Equimolar Ratio Research Articles

High Entropy Induced Local Charge Enhancement Promotes Frank–Van der Merwe Growth for Dendrite‐Free Potassium Metal Batteries

AbstractPotassium metal batteries (PMBs) are promising for next‐generation energy storage. However, the high reactivity of the anode causes instability in the solid electrolyte interface (SEI), resulting in Volmer‐Weber (V‐W) type deposition. To achieve uniform Frank‐van der Merwe (F‐M) type deposition, high entropy alloy nanoparticles are designed (HEA NPs) with equimolar ratios of Mn, Fe, Co, Cu, and Ni to enhance the substrate‐K metal interface. HEA NPs enhance the K affinity of the N‐doped nanocarbon fiber substrate (N‐PCNF) and maximize ion and electron transport efficiency. The dendrite‐free horizontal growth of K metal confirmed through Operando X‐ray diffraction (XRD) and optical microscopy (OM). Consequently, the asymmetric cell exhibits ultra‐long cycling stability of 2350 hours at a high current density of 8 mA cm−2. The full cell composed of molten K diffusion into HEA NPs decorated N‐PCNF anode with perylene‐3,4,9,10‐tetracarboxylic dianhydride cathode (HEA‐N‐PCNF‐K||PTCDA) delivers an energy density of 331 W h kg−1 and remains stable over 2000 cycles. This study offers a promising pathway for innovative PMBs designs with broad application prospects.

Application of Sortase-Mediated Ligation for the Synthesis of Block Copolymers and Protein-Polymer Conjugates.

Sortase-mediated ligation (SML) has become a powerful tool for site-specific protein modification. However, sortaseA (SrtA) suffers from low catalytic efficiency and mediates an equilibrium reaction. Therefore, ligations with large macromolecules may be challenging. Here, the synthesis of polymeric building blocks for sortase-mediated ligation constituting peptide-polymers with either the recognition sequence for sortaseA (LPX1TGX2) or its nucleophilic counterpart (Gx) is demonstrated. The peptide-polymers are synthesized by solid-phase peptide synthesis followed by photo-iniferter (PI) reversible addition-fragmentation chain-transfer (RAFT) polymerization of various monomers. The building blocks are subsequently utilized to investigate possibilities and limitations when using macromolecules in SML. In particular, diblock copolymers are obtained even when using the orthogonal building blocks in equimolar ratio by exploiting a technique to shift the reaction equilibrium. However, ligations of two polymers can not be achieved when the degree of polymerization exceeds 100. Subsequently, C-terminal protein-polymer conjugates are synthesized. Several polymers are utilized that can replace the omnipresent polyethylene glycol (PEG) in future therapeutics. The conjugation is exemplified with a nanobody that is known for efficient neutralization of SARS-CoV-2. The study demonstrates a universal approach to polymer-LPX1TGX2 and Gx-polymer building blocks and gives insight into their application in SML.

A novel cocrystal approach celecoxib with piperine: Simultaneously enhance dissolution rate and compressibility

Celecoxib, a selective COX-2 inhibitor non-steroidal anti-inflammatory drug (NSAID), exhibits analgesic and anti-inflammatory properties similar to piperine, the secondary metabolite of Piper nigrum L. Unfortunately, celecoxib has a low compressibility and low dissolution rate in aqueous medium. This study aimed to prepare a cocrystal of celecoxib and piperine to enhance the dissolution rate and compressibility properties of celecoxib. The cocrystal was synthesized using the seeding method and thoroughly characterized using Powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), infrared spectrophotometry, and single-crystal X-ray diffraction techniques. The complete change in PXRD, decrease in melting point in DSC measurements, and shift in the NH stretching band in the FT-IR spectrum suggested the formation of cocrystals phase. Single-crystal XRD confirmed the formation of an equimolar ratio of cocrystals of celecoxib and piperine. The intrinsic dissolution test was conducted to confirm the impact on the cocrystal to dissolution, and it showed a slight increase compared to intact celecoxib. To assess the physico-mechanical properties, the cocrystal powders were compressed into tablets with varying forces. The results demonstrated a significant improvement in compressibility compared with intact celecoxib owing to the slip plane in the crystal lattice of the cocrystal. In conclusion, our novel celecoxib-piperine cocrystal exhibited distinct physicochemical characteristics compared to intact celecoxib, showing enhanced dissolution rate and compressibility.

