CA Molecules Research Articles

A Neural Network Potential Energy Surface and Quantum Dynamics Study of Ca(1S) + H2(v 0 = 0, j 0 = 0) → CaH + H Reaction.

The reactive collision between Ca and H2 molecules has attracted great interest experimentally due to the key role of the product CaH molecule in the field of astrophysics and cold molecules. However, quantum dynamics calculations for this system have not been reported due to the lack of a global potential energy surface (PES). Herein, a globally accurate PES of the ground-state CaH2 is developed by combining 11365 high-level ab initio points and permutation invariant polynomial neural network method. Based on the newly constructed PES, the state-to-state quantum dynamics calculations for the Ca(1S) + H2 (v 0 = 0, j 0 = 0) → CaH + H reaction are carried out using the time-dependent wave packet method. The dynamic results reveal that the reaction follows the complex-forming mechanism near the reactive threshold, whereas both the indirect insertion mechanism and direct abstraction mechanism have effects at higher collision energies. The newly constructed PES can be used to further study the influence of isotope substitution, rovibrational excitation, and spatial orientation of reactant molecules on reaction dynamics.

Effect of Citric Acid Modification on Physio‐Chemical, Structural, Rheological, Thermal Properties, and In Vitro Digestibility of Amaranthus paniculatus (Rajgeera) Starch

AbstractIn this study, starch is treated with different concentrations of citric acid (CA, 5, 10, 20, and 30 g/100 g dry basis) which leads to the production of citrate starch. The effect of CA concentration on physio‐chemical, structural, rheological, thermal properties, and digestibility is analyzed. A Fourier transform infrared (FTIR) spectroscopy Stands for FTIR peak at 1728 cm−1 is observed, indicating ester bond formation between CA and starch molecules. A nonsignificant change in the crystalline pattern is observed between native and citrate starch, whereas a decrease in relative crystallinity from 15.75% to 6.91% is observed. With the increase in the degree of substitution, gelatinization decreases, and gelatinization's enthalpy (ΔH) decreases from 13.72 to 9.63 J g−1. The rapid digestible starch (RDS) decreases by CA treatment, whereas slow digestible starch (SDS) and resistant starch (RS) increase significantly from 32.81 g/100 g dry basis to 39.45 g/100 g dry basis and 9.87 g/100 g dry basis to 25.26 g/100 g dry basis, respectively.

Effect of Fe3O4 Nanoparticles Modified by Citric and Oleic Acids on the Physicochemical and Magnetic Properties of Hybrid Electrospun P(VDF-TrFE) Scaffolds.

This study considers a fabrication of magnetoactive scaffolds based on a copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)) and 5, 10, and 15 wt.% of magnetite (Fe3O4) nanoparticles modified with citric (CA) and oleic (OA) acids by solution electrospinning. The synthesized Fe3O4-CA and Fe3O4-OA nanoparticles are similar in particle size and phase composition, but differ in zeta potential values and magnetic properties. Pure P(VDF-TrFE) scaffolds as well as composites with Fe3O4-CA and Fe3O4-OA nanoparticles demonstrate beads-free 1 μm fibers. According to scanning electron (SEM) and transmission electron (TEM) microscopy, fabricated P(VDF-TrFE) scaffolds filled with CA-modified Fe3O4 nanoparticles have a more homogeneous distribution of magnetic filler due to both the high stabilization ability of CA molecules and the affinity of Fe3O4-CA nanoparticles to the solvent used and P(VDF-TrFE) functional groups. The phase composition of pure and composite scaffolds includes a predominant piezoelectric β-phase, and a γ-phase, to a lesser extent. When adding Fe3O4-CA and Fe3O4-OA nanoparticles, there was no significant decrease in the degree of crystallinity of the P(VDF-TrFE), which, on the contrary, increased up to 76% in the case of composite scaffolds loaded with 15 wt.% of the magnetic fillers. Magnetic properties, mainly saturation magnetization (Ms), are in a good agreement with the content of Fe3O4 nanoparticles and show, among the known magnetoactive PVDF or P(VDF-TrFE) scaffolds, the highest Ms value, equal to 10.0 emu/g in the case of P(VDF-TrFE) composite with 15 wt.% of Fe3O4-CA nanoparticles.

