Resonant X-ray Diffraction Research Articles

Heterometallic Molecular and Ionic Isomers.

Numerous descriptions of structural isomerism in metal complexes do not list any molecular vs ionic isomers. At the same time, one of the most striking examples of structural isomerism in organic chemistry is molecular urea, which has the same atomic composition as the chemically distinct ionic ammonium cyanate. This iconic organic couple now meets its inorganic heterometallic counterpart. We introduce a new class of structural isomers, molecular vs ionic, that can be consummated in complex and coordinatively unsaturated polynuclear/heterometallic compounds. We report inorganic molecular and ionic isomers of the composition [NaCrFe (acac)3(hfac)3] (acac = acetylacetonate; hfac = hexafluoroacetylacetonate). Heterometallic molecular [CrIII(acac)3-Na-FeII(hfac)3] (1m) and ionic {[CrIII(acac)3-Na-CrIII(acac)3]+[FeII(hfac)3-Na-FeII(hfac)3]-} (1i) isomers have been isolated in pure form and characterized. While both ions are heterobimetallic trinuclear entities, the neutral counterpart is a heterotrimetallic trinuclear molecule. The two isomers exhibit distinctly different characteristics in terms of solubility, volatility, mass spectrometry ionization, and thermal behavior. Unambiguous assignment of the positions and oxidation/spin states of the Periodic Table neighbors, Fe and Cr, in both isomers have been made by a combination of characterization techniques that include synchrotron X-ray resonant diffraction, synchrotron X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and DART mass spectrometry. The transformation between the two isomers that does take place in solutions of noncoordinating solvents has also been tested.

Controlling 4f antiferromagnetic dynamics via itinerant electronic susceptibility

Optical manipulation of magnetism holds promise for future ultrafast spintronics, especially with lanthanides and their huge, localized 4f magnetic moments. These moments interact indirectly by spin polarizing the conduction electrons (the Ruderman-Kittel-Kasuya-Yosida exchange interaction), influenced by interatomic orbital overlap, and the conduction electron's susceptibility around the Fermi level. Here, we study this influence in a series of 4f antiferromagnets, GdT2Si2 (T = Co, Rh, Ir), using ultrafast resonant x-ray diffraction. We observe a twofold increase in the ultrafast intersublattice angular momentum transfer rate between the materials, originating from modifications in the conduction electron susceptibility, as confirmed by first-principles calculations. Published by the American Physical Society 2024

Two Distinct Charge Orders in Infinite-Layer PrNiO2+δ Revealed by Resonant X-Ray Diffraction

Abstract Research of infinite-layer nickelates has unveiled a broken translation symmetry, which has sparked significant interest in its root, its relationship to superconductivity, and its comparison to charge order in cuprates. In this study, resonant x-ray scattering measurements were performed on thin films of infinite-layer PrNiO2+δ . The results show significant differences in the superlattice reflection at the Ni L 3 absorption edge compared to that at the Pr M 5 resonance in their dependence on energy, temperature, and local symmetry. These differences point to two distinct charge orders, although they share the same in-plane wavevectors. It is suggested that these dissimilarities could be linked to the excess oxygen dopants, given that the resonant reflections were observed in an incompletely reduced PrNiO2+δ film. Furthermore, azimuthal analysis indicates that the oxygen ligands likely play a crucial role in the charge modulation revealed at the Ni L 3 resonance.

Study on the deterioration mechanism of hybrid basalt-polypropylene fiber-reinforced concrete under sulfate freeze-thaw cycles