Molecular dynamics simulations of lipid composition and its impact on structural and dynamic properties of skin membrane

The stratum corneum (SC) plays the most important role in the absorption of topical and transdermal drugs. In this study, we developed a multi-layered SC model using coarse-grained molecular dynamics (CGMD) simulations of ceramides, cholesterol, and fatty acids in equimolar proportions, starting from two different initial configurations. In the first approach, all ceramide molecules were initially in the hairpin conformation, and the membrane bilayers were pre-formed. In the second approach, ceramide molecules were introduced in either the hairpin or splayed conformation, with the lipid molecules randomly oriented at the start of the simulation. The aim was to evaluate the effects of lipid chain length on the structural and dynamic properties of SC. By incorporating ceramides and fatty acids of different chain lengths, we simulated the SC membrane in healthy and diseased states. We calculated key structural properties including the thickness, normalized lipid area, lipid tail order parameters, and spatial ordering of the lipids from each system. The results showed that systems with higher ordering and structural integrity contained an equimolar ratio of ceramides (chain length of 24 carbon atoms), fatty acids with chain lengths ≥ of 20 carbon atoms, and cholesterol. In these systems, strong apolar interactions between the ceramide and fatty acid long acyl chains restricted the mobility of the lipid molecules, thereby maintaining a compact lipid headgroup region and high order in the lipid tail region. The simulations also revealed distinct flip-flop mechanisms for cholesterol and fatty acid within the multi-layered membrane. Cholesterol is mostly diffused through the tail-tail interface region of the membrane and could flip-flop in the same bilayer. In contrast, fatty acids flip-flopped between adjacent leaflets of two bilayers in which the tails crossed the thinner headgroup region of the membrane. To conclude, our SC model provides mechanistic insights into lipid mobility and is flexible in its design and composition of different lipids, enabling studies of varying skin conditions.

The embedding of 1,8-diazabicyclo[5.4.0]undec-7-ene into hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure

The preparation of cyclic carbonates via CO2 cycloaddition reaction was crucial for the lithium industry. Herein, a series of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) based hyper-crosslinked ionic polymers with different ionic site densities were prepared by simultaneously Friedel-Crafts alkylation and quaternization reactions. The obtained P[DBU]DCX(1:1) with a high ionic site density (1.45 mmol g−1), prepared by the equimolar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene and α,α′-dichloro-p-xylene, exhibiting excellent catalytic performance with a chloropropylene carbonate (CPC) yield of 98.8 % and selectivity of 99.3 % at atmospheric pressure. Meanwhile, the conversion capacity was comparable with other catalysts. Moreover, the CO2 cycloaddition reaction over P[DBU]DCX(1:1) catalyst followed pseudo-first-order kinetics, and the activation energy (Ea) was obtained to be 28.7 kJ/mol by performing kinetic experiments at different temperatures. In addition, it also had a good reusability and universality for different epoxides. The synergistic effects of abundant quaternary nitrogen cations derived from DBU and chlorine anions on the activation of CO2 and epoxide were explored based on density functional theory calculation. This study offers a new approach for the design and application of hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure.

A robust bio-based polyurethane employed as surgical suture with help to promote skin wound healing

Designing bio-based polyurethane materials with excellent mechanical, biocompatibility, and self-healing properties simultaneously is currently a significant challenge due to the increasing demands for high-performance materials. In this study, we propose an asymmetric backbone strategy utilizing bio-based polycarbonate as the soft segment, equimolar ratios of lysine diisocyanate and isophorone diisocyanate as asymmetric hard segments, and isophorone diamine as the chain extender. The resulting polyurethane elastomers exhibit excellent mechanical properties, including high tensile stress (46.1 MPa), toughness (213.9 MJ/m3), and fracture energy (98.47 kJ/m3). The polyurethane elastomers demonstrate good self-healing and recyclable properties under simple heat treatment. Furthermore, biological experiments confirm the degradability and bio-safety of the bio-based polyurethane elastomers, which have shown potential in accelerating wound healing in mice when used as surgical sutures. These findings highlight the promising prospects of the obtained polyurethane elastomers in various applications, including biomedicine, flexible sensing, and electronic components.