Circumpentacene with Open‐Shell Singlet Diradical Character

AbstractCircumacenes (CAs) are a distinctive type of benzenoid polycyclic aromatic hydrocarbons where an acene unit is completely enclosed by a layer of outer fused benzene rings. Despite their unique structures, the synthesis of CAs is challenging, and until recently, the largest CA molecule synthesized was circumanthracene. In this study, we report the successful synthesis of an extended circumpentacene derivative 1, which represents the largest CA molecule synthesized to date. Its structure was confirmed by X‐ray crystallographic analysis and its electronic properties were systematically investigated by both experiments and theoretical calculations. It shows a unique open‐shell diradical character due to the existence of extended zigzag edges, with a moderate diradical character index (y0=39.7 %) and a small singlet‐triplet energy gap (ΔES‐T=−4.47 kcal/mol). It exhibits a dominant local aromatic character with π‐electrons delocalized in the individual aromatic sextet rings. It has a small HOMO–LUMO energy gap and displays amphoteric redox behavior. The electronic structures of its dication and dianion can be considered as doubly charged structures in which two coronene units are fused with a central aromatic benzene ring. This study provides a new route toward stable multizigzag‐edged graphene‐like molecules with open‐shell di/polyradical character.

Systematic Exploration of Structural Topologies in Hydrogen-Bonded Supramolecular Assemblies of Citric Acid with Different Heterocyclic Compounds.

Hydrogen-bonded supramolecular assemblies of citric acid, CA, with some heterocyclic compounds (N-donor and N-oxide)-acridine (acr), phenazine (phenz), 1,10-phenanthroline (110phen), 1,7-phenanthroline (17phen), 4,7-phenanthroline (47phen), 1,4-diazabicyclo[2.2.2]octane (dabco), and 4,4'-bipyridyl-N,N'-dioxide (bpydo)-have been reported. Among these, only the N-donors phenz and N-oxide (bpydo) form neutral co-crystals, while the others form salts owing to the deprotonation of -COOH. Thus, depending on the nature of the aggregate (salt/co-crystal), recognition between the co-formers is established through O-H···N/N+-H···O/N+H···O-heteromeric hydrogen bonding. Additionally, CA molecules establish homomeric interactions mediated by O-H···O hydrogen bonds. Moreover, CA forms a cyclic network with the co-formers or on its own, with a noteworthy feature of formation of host-guest networks in the assemblies with acr and phenz (solvated). In the assembly of acr, the CA molecules form a host network and captivate acr molecules as guest species, while in the case of phenz assembly, both the co-formers together encapsulate the solvent in the channels. However, the observed cyclic networks in the other structures form three-dimensional topologies in the form of ladders, a sandwich, lamellar layers, and interpenetrated networks. The structural features of the ensembles are evaluated unequivocally by the single-crystal X-ray diffraction method, while the homogeneity and phase purity are evaluated by using the powder X-ray diffraction method and differential scanning calorimetry. Further, conformational analysis of CA molecules reveals three types of conformations-T-shape (type I), syn-anti (type II), and syn (type III) as also observed in the literature for other CA co-crystals. In addition, the strength of the intermolecular interactions is quantified by performing Hirshfeld analysis.

Biomimetic redox-responsive smart coatings with resistance-release functions for reverse osmosis membranes.

