainties of each technique, ensuring that each method is applied correctly when calculating intrinsic activity metrics.

Remote Control of One‐Handed Helicity in Polyacetylenes through Flexible Spacers in Water: Impact of the Spacer Length

AbstractWe report the unprecedented sergeants and soldiers (S&S)‐type remote control of one‐handed helicity in copolymers of chiral/achiral biphenylylacetylenes bearing amphiphilic oligo(ethylene glycol) (OEG) side chains. A small amount of chiral binaphthyl residues (≤10 mol %) introduced at the terminal of the achiral OEG spacers as many as 80 bonds away from the polymer backbones induced a complete one‐handed helix in water through preferential intramolecular encapsulation of the binaphthyl groups within a cavity of the copolymers. A fully one‐handed helix can be induced virtually independent of the OEG spacer length and concentrations. At a specific spacer length, however, its helix‐sense was inverted. The copolymers also form an excess one‐handed helix in organic solvents in an OEG spacer‐length dependent manner, yet far from the polymer backbones. We show the superiority of the present covalent‐bond driven S&S‐type remote helicity control over the corresponding noncovalent helicity induction approach.

Remote Control of One-Handed Helicity in Polyacetylenes through Flexible Spacers in Water: Impact of the Spacer Length.

We report the unprecedented sergeants and soldiers (S&S)-type remote control of one-handed helicity in copolymers of chiral/achiral biphenylylacetylenes bearing amphiphilic oligo(ethylene glycol) (OEG) side chains. A small amount of chiral binaphthyl residues (≤10 mol %) introduced at the terminal of the achiral OEG spacers as many as 80 bonds away from the polymer backbones induced a complete one-handed helix in water through preferential intramolecular encapsulation of the binaphthyl groups within a cavity of the copolymers. A fully one-handed helix can be induced virtually independent of the OEG spacer length and concentrations. At a specific spacer length, however, its helix-sense was inverted. The copolymers also form an excess one-handed helix in organic solvents in an OEG spacer-length dependent manner, yet far from the polymer backbones. We show the superiority of the present covalent-bond driven S&S-type remote helicity control over the corresponding noncovalent helicity induction approach.

Quantitative Evaluation of Maize Emergence Using UAV Imagery and Deep Learning

Accurate assessment of crop emergence helps breeders select appropriate crop genotypes, and farmers make timely field management decisions to increase maize yields. Crop emergence is conventionally quantified by manual calculations to quantify the number and size of seedlings, which is laborious, inefficient, and unreliable and fails to visualize the spatial distribution and uniformity of seedlings. Phenotyping technology based on remote sensing allows for high-throughput evaluation of crop emergence at the early growth stage. This study developed a system for the rapid estimation of maize seedling emergence based on a deep learning algorithm. The RGB images acquired from an unmanned aerial vehicle (UAV) were used to develop the optimal model for the recognition of seedling location, spacing, and size, and the prediction performance of the system was evaluated in three stations during 2021–2022. A case study was conducted to show the evaluation of the system for maize seedlings and combined with TOPSIS (Technique for Order of Preference by Similarity to Ideal Solution) analysis. The results show that the system has good prediction performance for maize seedling count with an average R2 value of 0.96 and an accuracy of 92%; however, shadows and planting density influence its accuracy. The prediction accuracy reduces significantly when the planting density is above 90,000 plants/ha. The distribution characteristics of seedling emergence and growth were also calculated based on the average value and variation coefficient of seedling spacing, seedling area, and seedling length. The estimation accuracies for the average value of seedling spacing, the coefficient of variation of seedling spacing, the average value of the seedling area, the coefficient of variation of the seedling area, and the average value of the seedling length were 87.52, 87.55, 82.69, 84.51, and 90.32%, respectively. In conclusion, the proposed system can quickly analyze the maize seeding growth and uniformity characteristics of experimental plots and locate plots with poor maize emergence.

Salvianolic-Acid-B-Loaded HA Self-Healing Hydrogel Promotes Diabetic Wound Healing through Promotion of Anti-Inflammation and Angiogenesis.