Characterization of naproxen salts with amino acid esters and their application in topical skin preparations

In the study, the modification of naproxen (NAP) with esters of four amino acids (AAs): glycine (GlyOiPr), L-proline (ProOiPr), L-leucine (LeuOiPr), and L-serine (SerOiPr) isopropyl ester was performed to improve water solubility and enhance the permeation of the drug through the skin in comparison to the parent NAP. The NAP derivatives were prepared using the equimolar ratio of the components. In-depth NMR and FTIR analysis revealed that the salts formed with the proton transfer from the carboxylic group of NAP to the amine group of the appropriate AA ester. The NAP salts exhibited improved solubility in water and PBS solution (pH 7.4) when compared to parent NAP. The values of the partition coefficient (log PO/W) for prepared salts were lower than for NAP, however, the salts maintained hydrophobic character determined by the positive values of log P. The In vitro permeation through the pig skin performed in Franz diffusion cells showed that all NAP salts exhibited a higher cumulative mass of permeated NAP (Q24h) than the parent acid. The highest permeation value was noted for [ProOiPr][NAP], with a pseudo-steady state flux (Jss) 32.5 µg NAP cm−2h−1, and Q24h = 246.4 µg NAP cm−2, it was 2.5 % of the applied dose. Moreover, topical preparations with [ProOiPr][NAP] and NAP were prepared based on two vehicles − Celugel® and Pentravan®- approved in pharmacy recipes. The permeation experiments through the Strat-M® showed, that both the Jss and Q24h of permeated drug from preparations containing [ProOiPr][NAP], were statistically several times greater than from the respective preparations with the unmodified acid. Additionally, preparations with [ProOiPr][NAP] provided significantly improved permeation of NAP than two commercial preparations, one of which contained naproxen as the acid and the other – as the sodium salt.

Synthesis of bistricyclic aromatic enes and related polycyclic systems via Pd-catalyzed tandem Suzuki coupling/Heck cyclization reaction

A variety of bistricyclic aromatic enes (BAEs) and its derivatives have been prepared via the palladium-catalyzed Suzuki coupling/Heck cyclization tandem reaction in one pot. In the new proposal the expected products were obtained in exciting yields at nearly equimolar ratios of the substrates. It is very useful method for the synthesis of the fluorenylidene-based BAEs. Even the corresponding ladder-type conjugated polymer was also prepared by the tandem reaction.

Hydrophilic interaction liquid chromatography: An efficient tool for assessing thorium interaction with phosphorylated biomimetic peptides

In the field of nuclear toxicology, the knowledge of the interaction of actinides (An) with biomolecules is of prime concern in order to elucidate their toxicity mechanism and to further develop selective decorporating agents. In this work, we demonstrated the great potential of hydrophilic interaction liquid chromatography (HILIC) to separate polar thorium (Th) biomimetic peptide complexes, as a key starting point to tackle these challenges. Th4+ was used as plutonium (Pu4+) analogue and pS16 and pS1368 as synthetic di- and tetra-phosphorylated peptides capable of mimicking the interaction sites of these An in osteopontin (OPN), a hyperphosphorylated protein. The objective was to determine the relative affinity of pS16 and pS1368 towards Th4+, and to evaluate the pS1368 selectivity when Th4+ was in competition complexation reaction with UO22+ at physiological pH. To meet these aims, HILIC was simultaneously coupled to electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), which allowed to identify online the molecular structure of the separated complexes and quantify them, in a single step. Dedicated HILIC conditions were firstly set up to separate the new dimeric Th2(peptide)2 complexes with good separation resolution (peptide = pS16 or pS1368). By adding pS16 and pS1368 in different proportions relatively to Th4+, we found that lower or equal proportions of pS16 with respect to pS1368 were not sufficient to displace pS1368 from Th2pS13682 and pS16 proportion higher than pS1368 led to the formation of a predominant ternary complex Th2(pS16)(pS1368), demonstrating preferential Th4+ binding to the tetra-phosphorylated peptide. Finally, online identification and quantification of the formed complexes when Th4+ and UO22+ were mixed in equimolar ratio relatively to pS1368 showed that in spite of pS1368 has been specifically designed to coordinate UO22+, pS1368 is also Th4+-selective and exhibits stronger affinity for this latter than for UO22+. Hence, the results gathered through this approach highlight the impact of Th4+ coordination chemistry on its interaction with pS1368 and more widely to its affinity for biomolecules.