Membrane fouling induces catastrophic loss of separation performance and seriously restricts the applications of reverse osmosis (RO) membranes. Inspired by the mussel structure, polydopamine (PDA) and cystamine molecules (CA) with excellent anti-fouling properties were used to prepare accessible, biocompatible, and redox-responsive coatings for RO membranes. The PDA/CA-coated RO membranes exhibit a superior water flux of 65 L m-2 h-1 with a favourable NaCl rejection exceeding 99%. The water permeability through the PDA/CA-coated membrane is much higher than that of most membranes with similar rejection rates. Due to the formed protective hydration layers by PDA/CA coatings, anti-fouling properties against proteins, polysaccharides and surfactants were evaluated separately, and ultralow fouling properties were demonstrated. Moreover, the disulfide linkages in CA molecules can cleave in a reducing environment, yielding the degradation of PDA/CA coatings, thereby removing the foulants deposited on the coatings. The degradation endows the coated membranes with satisfying longtime anti-fouling properties, where the flux recovery reaches up to 90%. The construction of redox-responsive smart coatings not only provided a promising route to alleviate membrane fouling but can also be upscaled for use in numerous practical applications like sensors, medical devices, and drug delivery.

Experimental study on distillation and purification of reclaimed NMP

With the proposal of double carbon target, NMP is widely used in lithium battery industry, chemical process, petroleum industry and other industries. Its purity directly affects the production and quality of products. In this paper, the NMP recovered liquid is taken as the experimental object, and the atmospheric and vacuum distillation methods are used to distill the recovered liquid for many times to remove impurities, so as to reduce the content of impurity elements such as Ca, Na, Si and water molecules. The Karl Fischer moisture meter, ICP-OES and ultraviolet photometer are used to detect and compare the experimental results. It is found that the moisture in the NMP recovered by distillation can be gradually reduced. Through UV analysis, in the second temperature step of distillation, 274 nm and 325 nm impurity peaks can be removed to achieve the purpose of removing impurity peaks and effectively reduce the impurity content in NMP recovery solution. The experimental method for removing impurities of Ca, Na, Si elements and water molecules in NMP recovery solution proposed in this paper provides a certain reference for NMP purification research.

The incorporation of upper vs lower rim substituted thia- and calix[4]arene ligands into polydiacethylene polymeric bilayers for rational design of sensors to heavy metal ions

1,3-Diketone calix [4]arene (CA) and thiacalix [4]arene (TCA), with the hydrophobic substituents introduced onto lower or upper rims respectively, form mixed aggregates with 10,12-pentacosadiynoic acid (PCDA) through the thin film hydration technique. Computer simulations, showing the arrangement of TCA and CA molecules in supramolecular clusters with PCDA molecules, suggest that PCDA assemblies with both cyclophanes are a convinient basis for the coordination of metal ions. However, photopolymerization of mixed aggregates reveals more disruption of the vesicular nanostructure of polydiacetylene (PDA) when CA molecules are included compared to TCA. The incorporation of the TCA and CA ligands influences the ability of the mixed PDA-bilayers to conformational and spectral changes and provides tight coordination of Tb3+ ions and efficient sensitizing of the Tb3+-centered luminescence. The PDA-bilayers incorporated by terbium TCA complex provide more sensitive response on the series of heavy metal ions vs their CA-based analogues. The surface exposed TCA rims and carboxylate moieties of PDA provide two different binding sites for Tb3+ and heavy metal ions. Both distribution of Tb3+ and heavy metal ions between these sites and heterometallic complex formation are revealed as the factors affecting the luminescence response of PDA-TCA terbium complex in the solutions of heavy metal ions. The interplay between these factors is the reason for the different luminescence response of PDA-TCA terbium complex on Cd2+, Hg2+ and Pb2+ ions. The PDA-vesicles incorporated by terbium TCA complex exhibit easier phase separation vs the PDA vesicles themselves, which favors the extraction of Pb2+ ions.

Mediating the slow dynamics of polyacrylates by small molecule-bridged hydrogen bonds.