Inflammatory dysfunction and angiogenesis inhibition are two main factors leading to the delayed healing of diabetic wounds. Hydrogels with anti-inflammatory and angiogenesis-promoting effects have been considered as promising wound care materials. Herein, a salvianolic acid B (SAB)-loaded hyaluronic acid (HA) self-healing hydrogel (HA/SAB) with anti-inflammatory and pro-angiogenesis capacities for diabetic wound healing is reported. The HA hydrogel was prepared via the covalent cross-linking of aldehyde groups in oxidized HA (OHA) and hydrazide groups in adipic dihydrazide (ADH)-modified HA (HA-ADH) with the formation of reversible acylhydrazone bonds. The obtained HA hydrogel exhibited multiple favorable properties such as porous structures, excellent self-healing properties, a sustainable release capacity of SAB, as well as excellent cytocompatibility. In addition, the effects of the SAB-loaded HA self-healing hydrogel were investigated via a full-thickness skin defect model using diabetic rats. The HA/SAB hydrogel showed enhanced skin regeneration effects with accelerated wound closure, shorter remaining dermal space length, thicker granulation tissue formation, and more collagen deposition. Furthermore, reduced inflammatory response and enhanced vascularization were found with HA/SAB2.5 hydrogel-treated wounds, indicating that the hydrogel promotes diabetic wound healing through the promotion of anti-inflammation and angiogenesis. Our results suggest that the fabricated SAB-loaded HA self-healing hydrogel is promising as a wound dressing for the treatment of diabetic wounds.

Abstract 1787: Design of bispecific adapters for universal CAR T cell therapies of solid tumors

Abstract Recent success in the use of chimeric antigen receptor (CAR) T cell therapies to treat hematologic cancers has encouraged the exploration of CAR T cell technologies to treat solid tumors. For establishment of a productive immunologic synapse between the CAR T cell and cancer cell, multiple CARs on the T cell surface must engage multiple tumor antigens on the cancer cell surface. Whereas these binding interactions are mediated in classical CAR T cells by direct recognition of the tumor antigen by the scFv on the CAR, in the case of universal CAR T cells this recognition must be created by a bispecific adapter that can bridge between the tumor antigen and the CAR. While a diversity of bispecific adapters have been explored in the literature, the bispecific adapter used here is comprised of a low molecular weight ligand that binds avidly to the desired tumor antigen, the yellow dye fluorescein (FL) that binds tightly to an anti-fluorescein scFv on the CAR, and a polyethylene glycol (PEG) spacer that spans between the two. The length of this PEG spacer appears to be critical to ensure that 1) the bispecific adapter is long enough to mediate engagement of the universal CAR T cell with the cancer cell, and 2) the resulting intercellular distance is optimal for activating the necessary co-receptor interactions.In our study, we have utilized protein structure data and molecular modeling to estimate the optimal adapter spacer lengths for bridging between our CAR T cell and two important target cells, namely PSMA positive prostate cancer cells and fibroblast activation protein (FAP) expressing cancer associated fibroblasts. We then synthesized the desired bispecific adapters with a variety lengths of PEG spacer and evaluated their effects in mediating the cytotoxicity of our universal anti-FL CAR T cells both in vitro and in vivo. Our results reveal that the optimal spacer lengths in the bispecific adapters for targeting PSMA (DUPA-FL) and FAP (FAPL-FL) are different and depend on the locations of the adapter binding pockets on their respective protein targets, as predicted by molecular modeling. Specifically, a shorter PEG spacer is required for maximal cytoxicity when employing the PSMA-targeted adapter, whereas a much longer PEG spacer is needed to achieve maximal cell killing with the FAP-targeted adapter. In addition, spacer length can also be adjusted to avoid overactivation-induced T cell exhaustion. Taken together, our studies demonstrate that instead of optimizing the hinge length of a CAR for each antigen epitope, our bispecific adapter/universal CAR platform provides a highly flexible strategy for optimizing the intermembrane distance between the universal CAR T cell and cancer cell to achieve maximal target cell killing with minimal CAR T cell exhaustion. Citation Format: Suilan Zheng, Bo Huang, Yashapal Singh, Haiyan Chu, Suresh K. Bowroju, Md Sazzadul Bari, Madduri Srinivasarao, Sudarsan R. Kasireddy, Ramesh Mukkamala, Laurie Beitz, Byoung Ryu, Andrew M. Scharenberg, Michael Jensen, Philip S. Low. Design of bispecific adapters for universal CAR T cell therapies of solid tumors [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 1787.

Pathogenic human variant that dislocates GATA2 zinc fingers disrupts hematopoietic gene expression and signaling networks.

Although certain human genetic variants are conspicuously loss of function, decoding the impact of many variants is challenging. Previously, we described a patient with leukemia predisposition syndrome (GATA2 deficiency) with a germline GATA2 variant that inserts 9 amino acids between the 2 zinc fingers (9aa-Ins). Here, we conducted mechanistic analyses using genomic technologies and a genetic rescue system with Gata2 enhancer-mutant hematopoietic progenitor cells to compare how GATA2 and 9aa-Ins function genome-wide. Despite nuclear localization, 9aa-Ins was severely defective in occupying and remodeling chromatin and regulating transcription. Variation of the inter-zinc finger spacer length revealed that insertions were more deleterious to activation than repression. GATA2 deficiency generated a lineage-diverting gene expression program and a hematopoiesis-disrupting signaling network in progenitors with reduced granulocyte-macrophage colony-stimulating factor (GM-CSF) and elevated IL-6 signaling. As insufficient GM-CSF signaling caused pulmonary alveolar proteinosis and excessive IL-6 signaling promoted bone marrow failure and GATA2 deficiency patient phenotypes, these results provide insight into mechanisms underlying GATA2-linked pathologies.

A Lipidated Single-B-Chain Derivative of Relaxin Exhibits Improved In Vitro Serum Stability without Altering Activity.

Human relaxin-2 (H2 relaxin) is therapeutically very important due to its strong anti-fibrotic, vasodilatory, and cardioprotective effects. Therefore, relaxin's receptor, relaxin family peptide receptor 1 (RXFP1), is a potential target for the treatment of fibrosis and related disorders, including heart failure. H2 relaxin has a complex two-chain structure (A and B) and three disulfide bridges. Our laboratory has recently developed B7-33 peptide, a single-chain agonist based on the B-chain of H2 relaxin. However, the peptide B7-33 has a short circulation time in vitro in serum (t1/2 = ~6 min). In this study, we report structure-activity relationship studies on B7-33 utilizing different fatty-acid conjugations at different positions. We have shown that by fatty-acid conjugation with an appropriate spacer length, the in vitro half-life of B7-33 can be increased from 6 min to 60 min. In the future, the lead lipidated molecule will be studied in animal models to measure its PK/PD properties, which will lead to their pre-clinical applications.

Synthesis and Structures of Lead(II) Complexes with Hydroxy-Substituted Closo-Decaborate Anions

Mixed-ligand lead(II) complexes with 2,2′-bipyridyl and [B10H9OH]2− or monosubstituted hydroxy-substituted closo-decaborate anions with a pendant hydroxy group, separated from the boron cage by an alkoxylic spacer of different lengths [B10H9O(CH2)xO(CH2)2OH]]2− (x = 2 or 5) have been synthesized. Compounds have been characterized by IR and multinuclear NMR spectroscopies. The structures of binuclear complex [Pb(bipy)2[B10H9OH]]2·CH3CN (1·CH3CN), mononuclear complex [Pb(bipy)2[B10H9O(CH2)2O(CH2)2OH]]·0.5bipy·CH3CN (2·0.5bipy·CH3CN), and polymeric complex [Pb(bipy)[B10H9O(CH2)5O(CH2)2OH]]n (3) have been determined by single-crystal X-ray diffraction. In all three compounds, the co-ordination polyhedra of lead(II) are formed by N atoms from two bipy molecules, O atoms of the substituent attached to the boron cage, and BH groups of the boron cage.

Semi-microscopic Theory for the Current Rectification Phenomenon in Nanogap Molecular Devices.

A semi-microscopic theory is developed for heterogeneous electron transfer (HET) kinetics based on the energy level alignment approach at self-assembled monolayer (SAM) covered metal electrodes. Theory provides the electronic and molecular property-dependent equations for the HET rate constant (k0) and the transfer coefficient (α) for potential. k0 is formulated using the activation free energy as a product of the SAM covered metal work function (WF) and fractional electronic charge exchanged at the transition state (attained through the alignment of the frontier molecular orbital (FMO) energy level of the electroactive group with the WF of metal). k0 is a function of the metal jellium electronic screening length and dielectric and of the molecular self-assembly (through its dipole moment, size, and packing density) and the FMO energies of electroactive groups. The operative potential at the transition state is governed by α, which is a function of molecular spacer length and characteristic electronic-dipolar coupling length. The current rectification phenomenon in nanogap molecular devices is theoretically analyzed using equations for k0 and α for SAM covered source and drain electrodes. Theory unravels the LUMO or HOMO dichotomy for a given metal: (i) for the HOMO assisted ET, the metal with a high WF has a high current rectification ratio (RR), while (ii) for the LUMO assisted ET, the metal with a low WF has a high current RR in asymmetrical devices. Theory predicts the reversal in current rectification by altering the dipole moment of the anchoring molecule, the HOMO/LUMO energy of the electroactive groups, and the nature of the metal. Finally, theory shows qualitative and quantitative coherence with the reported experimental current-potential response of molecular device.

Preparation of a Monovalent-Selective Anion-Exchange Membrane: Effect of Alkyl Chain Length and Crystallinity

Crosslinked anion-exchange membranes (AEMs) with reasonable water uptake are used for the separation of monovalent anions from their mixture with bivalent anions by electrodialysis (ED). Herein, we report the preparation of a series of monovalent-selective crosslinked AEMs containing imidazole rings from the polyacrylonitrile-co-poly(vinylimidazole) (PAN-co-PVIm) copolymer (AN/VIm ratio = 75:25 mol/mol), followed by N-alkylation with alkyl halide of different chain lengths (carbon number: 1,6,10,18), followed by reaction with 1,6-diamino hexane. The difference in the obtained permselectivity (PSO42–Cl–) was compared with those of un-crosslinked and commercial Ionsep membranes. The effects of crosslinking, the chain length of the alkyl spacer attached to imidazolium nitrogen of the membrane matrix, and the partial crystallinity occurring due to the arrangement of long alkyl chains on PSO42–Cl– were investigated. A representative crosslinked membrane (MQ18) with an octadecyl alkyl chain length (C18) attached to the imidazole moiety exhibited moderate water uptake (22%), high fixed charge density (0.037 meq/cm3), and high PSO42–Cl– (6.4) during the separation of a mixture of 0.01 M sodium chloride and 0.01 M sodium sulfate (2000 mg/L) by the ED process. The PSO42–Cl– value is further increased from 6.4 to 16.7 by increasing the electrolyte concentration to 0.05 M sodium chloride and 0.05 M sodium sulfate. The rigid imidazolium structure, locally organized higher chain length of the alkylating group, and the crosslinked network structure provide steric hindrance for the passage of more hydrophilic sulfate anions, which facilitates higher selectivity.

Experimental and Numerical Investigation of the Behavior of Steel Beams Strengthened by Bolted Hybrid FRP Composites

The strengthening of steel beams using hybrid fiber-reinforced polymers (HFRPs) has gained enormous attention over the last decades. Few researchers have investigated the effectiveness of the fastening techniques without a bonding agent to overcome the undesirable debonding failure of the bonded FRP–steel system. This paper reports the outcomes of experimental and numerical investigations conducted on steel beams strengthened by HFRP using steel bolts. Twenty-two steel beams were tested in four-point loading to investigate the effect of the HFRP length and the bolt arrangement on the flexural behavior of the strengthened systems. The observed failure modes, load-deflection relations, deflection profiles, and strain measurements were also studied. The tested beams showed a ductile behavior, with 15.1 and 22.2% enhancements in the yield and ultimate flexural capacities, respectively. Simplified empirical equations were developed to predict the ultimate load of the bolted HFRP–steel beams. ANSYS software was used to model the beams’ behavior and investigate the effects of the HFRP thickness, bolt spacing, steel grade, loading scheme, and beam length on the effectiveness of the adopted fastening technique. Increasing the HFRP length enhanced the utilization of HFRPs as well as the beam’s ductility, with a reduction of up to 51.2% in the mid-span deflection. Moreover, the strain compatibility of the HFRP–steel beams was improved with an 87.2% reduction in the interfacial slippage. The bolt arrangement showed an insignificant effect on the overall performance of the beams. The numerical results verified the effectiveness of the fastening technique in enhancing the flexural performance of the steel beams, with gains of up to 16.7% and 34.5% in the yield and ultimate load-carrying capacities, respectively.

Wettability alteration of organo-vermiculites induced by layer charge and tailored bis-N-heterocyclic quaternary ammonium salts

Wettability is an important surface property that deserves to further explore the factors on its alteration. Series of bis-N-heterocyclic quaternary ammonium salts with different spacer length and N-heterocyclic headgroups (morpholinium (BMMB, BMMD and BMMH), piperidinium (BPMH) and piperazinium (BMPMH)) have been synthesized and employed for altering the wettability of vermiculite and its derivates (Vts) treated by Li+-saturated heating method. The results of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG-DTG), scanning electron microscopy (SEM) and N2 adsorption/desorption isotherms indicate that all of the bis-N-heterocyclic quaternary ammonium salts have been successfully inserted into the vermiculite layers, leading to the organic monolayer. The results of capillary rise tests combined with Lipophilic to Hydrophilic Ratio (LHR) values unveil the wettability alteration of the organo-Vts. As the layer charge decreases, the hydrophilicity of the organo-Vts gradually increases, which is probably caused by the decline in binding sites. As the result of the change in spacer length of modifier, the wetting properties of morpholinium-based organo-Vts change in order of BMMD-Vts > BMMH-Vts > BMMB-Vts, and difference in N-heterocyclic headgroups leads to the sequence of wettability: BMPMH-Vts > BPMH-Vts > BMMH-Vts. Layer charge of Vt, spacer length and the type of the N-heterocyclic headgroup of modifier have the synergistic effect on the regulation of the wettability.