Magnetic studies and Hirshfeld surface analysis of acetato bridged 2D Mn(II) coordination polymer with 4-aminobenzohydrazide ligand

A new acetato bridged 2D coordination polymer with general formula of [Mn(µ-4-ambh)(µ-OAc)(OAc)]n (1) was prepared by the reaction of Mn(OAc)2·4H2O with 4-aminobenzohydrazide (4-ambh) in equimolar ratio. The reaction was done in methanol under reflux condition and the single crystals of 1 were obtained by evaporation of the solvent. The structure of this compound was determined by X-ray analysis, and its spectroscopic properties and thermal stability were also studied. These studies indicated that in this compound, the manganese ions are connected by a mixture of acetate and 4-ambh bridges to form a 2D polymeric network at the bc crystallographic plane. The intermolecular and intramolecular interactions were investigated by Hirshfeld surface analysis. Magnetic studies revealed a dominant antiferromagnetic intermetallic coupling of J = −0.78 cm−1 magnitude. Magnetization measurements suggest a diamagnetic ground state and a small gap of 1.59 cm−1 with the first excited state; while the axial zero-field splitting parameter, D, was calculated at −0.21 cm−1.

The effects of refractory elements on the properties of quaternary high entropy carbides—A first-principles and experiment study

In this work, the effects of refractory transition metal elements on the properties of quaternary equimolar ratio high entropy carbides composed of ⅣB, ⅤB and ⅥB transition metals and C element were studied by first-principles calculations and experiments.The calculation results show that all 75 kinds of high entropy carbides were thermodynamically and mechanically stable and can be formed spontaneously. Among them, Hf can promote the synthesis of high entropy carbides, while Cr has the opposite effect. In addition, single phase solid solution structures can be formed for all 73 HECs except (TiZrHfCr)C and (ZrHfVCr)C. Thereafter, the mechanical properties of these 75 quaternary HECs were compared. The calculation results show that W, Mo, and Ta have a positive effect on improving the elastic modulus, fracture toughness, hardness and melting point of high entropy carbides, while Cr has the opposite effect. The calculation results of phonon spectra show that the six high entropy carbides represented by (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbCr)C, (TiZrNbMo)C and (TiZrNbW)C have lattice dynamic stability. (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbMo)C and (TiZrNbW)C face-centered cubic high entropy carbides were prepared by spark plasma sintering and the microstructure and properties were tested. The experimental results are basically consistent with the calculated results.

Narrow Range of Coagulation of Ion Associates of Poly(styrene sulfonate) with Alcian Blue Dye.

The ionic association of Alcian Blue dye with poly(styrene sulfonate) in aqueous solutions was studied for analytical purposes. The quadruple-charged cationic dye, Alcian Blue, was found to form colloidal ionic associates with poly(styrene sulfonate) anions. When the amounts of opposite charges are nearly equal, the resulting ionic associates lose solubility and coagulate rapidly. This effect occurs within a narrow range of the ratio of poly(styrene sulfonate) to Alcian Blue. At the point of charge equivalence, the zeta potential of the resulting particles is zero, which facilitates flocculation. The resulting flocs enlarge to approximately 0.05-0.5 mm and precipitate rapidly. FTIR spectroscopy confirms that the precipitate contains both poly(styrene sulfonate) and Alcian Blue dye. Sedimentation kinetics was studied in detail using scanning turbidimetry. Due to the high molar absorbance of the Alcian Blue dye at 600 nm, the point of equimolar charge ratio was precisely determined by spectrophotometry. The complete precipitation of ionic associates occurs when the amount of poly(styrene sulfonate) ranges from 1.4 to 1.55 mmol per 1 g of Alcian Blue dye. Such a narrow coagulation range allows for the use of the studied effect for quantitative analysis. Both Alcian Blue dye and poly(styrene sulfonate) can be quantified if one of their concentrations is known.