This report studied the changes in the slow dynamics of polyacrylate by adding a hindered phenol (CA) capable of forming three intermolecular hydrogen bonds (inter-HBs) per molecule with the polymer chain. The CA molecule apparently diminishes the slow modes (with lower peak temperatures and peak heights) of the polyacrylate, although it has a higher glass transition temperature (Tg) than the acrylic matrix, and the rigid CA-bridged HB network significantly amplifies the α-relaxation near Tg (with higher peak temperatures and peak heights). Consequently, the mixtures exhibit a diminishing slow mode that gradually merges with the prominent α-peak with increasing CA loadings. The anomalous dynamics concerning the opposite behaviors of the slow mode and α-relaxation was further rationalized in terms of dissociation of inter-HBs when the temperature is higher than Tg, together with the small molecule-alleviated macromolecular connectivity. This work provides essential insights into the slow dynamics of such HB-driven hybrids, and paves the way for tailoring the viscous flow properties of the hybrid material from a molecular level perspective.

Structural basis of cyclic oligoadenylate degradation by ancillary Type III CRISPR-Cas ring nucleases.

Type III CRISPR-Cas effector systems detect foreign RNA triggering DNA and RNA cleavage and synthesizing cyclic oligoadenylate molecules (cA) in their Cas10 subunit. cAs act as a second messenger activating auxiliary nucleases, leading to an indiscriminate RNA degradation that can end in cell dormancy or death. Standalone ring nucleases are CRISPR ancillary proteins which downregulate the strong immune response of Type III systems by degrading cA. These enzymes contain a CRISPR-associated Rossman-fold (CARF) domain, which binds and cleaves the cA molecule. Here, we present the structures of the standalone ring nuclease from Sulfolobus islandicus (Sis) 0811 in its apo and post-catalytic states. This enzyme is composed by a N-terminal CARF and a C-terminal wHTH domain. Sis0811 presents a phosphodiester hydrolysis metal-independent mechanism, which cleaves cA4 rings to generate linear adenylate species, thus reducing the levels of the second messenger and switching off the cell antiviral state. The structural and biochemical analysis revealed the coupling of a cork-screw conformational change with the positioning of key catalytic residues to proceed with cA4 phosphodiester hydrolysis in a non-concerted manner.

In vivo study of light-driven naproxen release from gated mesoporous silica drug delivery system

A drug delivery system based on mesoporous particles MCM-41 was post-synthetically modified by photo-sensitive ligand, methyl-(2E)-3-(4-(triethoxysilyl)-propoxyphenyl)-2-propenoate (CA) and the pores of MCM-41 particles were loaded with Naproxen sodium salt (NAP). The CA was used as a photoactive molecule that can undergo a reversible photo-dimerization by [2π + 2π] cycloaddition when irradiated with UV light of specific wavelengths. Thus, it has a function of gate-keeper that is responsible for opening/closing the pores and minimizing premature release of NAP. The physicochemical properties of the prepared system were studied by infrared spectroscopy (IR), nitrogen adsorption measurements, thermogravimetric analysis (TGA), scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX). The mechanism of the opening/closing pores was confirmed by UV measurements. In vitro and in vivo drug release experiments and the concentration of released NAP was determined by UV spectroscopy and high-performance liquid chromatography (HPLC). In vivo drug release in the blood circulatory system of rats has demonstrated the effective photo-cleavage reaction of CA molecules after UV-light stimulation. The localization and morphological changes of the particles were studied in the blood and liver of rats at different time intervals. The particles in the blood have been shown to retain their original rod-like shape, and the particles in the liver have been hydrolysed, which has resulted in spherical shape with a reduced size.

Role of Dynamical Electron Correlation in the Differences in Bonding between CaAlH3 and MgAlH3.