This paper focuses on the deterioration mechanism of hybrid basalt-polypropylene fiber-reinforced concrete (HBPRC) under the coupling of sulfate freeze-thaw cycles. The changes in the macroscopic properties of HBPRC under the influence of different volume contents of basalt fiber (BF), polypropylene fiber (PF) and hybrid BF-BF were investigated. The microstructure of HBPRC was characterized using the nuclear magnetic resonance (NMR) technique, X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the deterioration models of the BF- matrix interfacial transition zone (BF-ITZ) and the PF- matrix interfacial transition zone (PF-ITZ) in HBPRC were developed. The results showed that the fibers effectively reduced the cracking and macroscopic property damage induced by sulfate freeze-thaw cycles as the number of freeze-thaw cycles increased. When both BF and PF volume contents are mixed at 0.05 %, they can produce complementary effects, and their formation of a uniformly distributed three-dimensional mesh structure is more conducive to reducing the damage to the concrete, and their relative dynamic modulus of elasticity and compressive strength after 300 times of sulfate freeze-thaw cycles were increased by 67.10 % and 46.92 % compared with control concrete. At the same time, the addition of fibers resulted in a more stable evolution of the pore structure of the concrete, and the porosity of the specimens with fibers added at a volume admixture of 0.05 % and 0.1 % was reduced by 13.69–21.35 % after 300 cycles of sulfate freeze-thaw cycling, compared with control concrete. From the BF-ITZ and PF-ITZ deterioration models, it was concluded that the differences in the bonding performance of BF and PF to the concrete matrix affected the degree of frost damage to which they were subjected to coupling and the efficiency of salt solution replenishment, which in turn led to differences in the damage of each group of HBPRC. The reliability of the model was further verified by SEM observation of the morphological changes of different fiber-matrix ITZs before and after sulfate freeze-thaw cycles.

A New Class of Oxyhalide Solid Electrolytes NaNbCl6-2xOx for Solid-state Sodium Batteries.

Sodium-based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid-state sodium batteries can also provide further safety advantages. However, sodium-based solid-state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium-based oxyhalide electrolytes NaNbCl6-2xOx with a facile mechanochemical synthesis. The oxyhalide NaNbCl4O exhibits close to two orders of magnitude higher ambient-temperature sodium-ion conductivity (1.03 x 10-4 S cm-1) compared to the halide counterpart NaNbCl6 (3 x 10-6 S cm-1). Structural motifs unique to the oxygen content in NaNbCl6-2xOx are identified with 23Na and 93Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x-ray diffraction (XRD). Solid-state sodium batteries assembled with NaNbCl4O electrolyte and the cobalt- and nickel-free layered Na0.70Fe0.3Mn0.65Al0.05O2 cathode exhibit a maximum discharge capacity of 155 mA h g-1 with good cycle life at ambient temperature.

A soft processing technology for the extraction of cellulose from plant residues and agri-food wastes

In this study, cellulose was extracted from giant cane (GC), Posidonia oceanica seagrass (PO), coffee silverskin (CS), and brewer's spent grain (BSG) as alternatives to conventional sources of cellulose. The extraction protocol involved three steps: i) hemicellulose and lignin removal through alkaline hydrolysis in a 5% (w/v) NaOH solution (solid-to-liquid ratio = 1:100 g/mL, T = 25 °C, t = 2 h, ω = 300 rpm), ii) removal of organic compounds and ashes through a 95% (v/v) ethanol solution (solid-to-liquid ratio = 1:25 g/mL, T = 25 °C, t = 0.5 h, ω = 500 rpm), and iii) double bleaching in a 1% (w/v) acidic (pH = 4) NaClO2 solution (solid-to-liquid ratio = 1:50 g/mL, T = 90 °C, t = 1.5 h, ω = 500 rpm). Yield, purity, crystallinity degree, and morphology of cellulose extracted through a soft-chemical cascade process were assessed by gravimetric, infrared (FT-IR), nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses. Averaged cellulose extraction yields of 36.4, 38.6, 23.1, and 22.2% for GC, PO, CS, and BSG were obtained, respectively. All cellulose samples had high purity, though lower than the ultra-pure bacterial cellulose, which was due to the slight contamination from unremoved hemicellulose and lignin residues. Cellulose samples exhibited similar chemical features and the typical fibril-like morphology of microcrystalline cellulose (6–13 μm in width). The versatility of the proposed extraction procedure supports the sustainable conversion of low-cost organic biomasses to valuable products with manifold industrial applications (e.g., food packaging).

Resolving intermediates during the growth of aluminum deuteroxide (Hydroxide) polymorphs in high chemical potential solutions

Aluminum hydroxide polymorphs are of widespread importance yet their kinetics of nucleation and growth remain beyond the reach of current models. Here we attempt to unveil the reaction processes underlying the polymorphs formation at high chemical potential. We examine their formation in-situ from supersaturated alkaline sodium aluminate solutions using deuteration and time-resolved neutron pair distribution function analyses, which indicate the formation of individual Al(OD)3 layers as an intermediate particle phase. These layers ultimately stack to form gibbsite- or bayerite-like layered heterostructures. Ex-situ characterization of the recovered precipitates using 27Al magic angle spinning nuclear magnetic resonance spectroscopy, Raman, X-ray diffraction, and scanning electron microscopy, suggests the presence of additional intermediate states, an amorphous compound bearing both tetrahededrally- and penta-coordinated Al3+. These observations reveal the complex pathways to form Al(OD)3 monolayers via either transient pentacoordinate species or amorphous-to-ordered transitions. The subsequent crystallization of admixed gibbsite/bayerite is followed by an Al(OD)3 monolayer attachment process.

Coherent control of rare earth 4f shell wavefunctions in the quantum spin liquid Tb2Ti2O7

The resonant excitation of electronic transitions with coherent laser sources creates quantum coherent superpositions of the involved electronic states. Most time-resolved studies have focused on gases or isolated subsystems embedded in insulating solids, aiming for applications in quantum information. Here, we focus on the coherent control of orbital wavefunctions in the correlated quantum material Tb2Ti2O7, which forms an interacting spin liquid ground state. We show that resonant excitation with a strong THz pulse creates a coherent superposition of the lowest energy Tb 4f states. The coherence manifests itself as a macroscopic oscillating magnetic dipole, which is detected by ultrafast resonant x-ray diffraction. We envision the coherent control of orbital wavefunctions demonstrated here to become a new tool for the ultrafast manipulation and investigation of quantum materials.

Probing the Structure of the Electrochemical Interface Using in-Situ Surface X-Ray Scattering Techniques

Surface X-ray Scattering (SXS) or Surface X-ray Diffraction (SXRD) using synchrotron radiation is a powerful tool for the study of single crystal metal electrodes in the electrochemical environment. The single crystal surfaces have well defined adsorption sites and this enables fundamental links to be made between the surface atomic structure and the electrochemical response as has been illustrated, for example, in electrocatalysis [1]. As the development of electrochemical surface science progresses, there is a growing need for a comprehensive understanding of the atomic sturcture of electrochemical interface, both of the solid electrode and in the liquid electrolyte. This is because changes in the atomic structure across the interface induced by changes in the electric field can affect the system’s reactivity and stability [2]. These processes can be subtle and do not always involve the direct transfer of charge between electrode and electrolyte. Examples include metal surface relaxation and surface reconstruction, as well as charging of the double layer, which leads to rearrangement of the electrolyte side of the interface [3]. To further extend the fundamental understanding of the electrochemical interface structure, we have been developing resonant surface x-ray diffraction (RSXRD), a technique which combines diffraction with spectroscopy, to investigate the charge distribution in the double layer region. Combining experimental data and first-principles calculations, in-situ RSXRD was used to establish the charge distribution both at the Pt(111) electrode surface and at the Cu(001)-c(2x2)-Br electrode surface [5,6].In this talk results of recent studies of single crystal metal electrodes to probe the liquid side of the interface, particularly the role of cations in the electrochemical double layer, will be presented. The results include a systematic study of the low index Ag(hkl) surfaces to explore the role of the surface atomic geometry in determining the electrolyte layering and an exploration of the role that Cs+ cations play in forming the double layer structures on single crystal Au and Pt electrodes.[1] Y. Gründer and C. A. Lucas, Surface X-ray Diffraction Studies of Single Crystal Electrocatalysts, Nano Energy, 29, 378 (2016)[1] O. M. Magnussen and A. Groß, Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics. Journal of the American Chemical Society, 141, 4777 (2019)[2] Y. Gründer and C.A. Lucas, Potential-induced structural deformation at electrode surfaces. Current Opinion in Electrochemistry, 19, 168 (2020)[3] Y. Soldo-Olivier et al., Unraveling the Charge Distribution at the Metal-Electrolyte Interface Coupling in Situ Surface Resonant X-ray Diffraction with Ab Initio Calculations, ACS Catalysis, 12, 2375 (2022)[4] Y. Gründer et al., Charge Reorganization at the Adsorbate covered Electrode Surface probed through in-situ resonant X-ray Diffraction Combined with Ab-initio Modelling, Journal of Physical Chemistry C, 126, 4612 (2022)

Palmitic acid-mediated modulation of crystallization dynamics in amylose microparticle formation: From spherical to macaron and disc shapes

Here, we investigated the complexation of short chain amylose (SCAs) and palmitic acid (PA), serving as polymeric building blocks that alter the selectivity and directionality of particle growth. This alteration affects the shape anisotropy of the particles, broadening their applications due to the increased surface area. By modifying the concentration of PA, we were able to make spherical, macaron, and disc-shaped particles, demonstrating that PA acts as a structure-directing agent. We further illustrated the lateral and longitudinal stacking kinetics between PA-SCA inclusion complexes during self-assembly, leading to anisotropy. Transmission electron microscope (TEM) and scanning electron microscope (SEM) revealed the structural difference between the initial and final morphologies of palmitic acid-short chain amylose particles (PA-SCAPs) compared to those of short-chain amylose particle (SCAPs). The presence of PA-SCA inclusion complex in the anisotropic particles was confirmed using nuclear magnetic resonance (NMR) and powder x-ray diffraction (XRD) analysis.

Synthesis, characterization, in vitro and in silico assessment of novel diclofenac derivative metal complexes

A novel hydrazone ligand was synthesized by condensing diclofenac hydrazide with salicylaldehyde. This ligand was then used to create complexes with cobalt(II), nickel(II), copper(II), gadolinium(III), lanthanum(III), and silver(I). Structural characterization of these compounds was achieved through various techniques, including nuclear magnetic resonance spectroscopy, infrared spectroscopy, ultraviolet-visible spectroscopy, mass spectrometry, elemental analysis, thermal analysis, magnetic susceptibility measurements, electron spin resonance spectroscopy, X-ray diffraction, and conductivity measurements. The inhibitory effects of the synthesized compounds on cyclooxygenase-1 (COX-1) and cyclooxygenase-2 (COX-2) enzymes, critical targets for anti-inflammatory drugs, were assessed. Notably, the cobalt(II) and silver(I) complexes exhibited high selectivity for inhibiting COX-2, with selectivity indices of 118.75 and 105.00, respectively. The antitumor potential of the compounds was evaluated against MCF-7 (breast cancer) and HepG-2 (liver cancer) cell lines. The copper(II) and gadolinium(III) complexes demonstrated the highest efficacy, significantly inhibiting the growth of both cancer cell lines with half-maximal inhibitory concentration (IC50) values as low as 0.37 µM and 0.58 µM (MCF-7) and 0.35 µM and 0.67 µM (HepG-2), respectively. These complexes outperformed the original ligand in inhibiting cancer cell growth. In silico studies, using the SwissADME web tool and AutoDocke Vina, corroborated the experimental findings and provided insights into the compounds' physicochemical properties, pharmacokinetics, drug-likeness, and potential binding interactions with COX-1, COX-2, and the target proteins in the cancer cell lines.

New steroids from mangrove-associated fungus Trichoderma asperellum SCNU-F0048

Chemical investigation of the fungus Trichoderma asperellum SCNU-F0048 led to the discovery of two new steroids, ergosta-4,6,8 (14),22-tetraen-3-(3′-methyl-4′-hydroxyl-γ-butenolide) (1) and camphosterol B (2), as well as two known compounds, i.e. stigmasta-4,6,8(14),22-tetraen-3-one (3) and 4-hydroxy-17- methylincisterol (4). Their structures were elucidated by extensive nuclear mangnetic resonance, spectrum analysis and single crystal X-ray diffraction analysis. Bioassay disclosed that compound 1 showed strong cytotoxicity to a panel of tumor cell lines. Moreover, compounds 1 and 2 showed excellent antifungal activity against Penicillium italicum with IC50 values of 0.016 and 0.022 μM, respectively.

Molecular structure and selective theophylline complexation by conformational change of diethyl N,N'-(1,3-phenylene)dicarbamate.

The receptor ability of diethyl N,N'-(1,3-phenylene)dicarbamate (1) to form host-guest complexes with theophylline (TEO) and caffeine (CAF) by mechanochemistry was evaluated. The formation of the 1-TEO complex (C12H16N2O4·C7H8N4O2) was preferred and involves the conformational change of one of the ethyl carbamate groups of 1 from the endo conformation to the exo conformation to allow the formation of intermolecular interactions. The formation of an N-H...O=C hydrogen bond between 1 and TEO triggers the conformational change of 1. CAF molecules are unable to form an N-H...O=C hydrogen bond with 1, making the conformational change and, therefore, the formation of the complex impossible. Conformational change and selective binding were monitored by IR spectroscopy, solid-state 13C nuclear magnetic resonance and single-crystal X-ray diffraction. The 1-TEO complex was characterized by IR spectroscopy, solid-state 13C nuclear magnetic resonance, powder X-ray diffraction and single-crystal X-ray diffraction.

PREPARATION AND CHARACTERIZATION OF PERFLUOROETHYLSUBSTITUTED ALKYLAMMONIUM OLIGOFLUOROPHOSPHATES

Mono-, di-, triperfluoroethyl substituted fluorophosphate anions are building blocks in the molecular design of salts with onium cations, and are used to increase hydrophobicity, modify surfactant properties and electrical conductivity. The work proposes methods for the synthesis of superacid H+[PF3(C2F5)3]- by the reaction of tri(pentafluoroethyl)difluorophosphorane with a solution of hydrofluoric acid, as well as superacids H+[PF4(C2F5)2]- and H+[PF5C2F5]- by step-by-step removal of the pentafluoroethyl substituent by hydrolysis with subsequent treatment with HF solution. Ionic compounds were synthesized by metathesis of anions at 0 °C from the corresponding quaternary ammonium chloride based on the obtained superacids. The article presents NR4FAP-class ionic compounds with the tributylmethylammonium (TBMA) cation of the general formula [(C4H9)3NCH3]+[PF6-n(C2F5)n]-, where n = 1, 2, 3. The square bipyramidal structure of the three studied anions was confirmed by nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) data. The study shows, the synthesized compounds are characterized by extremely low vapor pressure up to 300 °C, a wide range of the liquid state with a width of up to 310 K by the methods of differential scanning calorimetry (DSC) and synchronous thermal analysis (STA). Melting temperatures and enthalpies were determined. The TBMA salts belong to ionic liquids (IL's), including one type liquid at room temperature (RT-IL). The general patterns of compounds decomposition were analyzed by the analysis of evolved gases (STA-EGA); it was shown that in all cases, the decomposition of the studied ionic liquids begins with the destruction of the anion. The electrical resistance of a pure ionic liquid at room temperature was studied. The described characteristics of perfluoroethylsubstituted alkyl ammonium oligofluorophosphates open up prospects for their use as electro conducting and antistatic additives for petrochemicals, fuels and polymers. For citation: Mokrushin I.G., Pinegina O.A., Krasnovskikh M.P., Dmitriev M.V., Markin I.V., Kozen A.L. Preparation and characterization of perfluoroethylsubstituted alkylammonium oligofluorophosphates. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 5. P. 54-61. DOI: 10.6060/ivkkt.20246705.6916.

TENOFOVIR DISOPROXIL FUMARATE RELEASE FROM GLUTARALDEHYDE CROSS-LINKED CHITOSAN/Β-CYCLODEXTRIN HYDROGEL

In this study, chitosan was produced from crayfish Astacus leptodactylus, and then it was used to synthesize chitosan-graft-β-cyclodextrin (CS-g-β-CD) hydrogel. The produced chitosan (CS) and the sythesized CS-g-β-CD hydrogel were characterized using a Fourier Transform Infrared Spectroscopy (FTIR), Proton Nuclear Magnetic Resonance Spectroscopy (1H-NMR), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). Tenofovir disoproxil fumarate (TDF) was used as a model to investigate the antiviral drug release properties of the CS-g-β-CD hydrogel. The synthesized hydrogel had an almost homogeneous pore structure and a high swelling capacity which increases depending on the amount of β-Cyclodextrin (β-CD). The drug-loaded CS-g-β-CD hydrogels was examined by XRD and 1H-NMR, and SEM analyses. Seventy-three percent of the TDF loaded on the synthesized hydrogels was released into phosphate-buffered saline (PBS) solution at 37 ºC. The drug release behavior of all prepared CS-g-β-CD hydrogels fitted the Korsmeyer-Peppas model. The addition of β-CD into the gel improved the swelling ability and TDF release of the CS-g-β-CD hydrogel system.

A versatile food packaging film fabricated by gallic acid/octanoic acid grafted chitosan: Preparation, characterization, high-efficient cells capture and photodynamic eradication of bacteria and biofilms

This study aims to construct a versatile film fabricated by gallic acid/octanoic acid-grafted-chitosan (GA/OA-g-CS) for high photodynamic antibacterial and antibiofilm efficacy with blue light (BL, 420 nm) irradiation. First, the GA/OA-g-CS conjugates were synthesized by a green radical-induced grafting reaction in the redox system composed of ascorbic acid/hydroxyl peroxide (AA/H2O2). Then, the molecular structural and physicochemical characteristics of the conjugates, as well as the mechanisms of the free radical grafting reaction were further studied. Ascorbate radical (Asc•−) and hydroxyl radical (•OH) were produced in the AA/H2O2 system, and •OH reacted with CS to produce CS macro-radicals (•CS). UV–vis, Fourier transform infrared, nuclear magnetic resonance spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis confirmed that GA/OA was attached onto CS through •OH. Notably, the films constructed by GA/OA-g-CS exhibited robust multi-modal functionalities, including intriguing bacteria-capturing and contact-killing, as well as BL-driven photodynamic sterilization, ascribed to the inherent merits based on the massive photoactive GA, hydrophobic and high membrane affinity of OA within the CS chains. As a result, the GA/OA-g-CS (2:1) film plus BL irradiation can efficiently eradicate Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and their biofilms. After BL irradiation for 30 min, the GA/OA-g-CS (2:1) film showed a reduction of 5.2 Log CFU/mL against E. coli. More importantly, the film with BL irradiation can efficiently not only inhibit the formation of biofilms but also jeopardize the matured biofilms. This research provides a potential platform and promises for applications in active and intelligent food packaging.

Resonant x-ray diffraction measurements in charge ordered kagome superconductors KV3Sb5 and RbV3Sb5

We report on (resonant) x-ray diffraction experiments on the normal state properties of kagome-lattice superconductors KV3Sb5 and RbV3Sb5. We have confirmed previous reports indicating that the charge density wave (CDW) phase is characterized by a doubling of the unit cell in all three crystallographic directions. By monitoring the temperature dependence of Bragg peaks associated with the CDW phase, we ascertained that it develops gradually over several degrees, as opposed to CsV3Sb5, where the CDW peak intensity saturates promptly just below the CDW transition temperature. Analysis of symmetry modes indicates that this behavior arises due to lattice distortions linked to the formation of CDWs. These distortions occur abruptly in CsV3Sb5, while they progress more gradually in RbV3Sb5 and KV3Sb5. In contrast, the amplitude of the mode leading to the crystallographic symmetry breaking from P6/mmm to Fmmm appears to develop more gradually in CsV3Sb5 as well. Diffraction measurements close to the V K edge and the Sb L1 edge show no sensitivity to inversion- or time-symmetry breaking, which are claimed to be associated with the onset of the CDW phase. The azimuthal angle dependence of the resonant diffraction intensity observed at the Sb L1 edge is associated with the difference in the population of unoccupied states and the anisotropy of the electron density of certain Sb ions.

Preparation of reed fibers reinforced graft-modified starch-based adhesives based on quantum mechanical simulation and molecular dynamics simulation

Starch is a biomass polymer material with a high yield and comprehensive source. It is used as a raw material for preparing adhesives because of its highly active hydroxyl group. However, poor adhesion and water resistance hinder the application of starch-based adhesives (SBAs). Based on this, the starch was modified through graft copolymerization with itaconic acid as a cross-linking agent, methyl methacrylate and methyl acrylate as copolymers. Additionally, reed fibers were synergistically modified with polydopamine deposition to prepare an environmentally friendly SBA used in plywood production. Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H NMR), X-ray diffraction (XRD), and thermogravimetric analysis (TG) demonstrate that copolymerization of methyl methacrylate and methyl acrylate with starch improves the shear strength, water resistance, and thermal stability of the SBA. Compared to unmodified starch, the modified SBA exhibits a 129 % increase in dry strength and achieves a wet strength of 1.36 MPa. Fukui function, Frontier orbit theory, and molecular dynamics simulation have shown that itaconic acid promotes the copolymerization of starch and acrylate monomers. The modified starch has fewer hydrogen bonds, less order, and a denser macromolecular network structure, which provides a reference for studying the molecular interaction mechanisms of SBAs.

Design of Promising Uranyl(VI) Complexes Thin Films with Potential Applications in Molecular Electronics.

In this work, it is proposed the development of organic semiconductors (OS) based on uranyl(VI) complexes. The above by means of the synthesis and the characterization of the complexes by Infrared spectroscopy, Nuclear magnetic resonance spectroscopy, mass spectrometry, and X-ray diffraction. Films of these complexes were deposited and subsequently, topographic and structural characterization was carried out by Scanning Electron Microscopy, X-ray diffraction, and Atomic Force Microscopy. Additionally, the nanomechanical evaluation was performed to know the stiffness of uranyl films using their modulus of elasticity. Also, the optical characterization took place in the devices and their bandgap value ranges between 2.40 and 2.93 eV being the minor for the film of the uranyl complex with the N on pyridine in position 4 (2 c). Finally, the electrical behavior of the uranyl(VI) films was evaluated, and important differences were obtained: the uranyl complex with the N on pyridine in position 2 (2 a) film is not influenced by changes in lighting and its current density is in the order of 10-3 A/cm2. The film with uranyl complex with the N on pyridine in position 3 (2 b) and 2 c presents a greater current flow under lighting conditions and two orders of magnitude larger than in film 2 a. In these films 2 b and 2 c, ohmic behavior occurs at low voltages, while at high voltages the charge transport changes to space-charge limited current behavior.

Experimental Studies of Schiff Base (E)-4-methoxy-2-(((2-phenoxyphenyl)imino)methyl) phenol Compound with Various Spectroscopic Methods

Schiff-based compounds, which represent an important class in the field of organic compounds, form the basis of this research article. This research article aims to investigate the synthesized compound (E)-4-methoxy-2-(((2-phenoxyphenyl) imino) methyl) phenol using experimental methods.FT-IR, UV-Vis, 13C and 1H Nuclear Magnetic Resonance (NMR) Spectroscopy and X-ray diffraction methods were used to elucidate the structural properties of the compound synthesized at the end of chemical processes. The structure solution was carried out from the data obtained as a result of X-ray analysis. According to these results, one of the two compounds in the asymmetric cell completed their formation in the enol-imine form and the other in the keto-amine form. This structural situation, which is rare in the literature, was supported and explained by FT-IR, 13C and 1H Nuclear Magnetic Resonance (NMR) spectroscopy studies.According to the results obtained as a result of UV-Vis spectroscopy, the structure revealed that the enol-imine form was dominant. The reasons for this situation were explained.