Pd(II), Pt(II), and novel Hg(II) metal complexes of N-(diphenylphosphinothioyl)-2-(4-methylpyridyl) amine chelating ligand: Synthesis, characterization, X-ray structures and catalytic activity of Pd(II) derivative in the Suzuki cross-coupling reaction

The reaction of monooxidized thioyl (4-CH3)C6H3N-2-NH(P(S)Ph2) (1) ligand with MCl2(COD)(M = Pd, Pt) in equimolar ratio resulted in cis-[MCl2{1-κ2S,Npy}] (M = Pd (2), Pt(3)) complexes. Also, The reaction of 1 with HgX2 (X = Cl, I) produced cis-[HgX2{1-κ2S,Npy }] (X = Cl(4), I(5)). Complexes 2–5 have been isolated and characterized by multinuclear NMR (1H, 13C, and 31P) and IR spectroscopy. The molecular structures of 2, 4, and 5 were determined using single X-ray crystallography. 4 and 5 are the first structurally defined instances of this type of κ2S,Npy -bidentate ligand with Hg(II) metal complexes. The new palladium(II) complex 2 as a pre-catalyst in the Suzuki cross-coupling process was also investigated.

Spectrophotometric analysis and mechanistic insights investigation of a developed CT complex as colorimetric real-time sensing performance towards Fe2+ in aqueous medium

A newly developed charge transfer complex (CTC) is explored for colorimetric real-time sensing behavior towards the Fe2+ ion, as a highly selective real-time colorimetric chemosensor material. The synthesized and characterized CTC / P1, [(2HP)+(SA)−] is cheap, remarkably distinctive, and simple to manufacture. Beyond the exposure limitations, iron is also the most common cofactor in enzyme reactions, which is, therefore a crucial part of life. However, too much or not enough iron leads to anemia, liver damage, cancer, Alzheimer's disease, and Parkinson's disease. In this report, unusual sensing capacity has been reported with a relatively low detection limit of 1.247 ppb for Fe2+ ions in aqueous medium, which was lowest at 1.267 ppb in previous reports of CTC sensors. By using a static quenching process, the incredible sensing behavior of this material as a chemosensor was determined. Colorimetric sensing behavior in real-time has also been observed. The complex has been described using a variety of methods, including UV-visible and FTIR spectroscopy. In FTIR spectra, the CTC (P1) showed a change in wavenumber when compared to its reactants. Furthermore, the complex's stoichiometry was measured using UV-visible spectroscopy by taking mixture with an equimolar ratio using the straight-line approach known as the Benesi-Hildebrand equation, which was found to be 1:1. Oscillator strength (f), transition dipole moment (μEN), molar extinction coefficient (εCT), energy of interaction (ECT), and stability constant (KCT) were among the thermodynamic and physical characteristics studied. Van't Hoff's equation was used to compute other parameters such as Gibbs free energy (G°), absorptivity coefficient (ε), Resonance energy (RN), etc. [O+—H……O−] hydrogen bonding was used to depict the interaction between reactants (salicylic acid and 2-hydroxypyridine). The stability of the P1 as a function of temperature is demonstrated through TG/DTA analysis.

Chemical Structure and Thermal Properties versus Accelerated Aging of Bio-Based Poly(ether-urethanes) with Modified Hard Segments.