The most important factor behind the intriguing differences between the geometries of the M′AlH3 (M′ = Mg, Ca) molecules is shown to be dynamical electron correlation and not intramolecular Coulombic interactions, as previously thought. Spin-coupled generalized valence bond (SCGVB) calculations reveal the different bonding situations in the two molecules at their optimal geometries but do not explain why these geometries differ so much; the solution to this conundrum comes instead from detailed analysis of coupled-cluster (CCSD(T)) energies at model and optimal geometries.

Tailored Catalytic Nanoframes from Metal-Organic Frameworks by Anisotropic Surface Modification and Etching for the Hydrogen Evolution Reaction.

A facile anisotropic surface modification and etching strategy is presented for the synthesis of hollow structured ZIF-67 nanoframes. The strategy uses structural and compositional distinctions between each crystallographic facet of truncated rhombic dodecahedrons ZIF-67 (tZIF-67 RDs) and the moderate coordinating and etching effects of cyanuric acid (CA). The CA can anisotropically modify and protect the {110} facets from etching, causing the six {100} facets be selectively etched via an inside-out manner, and finally forming the hollow nanoframes. The surface-modified hollow tZIF-67 RDs can be facet-selectively etched by metal salts in an outside-in manner to give metal-doped tZIF-67 nanoframes. After calcination, the metal-tZIF-67 hybrids are converted into metal-Co alloy/C composite catalysts with hollow nanoframed structures. The PtCo/C catalyst with only 5.9 wt % Pt exhibits high catalytic activities and stabilities in the hydrogen evolution reaction (HER) in acidic solutions.

Limousinite, BaCa[Be4P4O16]·6H2O, a new beryllophosphate mineral with a phillipsite-type framework

ABSTRACT Limousinite, ideally BaCa[Be4P4O16]·6H2O, is a new beryllophosphate mineral discovered in the Vilatte-Haute pegmatite, Chanteloube near Razès, Limousin, Haute-Vienne, France. The new mineral is intimately associated with microcrystalline pale brown greifensteinite, black amorphous vitreous Mn-oxyhydroxide, triplite, and quartz. It forms isolated, partly corroded, colorless to snow-white crystals up to 0.9 mm long, showing rhombic cross sections. Limousinite is transparent with a vitreous luster, non-fluorescent, without cleavage planes; its calculated density is 2.58 g/cm3. Optically, the mineral is biaxial negative, α = 1.532(2), β = 1.553(3), γ = 1.558(2) (measured under 589 nm wavelength light), 2Vcalc. = 18°, non-dispersive, with Z parallel to the elongation of the prismatic crystals. Electron-microprobe analyses indicate an empirical formula of (Ba0.91K0.07)Σ0.98(Ca0.87Na0.05)Σ0.92[(Be3.87Al0.13)Σ4P4O16]·5.56H2O, calculated on the basis of 4 P atoms per formula unit, assuming 4 (Be + Al) pfu and a water content calculated from refined site-occupancy factors. A single-crystal structure refinement was performed to R1 = 4.90%, in the P21/c space group, with a = 9.4958(4), b = 13.6758(4), c = 13.4696(4) Å, β = 90.398(3)°, V = 1749.15(10) Å3, Z = 4. The crystal structure is characterized by a beryllophosphate framework similar to that of phillipsite-group zeolites, based on corner-sharing BeO4 and PO4 tetrahedra forming interconnected four- and eight-membered rings. Large cages within this zeolite framework contain Ba, Ca, and water molecules. Limousinite is the third known natural zeolite-type beryllophosphate, together with pahasapaite and wilancookite; it is also the first phosphate with a framework identical to that of a natural zeolite silicate.

Tailored-design of electrospun nanofiber cellulose acetate/poly(lactic acid) dressing mats loaded with a newly synthesized sulfonamide analog exhibiting superior wound healing

To effectively allow for controlled release of a newly synthesized sulfonamide analog, biodegradable poly(lactic acid) nanofibrous dressing mats tailored-designed for maximum wound healing efficacy were developed. The heterocyclic analog, N-(3,4-diamino-7-(benzo [d]thiazol-2-yl)-6-oxo-1H-pyrazolo[4,3-c]pyridin-5(6H)-yl)benzenesulfonamide, has been specifically synthesized to possess superior antibacterial and anti-inflammatory characteristics. Hydrophilic cellulose acetate and/or poly(ethylene oxide) were blended with the hydrophobic PLA to control the hydrophilicity/hydrophobicity ratio for the sustained release of the drug. SEM detected no drug crystals on the surface of the nanofibers confirming the homogeneous dispersion and compatibility of the drug with the nanofibers. BET indicated almost-reversible Type II sorption isotherms. The swelling studies revealed that the presence of hydrogen bonds between the hydroxyl groups of CA with the carbonyl ester groups of PLA limited the ability of CA molecules to leach from the polymer matrix. Water vapor permeability were all determined to be within the range of 15–19 g/m2/h. In-vitro cell viability and cell proliferation studies revealed the superiority of the fabricated dressing mats in terms of its bioactivity and cellular interaction. In-vivo studies confirmed the major improvement in its wound healing capabilities attributed to an enhanced epithelization, anti-inflammation, neo-angiogenesis, fibroplasias and collagen deposition that surpassed that of commercially available ones.

Intrinsic curvature of the HIV-1 CA hexamer underlies capsid topology and interaction with cyclophilin A.

The mature retrovirus capsid consists of a variably curved lattice of capsid protein (CA) hexamers and pentamers. High-resolution structures of the curved assembly, or in complex with host factors, have not been available. By devising cryo-EM methodologies for exceedingly flexible and pleomorphic assemblies, we have determined cryo-EM structures of apo-CA hexamers and in complex with cyclophilin A (CypA) at near-atomic resolutions. The CA hexamers are intrinsically curved, flexible and asymmetric, revealing the capsomere and not the previously touted dimer or trimer interfaces as the key contributor to capsid curvature. CypA recognizes specific geometries of the curved lattice, simultaneously interacting with three CA protomers from adjacent hexamers via two noncanonical interfaces, thus stabilizing the capsid. By determining multiple structures from various helical symmetries, we further revealed the essential plasticity of the CA molecule, which allows formation of continuously curved conical capsids and the mechanism of capsid pattern sensing by CypA.

Experimental and theoretical studies of cinnamyl alcohol as a novel corrosion inhibitor for copper foils in rolling oil

AbstractCinnamyl alcohol (CA) was added to the rolling oil of copper foils as a novel corrosion inhibitor, and its anticorrosion performance and mechanism were studied using potentiodynamic polarization and electrochemical impedance spectroscopy. Microstructure and chemical composition of the copper electrode surface were analyzed by scanning electron microscopy, energy‐dispersive spectroscopy, and X‐ray photoelectron spectroscopy. The results showed that CA acted as a mixed‐type inhibitor, and the maximum inhibition efficiency of 87.7% was achieved at 2.4 mM. Moreover, a protective film was formed on the copper surface, which attributed to the C–OH groups in the CA molecule. The absorption of CA on the copper surface was physisorption, which conformed to Langmuir adsorption isotherm, with a standard adsorption free energy of −11.38 kJ/mol. In the presence of CA, some flaky corrosion products changed into granular corrosion products. The synergistic effect of the granular corrosion products (copper chloride hydroxide) and the CA film further decreased the corrosion rate.

Analysis of CA Content and CPSF6 Dependence of Early HIV-1 Replication Complexes in SupT1-R5 Cells.