Aging of polymers is a natural process that occurs during their usage and storage. Predicting the lifetime of polymers is a crucial aspect that should be considered at the design stage. In this paper, a series of bio-based thermoplastic poly(ether-urethane) elastomers (bio-TPUs) with modified hard segments were synthesized and investigated to understand the structural and property changes triggered by accelerated aging. The bio-TPUs were synthesized at an equimolar ratio of reagents using the prepolymer method with the use of bio-based poly(trimethylene ether) glycol, bio-based 1,3-propanediol, and hexamethylene diisocyanate or hexamethylene diisocyanate/partially bio-based diisocyanate mixtures. The polymerization reaction was catalyzed by dibutyltin dilaurate (DBTDL). The structural and property changes after accelerated aging under thermal and hydrothermal conditions were determined using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Among other findings, it was observed that both the reference and aged bio-TPUs decomposed in two main stages and exhibited thermal stability up to approximately 300 °C. Based on the research conducted, it was found that accelerated aging impacts the supramolecular structure of TPUs.

Synthesis and characterization of biobased copolyesters based on pentanediol: (1) Poly(pentylene dodecanoate‐co‐furandicarboxylate)

AbstractA series of biobased aliphatic‐aromatic copolyesters, poly(pentylene dodecanoate‐co‐furandicarboxylates) (PPeDFs) were synthesized via an esterification and polycondensation melt process. The copolyesters were characterized using gel permeation chromatography, Fourier transform infrared spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, wide angle x‐ray scattering, and tensile testing. The thermal transition behavior was strongly dependent on composition, with the melting and glass transition temperatures reaching a minimum at approximately equimolar ratio of D to F. All copolyesters were stable below 300°C with their R600 (the weight of material remaining at 600°C) values increasing with F fraction. PPeD to PPeDF30 (e.g., mole ratio D/F = 7:3) show sharp PPeD crystalline reflections only while broad PPeF reflections are shown in PPeF and PPeDF90. PPeDF40 to PPeDF80 showed both crystal structures. The fractional crystallinity for the PPeD was much higher than PPeF and the fractional crystallinity of the copolymers showed a minimum at D/F ratios closer to the latter. The stress at break and modulus both exhibited maxima at D/F ratios that were either high or low, but somewhat surprisingly a strong maximum in percent elongation at break of over 600% occurs at PPeDF40. For this composition, a typical plastic behavior curve was found including a yield point, high elongation at break, and strain hardening.Highlights Poly(pentylene dodecanoate‐co‐furandicarboxylates) (PPeDFs) are synthesized Mechanical properties, a function of D:F ratio. High elongation at 40 mol% F. Two melting temperatures/crystal structures, one PPeD, the other PPeF Glass transition temperature minimum at intermediate D:F ratios

Reversible Hydrophobic Deep Eutectic Solvent-Based Uranyl-Sensing Optode Film in Aqueous Streams: Color Transformation and Reusability.

A hydrophobic deep eutectic solvent (HDES)-based optode was designed for the preconcentration and determination of the UO22+ ion in aqueous media using spectroscopic techniques [energy-dispersive X-ray fluorescence (EDXRF) and solid-state absorption]. The optode was developed by incorporation of HDES (tri-n-octyl phosphine oxide and decanoic acid in an equimolar ratio), tri-(2-ethylhexyl) phosphate, and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol into a cellulose triacetate matrix. Characterization studies were carried out using different techniques to understand the roles of HDES as a plasticizer, UO22+ extractant, and Br-PADAP immobilizer. Uptake studies revealed that the optimal pH was 3 and sorption followed the type II adsorption isotherm. Uranium in the U-sorbed optode can be directly analyzed over a large concentration range of 0.021 × 10-3-2.1 × 10-3 Mol L-1 using EDXRF. The optode film exhibited a linear dynamic range of 0.84 × 10-6-84 × 10-6 Mol L-1 for uranium, with a lowest limit of detection of 0.084 × 10-6 Mol L-1 by colorimetric analysis. This optode-based method was employed for seawater analysis for its UO22+ concentration without any matrix separation, and the concentration was found to be 1.30 ± 0.06 × 10-8 Mol L-1. The optode exhibited better selectivity for UO22+ in the presence of various cations including Sr2+ and Cs+ in an aqueous medium. Compared to other prevailing optical sensors, this optode performed better in terms of key factors like pH, equilibration time, reusability, and detection limit.

Elucidating Factors Contributing to Dicamba Volatilization by Characterizing Chemical Speciation in Dried Dicamba-Amine Residues.

Dicamba is a semivolatile herbicide that has caused widespread unintentional damage to vegetation due to its volatilization from genetically engineered dicamba-tolerant crops. Strategies to reduce dicamba volatilization rely on the use of formulations containing amines, which deprotonate dicamba to generate a nonvolatile anion in aqueous solution. Dicamba volatilization in the field is also expected to occur after aqueous spray droplets dry to produce a residue; however, dicamba speciation in this phase is poorly understood. We applied Fourier transform infrared (FTIR) spectroscopy to evaluate dicamba protonation state in dried dicamba-amine residues. We first demonstrated that commercially relevant amines such as diglycolamine (DGA) and n,n-bis(3-aminopropyl)methylamine (BAPMA) fully deprotonated dicamba when applied at an equimolar molar ratio, while dimethylamine (DMA) allowed neutral dicamba to remain detectable, which corresponded to greater dicamba volatilization. Expanding the amines tested, we determined that dicamba speciation in the residues was unrelated to solution-phase amine pKa, but instead was affected by other amine characteristics (i.e., number of hydrogen bonding sites) that also correlated with greater dicamba volatilization. Finally, we characterized dicamba-amine residues containing an additional component (i.e., the herbicide S-metolachlor registered for use alongside dicamba) to investigate dicamba speciation in a more complex chemical environment encountered in field applications.

A self-catalyzing strategy for co-immobilization of two distinct proteins at equimolar ratio: A case study of 3A and 2C to develop a chromatographic method for finding prospective dual-target compoundsfrom complex matrices

BackgroundImmobilized proteins hold promise as the basic units that have enabled a broad range of analytical applications within chemical measurement science. As yet, the co-immobilization of diverse proteins at precise ratio and whether they give rise to improved analytical performance remain challengeable. Herein, we utilized a circularly permuted HaloTag (cpHaloTag) to achieve the co-immobilization of two proteins at precise ratio, which was applied in developing a chromatographic method with improved specificity for pursuing dual-target compounds. ResultsThe methodology involved the fusion 3A and 2C at N- and C-terminuses of cpHaloTag, the immobilization of the fusion protein onto silica gel through bioorthogonal reaction, the morphological and functional characterization, the application in finding dual-target compounds. Expression of the fusion protein in E. coli system showed a yield of milligram level with the presence of 3A and 2C domains. Immobilization of the protein was achieved in 10 min with a reaction efficiency more than 88.5 %. Immobilized 3A-cpHalo-2C exhibited higher specificity and better retentions of canonical compounds of the two enzymes in comparison with the column containing immobilized 3A or 2C alone. In real sample application, screening analysis found that hyperoside, cymaroside, and baicalin were dual-target compounds in concert with 3A and 2C in Shuanghuanglian extract. SignificanceTaking 3A and 2C as probe, we proposed a simple method for direct co-immobilization of diverse proteins from cell lysates and demonstrated an affinity chromatographic-based dual-target compound screening platform. The implications of these methodology are possible to insight the de novo design of multi-target surface for fabricating new bioanalytical methods with improved performance.

Structural, optical, and electrical properties of multi-component P-type oxide-semiconductor Cu-Mn-Sn-O thin films

P-type oxide semiconductors have attracted significant attention as conducting channel layers due to their wide applications in electronic devices. In this study, multi-component oxide-semiconductor Cu1–2xMnxSnxO thin films with x = 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, and 0.33 were prepared on glass substrates using a solution process accompanied by a spin-coating technique. A phase transition between the cupric oxide monoclinic structure and the rock salt structure was observed with increasing concentrations of Mn and Sn, while the concentration of Cu simultaneously decreased in the precursors. The crystallite size decreased throughout the samples, reaching a minimum value of 9.8 nm at an equimolar ratio. Scanning electron microscopy further confirmed this downward trend and indicated an improvement in the quality of the film surfaces. According to the optical absorption measurements, the bandgap energy ranged from 2.68 to 3.44 eV. Interestingly, the sheet resistance of Cu1–2xMnxSnxO films dropped sharply from 5.24 kΩ/sq for CuO to 0.034 kΩ/sq for the film with a molar ratio of Cu:Mn:Sn being 34:33:33.