HIV-1 infects host cells by fusion at the plasma membrane, leading to cytoplasmic entry of the viral capsid encasing the genome and replication machinery. The capsid eventually needs to disassemble, but time and location of uncoating are not fully characterized and may vary depending on the host cell. To study the fate of the capsid by fluorescence and superresolution (STED) microscopy, we established an experimental system that allows discrimination of subviral structures in the cytosol from intact virions at the plasma membrane or in endosomes without genetic modification of the virus. Quantitative microscopy of infected SupT1-R5 cells revealed that the CA signal on cytosolic HIV-1 complexes corresponded to ∼50% of that found in virions at the cell surface, in agreement with dissociation of nonassembled CA molecules from entering capsids after membrane fusion. The relative amount of CA in postfusion complexes remained stable until they reached the nuclear pore complex, while subviral structures in the nucleus of infected cells lacked detectable CA. An HIV-1 variant defective in binding of the host protein cleavage and polyadenylation specificity factor 6 (CPSF6) exhibited accumulation of CA-positive subviral complexes close to the nuclear envelope without loss of infectivity; STED microscopy revealed direct association of these complexes with nuclear pores. These results support previous observations indicating capsid uncoating at the nuclear pore in infected T-cell lines. They suggest that largely intact HIV-1 capsids dock at the nuclear pore in infected SupT1-R5 cells, with CPSF6 being a facilitator of nucleoplasmic entry in this cell type, as has been observed for infected macrophages.IMPORTANCE The HIV-1 capsid performs essential functions during early viral replication and is an interesting target for novel antivirals. Thus, understanding molecular and structural details of capsid function will be important for elucidating early HIV-1 (and retroviral in general) replication in relevant target cells and may also aid antiviral development. Here, we show that HIV-1 capsids stay largely intact during transport to the nucleus of infected T cells but appear to uncoat upon entry into the nucleoplasm. These results support the hypothesis that capsids protect the HIV-1 genome from cytoplasmic defense mechanisms and target the genome toward the nucleus. A protective role of the capsid could be a paradigm that also applies to other viruses. Our findings raise the question of how reverse transcription of the HIV-1 genome is accomplished in the context of the capsid structure and whether the process is completed before the capsid is uncoated at the nuclear pore.

Molecular Assembly between Weak Crosslinking Cyclodextrin Polymer and trans-Cinnamaldehyde for Corrosion Inhibition towards Mild Steel in 3.5% NaCl Solution: Experimental and Theoretical Studies.

Constructing molecular assembly between a soluble cyclodextrin polymer (SCDP) and an anticorrosive component is conducive to increasing the availability of a corrosion inhibitor with low molecular polarity in aqueous solution. The SCDP was prepared via the weak crosslinking effect of glutaraldehyde using β-cyclodextrin as the subunit, whose structure was confirmed by proton nuclear magnetic resonance spectra (1H NMR), X-ray diffraction and morphology. An assembly between SCDP (host) and trans-cinnamaldehyde (guest, CA) was constructed, and the intermolecular interactions were disclosed by Fourier transform infrared spectra (FTIR). The corrosion inhibition of SCDP/CA assembly for mild steel in 3.5% NaCl solution was assessed through electrochemical and surface analyses. 1H NMR results showed that exterior hydroxyls of β-cyclodextrin were the active sites for crosslinking. Hydrogen bonds might be the binding force between SCDP and CA according to FTIR analyses. Electrochemical measurements revealed that SCDP/CA assembly could suppress both cathodic and anodic reactions and enhance the polarization impedance for mild steel in the corrosive medium with a maximum efficiency of 92.2% at 30 °C. Surface analyses showed that CA molecules could be released from the assembly followed by the energy competition mechanism, and solely adsorb on the steel surface in parallel form, which was further evidenced by theoretical modeling.

Understanding the nature of bonding interactions in the carbonic acid dimers.

Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H-O, H-O⋯H-O, C=O⋯C=O, C=O⋯O-H, and C-O⋯O-H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H-O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti-anti monomers interacting via the strongest C=O⋯H-O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. Graphical Abstract Carbonic acid dimer, (CA)2, (H2CO3)2, helps explaining the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well-characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H-O, H-O⋯O-H, C=O⋯C=O, C=O⋯O-C, and C-O⋯O-C. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer.