NMR Studies Research Articles

Synthesis, Characterization and Interconversion of p-Tolylsulfone-Functionalized Norbornadiene/Quadricyclane Couples.

We report the synthesis and characterization of library of new 2,3-disubstituted norbornadiene/quadricyclane couples. For the first time, the para-tolylsulfone moiety was employed as electron-withdrawing substituent in combination with a variety of different electron donors as counterparts. Comprehensive characterization was conducted for every interconversion couple. By comparison with structurally related molecules published previously we established the tosyl moiety as suitable alternative to previously investigated ester functionalities by providing similar photophysical properties. The photo-induced interconversion behavior was investigated via UV/Vis- and NMR-spectroscopy. The UV/Vis experiments were carried out exclusively in acetonitrile, whereas several solvents were investigated in the NMR studies. A detailed description and comparison of the isomerization behavior is provided, while examining relevant optical properties like λmax and λonset. Thereby, an enhanced red-shift up to λmax = 394 nm combined with an λonset value of 469 nm could be generated which is necessary for potential applications.

Solid Handmade Ternary Coinage Metal Mentors for Organic Bond-Making and Bond-Breaking Applications.

A comparative approach is employed for the novel synthesis of a magnetically recoverable ternary nanocomposite consisting of g-C3N4-supported Fe3O4 decorated with coinage metals (Au, Ag, and Cu). This synthesis is achieved through a straightforward and convenient one-step grinding protocol. In situ, the nanoparticles were grown on the g-C3N4-assist Fe3O4 matrix (GCFM), and the agglomeration of these nanoparticles on the matrix creates a pathway for the formation of the nanocomposite (NC). The as-formed CNC was confirmed with the help of characterization analyses, namely XRD, FT-IR, HR-TEM, FE-SEM, XPS, VSM, UV-vis, and NMR studies. Together with NPs and GCFM, with the quantum consequence, the activity of the NC shows better electron transfer via transfer of electrons, which grabs tremendous attention toward it, resulting in enhanced plausible photocatalytic degradation toward pharmaceutical compounds, dyes, and anthropogenic pollutants. The activity of the C-NC hikes at 88% for ciprofloxacin (CX) and 90% for paracetamol (PM); furthermore, the activity of the C-NC hikes at 88% and 87% for xylene Cyanol FF (XCF) and malachite green (MLG), respectively. Interestingly, an added advantage is the formation of a C-C bond (homocoupling reaction) in phenylboronic acid (PA) via a greener solvent under ambient conditions. The yield percentage of the conversion product shows satisfactory results, and its reproducibility was good for the prepared ternary NC. The conversion treatment of anthropogenic pollutants, namely 4-nitrophenol, grasps a high percentage (98%). In addition, the NC shows good activity toward both types of bacteria. The reproducibility of the composite also shows virtuous activity against pharmaceutical as well as toxic contaminants. The as-prepared CNC was specifically engineered to perform both bond formation and bond cleavage of organic molecules under ambient conditions for multiple cycles.

On the Structure and Role of Avian Eggshells: A 31P, 1H, and 13C Solid-State NMR Study.

The eggshell is a composite and highly ordered structure formed by biomineralization. Besides other functions, it has a vital and intricate role in the protection of an embryo from various potentially harsh environmental conditions. Solid-state nuclear magnetic resonance (SSNMR) has been used for detailed structural investigations of the chicken, tinamou, and flamingo eggshell materials. 31P NMR spectra reveal that hydroxyapatite and β-tricalcium phosphate in the ratio 3:2 represent major constituents of phosphate species in the eggshells. All three eggshells exhibit similar spectra, except for the line widths, which implies different structural order of phosphate species in the chicken, tinamou, and flamingo eggshells. 1H NMR spectra for these materials are comparable, differentiating overlapped peaks in three spectral regions at around 7, 4-5, and 1-2 ppm. These spectral regions have been attributed to protons from NH or CaHCO3, water, and possibly isolated monomeric water molecules or hydroxyl groups in calcium-deficient hydroxyapatite. 1H-13C CP MAS NMR revealed the presence of organic matter in the form of lipids and proteins. Two overlapped resonances in the carbonyl region at around 173 and 169 ppm are assigned to the carbonyls of the peptide bonds and the bicarbonate unit in calcite, respectively. Fourier-transform infrared spectroscopy (FTIR) spectra confirmed the presence of structural units detected in the NMR spectra.

Fluorinated tags to study protein conformation and interactions using19F NMR.

The incorporation of fluorine atoms into a biomacromolecule provides a background-free and environmentally sensitive reporter of structure, conformation and interactions using19F NMR. There are several methods to introduce the19F reporter - either by synthetic incorporationviasolid phase peptide synthesis; by suppressing the incorporation or biosynthesis of a natural amino acid and supplementing the growth media with a fluorinated counterpart during protein expression; and by genetic code expansion to add new amino acids to the amino acid alphabet. This review aims to discuss progress in the field of introducing fluorinated handles into biomolecules for NMR studies by post-translational bioconjugation or 'fluorine-tagging'. We will discuss the range of chemical tagging 'warheads' that have been used, explore the applications of fluorine tags, discuss ways to enhance reporter sensitivity and how the signal to noiseratioscan be boosted. Finally, we consider some key challenges of the field and offer some ideas for future directions.

Backbone NMR resonance assignments for the VP1u N-terminal receptor-binding domain of the human parvovirus pathogen B19.

Parvovirus B19 (B19V) is a human pathogen that is the causative agent of several diseases in infants and adults. Due to a lack of antivirals against this virus, treatment options are limited. The minor capsid protein of B19V has a unique N terminus, named VP1u, which is essential for infection. The VP1u encodes a receptor binding domain (RBD), necessary for host cell entry, and a phospholipase A2 (PLA2) domain, crucial for endosomal escape during cellular trafficking. Both domains are indispensable for infection, making the RBD a plausible drug target for inhibitors against B19V, as it is located on the exterior surface of the virus. To date, no experimental structural information has been available for the VP1u component for any Parvovirus. Here we report the backbone NMR resonance assignments for the RBD of B19V and demonstrate it forms a stable structure. The backbone chemical shifts are in good agreement with a structure predicted by AlphaFold, validating that the RBD contains three helices connected by tight turns. This RBD construct can now be used for further NMR studies, including assignment of full-length VP1u, determination of protein-protein interaction interfaces, and development of B19 antivirals specific to the RBD domain.

Effect of tert‐Butylation on the Photophysics of Thermally Activated Delayed Fluorescence Emitters

Thermally activated delayed fluorescence (TADF) emitters potentially can provide organic light‐emitting diodes with 100% internal quantum efficiency by harvesting triplet excitons. Generally, TADF emitters are small molecules that are not applicable for solution processability. The addition of tert‐butyl groups to the periphery of TADF emitters has proven to improve their solubility in various organic solvents, reduce aggregation‐induced quenching, and enhance the photoluminescence quantum yield (PLQY). This article studies the photophysical influence of the tert‐butyl group attached to an emitter with a carbazole acceptor and a triazine donor. The resulting t3CzTrz‐F is a blue–green TADF emitter, in which the addition of a tert‐butyl group increases the rate of reverse intersystem crossing (rISC), while simultaneously decreasing the nonradiative decay rate substantially. In addition, dilution of t3CzTrz‐F in a host matrix in film results in an enhanced PLQY, which is associated with a decrease in the nonradiative decay constant, while there is no change in the rISC rate. Through a solid‐state NMR study, the change in rISC and nonradiative rate upon tert‐butylation by enlarged intermolecular spacing and reduced vibrational and rotational freedom is rationalized, resulting in improved photophysical performance.

1H, 13C and 15N backbone resonance assignment of Cel45A from Phanerochaete chrysosporium.

A glycoside hydrolase family 45 (GH45) enzyme from the white-rot basidiomycete fungus Phanerochaete chrysosporium (PcCel45A) was expressed in Pichia pastoris with 13C and 15N labelling. A nearly complete assignment of 1H, 13C and 15N backbone resonances was obtained, as well as the secondary structure prediction based on the assigned chemical shifts using the TALOS-N software. The predicted secondary structure was almost identical to previously published crystal structures of the same enzyme, except for differences in the termini of the sequence. This is the first NMR study using an isotopically labelled GH45 enzyme.

Photocontrolled Reversible Amyloid Fibril Formation of Parathyroid Hormone-Derived Peptides.

Peptide fibrillization is crucial in biological processes such as amyloid-related diseases and hormone storage, involving complex transitions between folded, unfolded, and aggregated states. We here employ light to induce reversible transitions between aggregated and nonaggregated states of a peptide, linked to the parathyroid hormone (PTH). The artificial light-switch 3-{[(4-aminomethyl)phenyl]diazenyl}benzoic acid (AMPB) is embedded into a segment of PTH, the peptide PTH25-37, to control aggregation, revealing position-dependent effects. Through in silico design, synthesis, and experimental validation of 11 novel PTH25-37-derived peptides, we predict and confirm the amyloid-forming capabilities of the AMPB-containing peptides. Quantum-chemical studies shed light on the photoswitching mechanism. Solid-state NMR studies suggest that β-strands are aligned parallel in fibrils of PTH25-37, while in one of the AMPB-containing peptides, β-strands are antiparallel. Simulations further highlight the significance of π-π interactions in the latter. This multifaceted approach enabled the identification of a peptide that can undergo repeated phototriggered transitions between fibrillated and defibrillated states, as demonstrated by different spectroscopic techniques. With this strategy, we unlock the potential to manipulate PTH to reversibly switch between active and inactive aggregated states, representing the first observation of a photostimulus-responsive hormone.

Investigating the effect of nitrogen and chlorine Co–doped carbon quantum dots in phenazine and quinoxaline sensitized solar cells

We investigated five dyes for dye-sensitized solar cells (DSSCs) relying upon derivatives of phenazine and quinoxaline and also studied their optical characteristics and the influence of functional groups such as (-CH3, -NO2, -C = O, -CN, and -OH) on these characteristics. When the prepared dyes are directly used at DSSCs, 9-Nitrobenzo[a]phenazin-5-ol (3b) dye device showed an improved Jsc (0.288 mA cm−2), Voc (0.437 V), FF (0.446), and η (0.056 %) than the sensitized solar cells by other dyes. In the following, nitrogen-doped carbon quantum dot and nitrogen, chlorine co-doped carbon quantum dot are used to improve the performance of DSSCs. The results showed that the device sensitized using the sensitizer (5-hydroxybenzo[α]phenazin-9-yl)(phenyl) methanone (3c)/NCQD has the highest photovoltaic efficiency with Jsc (0.979 mA cm−2), Voc (0.465 V), FF (0.370), and η (0.168 %). The N and Cl co-doped carbon dots were synthesized with a green approach to improve the performance of solar cells by the co-sensitization method. This approach is improving the efficiency of DCSSs with a simple, eco-friendly, and low-cost technique. Among the prepared sensitizers, (5-hydroxybenzo[α]phenazin-9-yl)(phenyl) methanone (3c)/N, Cl-CQD demonstrates the highest photovoltaic efficiency with Jsc (1.31 mA cm−2), Voc (0.495 V), FF (0.466), and η (0.303 %). FT-IR, XRD, 13C NMR, 1H NMR, TEM, EDS-Map, AFM, DLS, and PL studies were used to confirm the structure of the synthesized dyes and quantum dots.

A comprehensive solid-state NMR and theoretical modeling study to reveal the structural evolution of layered yttrium hydroxide upon calcination

Layered rare earth hydroxides (LREHs) are a new family of ion-exchangeable layered metal hydroxides, which have extensive applications in various fields due to the unique properties of rare earth cations in the layered structure and the anion exchange capacity. The transformation of layered metal hydroxides to new layered phases that can be restored through the memory effect is critical for their chemistry and applications. However, the structure details of these new phases such as the coordination environments of rare earth cations/counterions and their evolution as a function of calcination temperature remain unclear to date. Herein, a comprehensive 89Y/35Cl solid-state NMR (ssNMR) and theoretical modeling approach was used to reveal the structural evolution of a representative LREH, namely LYH-Cl, upon calcination. We first identified partial decomposition products of Y3O(OH)5Cl2 and Y(OH)3 during the dehydration stage, then uncovered the preferential removal of hydroxide ions on yttrium sites coordinated with chlorine during the dehydroxylation stage, and finally determined the preferential removal of chlorine exposed to the surface of layers during the dechlorination stage. The coordination environments of Y3+ and Cl− undergo significant changes upon calcination, revealed by ssNMR experiments. These findings thus help us to overcome the obstacles impeding the rational design and synthesis of LREH-based functional materials via memory effect, underscoring the vast potential of ssNMR in deepening the understanding of layered metal hydroxides and related materials.

Structure and reactivity of surface vanadia sites in bi-layered supported VOx/AlOx/SiO2 catalysts via solid-state NMR, first-principles calculations, and catalytic studies

By combining multinuclear 1H, 29Si, 27Al and 51V solid-state NMR experimental measurements with reactivity and selectivity data, as well as first-principles calculations, for ternary bi-layered supported VOx/Al2O3/SiO2 catalysts, the structure of the dehydrated surface vanadia species was determined for each combination of supported VOx and AlOx active components. The specific structure of the surface vanadia sites in the ternary bi-layered supported VOx/Al2O3/SiO2 catalyst system have been investigated for the first time.The following vanadia sites are proposed based on the current findings:At low vanadia content, surface VO(OH)(OSi)2 sites form on the alumina-free surface of the SiO2 support in the bi-layered supported VOx/Al2O3/SiO2 catalyst system. In addition, two types of VO(OSi)3 surface species are likely present in this system. On small alumina clusters, weakly bonded surface VO(OH)(OAl)2 sites also form, along with the sites containing mixed Si/Al pods VO(OH)(OAl)(OSi). As the size of alumina clusters increases, strongly bonded VO(OAl)3 centers form, alongside the surface sites containing mixed pods VO(OAl)2(OSi) and VO(OAl)(OSi)2. The content of these sites increases with the loading of vanadia. Comparing supported VOx/SiO2, VOx/Al2O3, and bi-layered VOx/Al2O3/SiO2 catalyst systems revealed differences in catalytic activity due to the presence of new sites with different pods, with OH groups as well as the influence of Al-O-Si bonds on the electronic structure of surface vanadia sites on the alumina clusters. During the formation of dimethyl ether (DME), the turnover frequency (TOFDME) of the catalysts decreases with increasing domain size of the alumina clusters on SiO2. Addition of surface VOx sites, however, slightly decreases the TOFDME with the higher vanadia content weakening the activity of the alumina clusters. When surface VOx exists predominantly as V/Al1 and V/Al2, TOFredox depend on the vanadia content with lower vanadia content resulting in higher the TOFredox values. The 51V NMR spectra show that this decrease in redox TOF value correlates with the appearance of vanadia sites associated with silica pods. The activity of the catalysts was tested in methanol conversion reactions.

Backbone NMR resonance assignments for the VP1u N-terminal receptor-binding domain of the human parvovirus pathogen B19.

Parvovirus B19 (B19V) is a human pathogen that is the causative agent of several diseases in infants and adults. Due to a lack of antivirals against this virus, treatment options are limited. The minor capsid protein of B19V has a unique N terminus, named VP1u, which is essential for infection. The VP1u encodes a receptor binding domain (RBD), necessary for host cell entry, and a phospholipase A2 (PLA2) domain, crucial for endosomal escape during cellular trafficking. Both domains are indispensable for infection, making the RBD a plausible drug target for inhibitors against B19V, as it is located on the exterior surface of the virus. To date, no experimental structural information has been available for the VP1u component for any Parvovirus. Here we report the backbone NMR resonance assignments for the RBD of B19V and demonstrate it forms a stable structure. The backbone chemical shifts are in good agreement with a structure predicted by AlphaFold, validating that the RBD contains three helices connected by tight turns. This RBD construct can now be used for further NMR studies, including assignment of full-length VP1u, determination of protein-protein interaction interfaces, and development of B19 antivirals specific to the RBD domain. Database: BMRB submission code: 52440.

Heteroallene Insertions into Tin(II) Alkoxide Bonds.

A series of iso-carbamate complexes have been synthesized by the reaction of [SnII(OiPr)2] or [SnII(OtBu)2] with either aryl or alkyl isocyanates, ONC-R (R = 2,4,6-trimethylphenyl (Mes), 2,6-diisopropylphenyl (Dipp), isopropyl (iPr), cyclohexyl (Cy) and tert-butyl (tBu)). In the case of aryl isocyanates, mono-insertion occurs to form structurally characterized complexes [Sn{κ2-N,O-R-NC(OiPr)O}(μ-OiPr)]2 (1: R = Mes, 2: R = Dipp) and [Sn{κ2-N,O-R-NC(OtBu)O}(μ-OtBu)]2 (3: R = Mes, 4: R = Dipp). The complicated solution-state chemistry of these species has been explored using 1H DOSY experiments. In contrast, reactions of tin(II) alkoxides with alkyl isocyanates result in the formation of bis-insertion products [Sn{κ2-N,O-R-NC(OiPr)O}2] (5: R = iPr, and 6: R = Cy) and [Sn{κ2-N,O-R-NC(OtBu)O}2] (7: R = iPr, 8: R = Cy), of which complexes 6-8 have also been structurally characterized. 1H NMR studies show that the reaction of tBu-NCO with either [Sn(OiPr)2] or [Sn(OtBu)2] results in a reversible mono-insertion. Variable-temperature 2D 1H-1H exchange spectroscopy (VT-2D-EXSY) was used to determine the rate of exchange between free tBu-NCO and the coordinated tBu-iso-carbamate ligand for the {OiPr} alkoxide complex, as well as the activation energy (Ea = 92.2 ± 0.8 kJ mol-1), enthalpy (ΔH‡ = 89.4 ± 0.8 kJ mol-1), and entropy (ΔS‡ = 12.6 ± 2.9 J mol-1 K-1) for the process [Sn(OiPr)2] + tBu-NCO ↔ [Sn{κ2-N,O-tBu-NC(OiPr)O}(OiPr)]. Attempts to form Sn(II) alkyl carbonates by the insertion of CO2 into either [Sn(OiPr)2] or [Sn(OtBu)2] proved unsuccessful. However, 119Sn{1H} NMR spectroscopy of the reaction of excess CO2 with [Sn(OiPr)2] reveals the presence of a new Sn(II) species, i.e., [(iPrO)Sn(O2COiPr)], VT-2D-EXSY (1H) of which confirms the reversible alkyl carbonate formation (Ea = 70.3 ± 13.0 kJ mol-1; ΔH‡ = 68.0 ± 1.3 kJ mol-1 and ΔS‡ = -8.07 ± 2.8 J mol-1 K-1).

Implication of carbohydrazide chemosensors in selective sensing of Fe(III) and construction of molecular devices

Two new and two reference sensors L1-L2 and R1-R2, respectively, based on the hydrazide core were synthesized in good yields (70–86 %). A variety of analytical methods, including NMR, HRMS, and single-crystal XRD, were used to characterize these sensors. Cyclic voltammetry, UV–visible absorption, and emission spectroscopies were then used to confirm the electrochemical and photophysical characteristics of these sensors. Moreover, theoretical calculations at the level of DFT and TD-DFT were carried out to compare the experimental findings with the theoretical ones. The sensors were found to exhibit luminescence attributed to singlet ligand-centered (1LC) transitions. Based on their luminescent properties and the previous literature reports where structurally analogous sensors have been used for the detection of metal ions, these sensors were investigated as selective chemosensors for Fe(III) detection, with a "turn-off" fluorescence behaviour in a binding stoichiometry of 1:1 = sensor:M(III) [M = Fe(III)] with a limit of detection of 2.71–39 µM, or 0.15–2.81 ppm. The mechanistic details regarding the sensing of Fe(III) ion by the sensors was provided by NMR, IR, XPS and UV-visible absorption spectroscopic studies. To increase the usefulness of the sensors, L2 was also applied for the successful fabrication of the molecular logic gate and molecular lock keypad. Paper strip test and sensing of Fe(III) contaminated water by the sensors accounted for the practical applicability of the sensors in real life.

Revealing the Mechanism of Combining Best Properties of Homogeneous and Heterogeneous Catalysis in Hybrid Pd/NHC Systems

AbstractThe formation of transient hybrid nanoscale metal species from homogeneous molecular precatalysts has been demonstrated by in situ NMR studies of catalytic reactions involving transition metals with N‐heterocyclic carbene ligands (M/NHC). These hybrid structures provide benefits of both molecular complexes and nanoparticles, enhancing the activity, selectivity, flexibility, and regulation of active species. However, they are challenging to identify experimentally due to the unsuitability of standard methods used for homogeneous or heterogeneous catalysis. Utilizing a sophisticated solid‐state NMR technique, we provide evidence for the formation of NHC‐ligated catalytically active Pd nanoparticles (PdNPs) from Pd/NHC complexes during catalysis. The coordination of NHCs via C(NHC)−Pd bonding to the metal surface was first confirmed by observing the Knight shift in the 13C NMR spectrum of the frozen reaction mixture. Computational modeling revealed that as little as few NHC ligands are sufficient for complete ligation of the surface of the formed PdNPs. Catalytic experiments combined with in situ NMR studies confirmed the significant effect of surface covalently bound NHC ligands on the catalytic properties of the PdNPs formed by decomposition of the Pd/NHC complexes. This observation shows the crucial influence of NHC ligands on the activity and stability of nanoparticulate catalytic systems.

Revealing the Mechanism of Combining Best Properties of Homogeneous and Heterogeneous Catalysis in Hybrid Pd/NHC Systems.

The formation of transient hybrid nanoscale metal species from homogeneous molecular precatalysts has been demonstrated by in situ NMR studies of catalytic reactions involving transition metals with N-heterocyclic carbene ligands (M/NHC). These hybrid structures provide benefits of both molecular complexes and nanoparticles, enhancing the activity, selectivity, flexibility, and regulation of active species. However, they are challenging to identify experimentally due to the unsuitability of standard methods used for homogeneous or heterogeneous catalysis. Utilizing a sophisticated solid-state NMR technique, we provide evidence for the formation of NHC-ligated catalytically active Pd nanoparticles (PdNPs) from Pd/NHC complexes during catalysis. The coordination of NHCs via C(NHC)-Pd bonding to the metal surface was first confirmed by observing the Knight shift in the 13C NMR spectrum of the frozen reaction mixture. Computational modeling revealed that as little as few NHC ligands are sufficient for complete ligation of the surface of the formed PdNPs. Catalytic experiments combined with in situ NMR studies confirmed the significant effect of surface covalently bound NHC ligands on the catalytic properties of the PdNPs formed by decomposition of the Pd/NHC complexes. This observation shows the crucial influence of NHC ligands on the activity and stability of nanoparticulate catalytic systems.

Multinuclear PFGSTE NMR description of 39K, 23Na, 7Li, and 1H specific activation energies governing diffusion in alkali nitrite solutions

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 (39K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that 39K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Analysis of the results indicates that 39K NMR diffusometry is feasible when the nuclei exhibit spin–lattice and spin–spin relaxation coefficients on the order of 60–100 ms and 50–100 ms, respectively. The diffusivity of 39K followed Arrhenius behavior, and comparative 23Na, 7Li, and 1H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of 39K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

Synthesis of isomeric β-cycloalkoxyphosphonated hydrazones containing a dioxaphosphorinane ring: configurational and conformational investigation and molecular docking analysis

A series of Z/E isomeric β-cycloalkoxyphosphonated hydrazones [R1R2C(CH2O)2P(=O)CH2-C{=N-N(H)R5}C(H)R3R4] 3 bearing a six-membered dioxaphosphorinane ring was prepared, structurally analysed, and subjected to in silico studies to assess their Acetylcholinesterase (AChE) and Butyrylcholinesterase (BuChE) inhibition activity. Furthermore, their ADMET (Absorption, Distribution, Metabolism, Excretion, Toxicity) properties were determined. Hydrazones 3 were prepared from their corresponding allenylphosphonates [R1R2C(CH2O)2P(=O)C(H)=C=CR3R4] 2 by addition of various hydrazines NH2-NHR5. Since NMR studies indicated the occurrence of several isomeric species in solution, conformational and configurational studies, based on mechanistic elucidation and energy stability using Density functional theory (DFT) calculation at the B3LYP/6311 G++(d,p) level of theory, were performed to determine their relative predominance. The hydrazone 1-(2-oxo-1,3,2-dioxaphosphoranyl)-3-phenylpropanone 3c was crystallographically analysed by single-crystal X-ray diffraction (SCXRD), revealing the occurrence of strong intra- and intermolecular N-H···O hydrogen bonding. These secondary interactions were further examined by a Hirshfeld surface analysis. The experimental SCXRD parameters are compared with the theoretical calculated ones and the preferred configuration of product 3c was determined. Furthermore, the crystal structure of the symmetric azine 2,2′-((2E,2′E)-hydrazine-1,2-diylidenebis(3-phenylpropan-1-yl-2-ylidene))bis(5-methyl-5-propyl-1,3,2-dioxaphosphinane 2-oxide) 4, resulting from the reaction between hydrazone 3a and allene 2a, has been determined. To predict whether hydrazones 3 are appropriate as anticholinesterase agents exhibiting a potential activity for treatment of the Alzheimer disease, in silico molecular docking simulations were employed to investigate the interaction modes between hydrazones 3 and the active sites of the BuChE and AChE enzymes . Additionally, an ADMET-properties prediction was carried out for selected hydrazones to determine their pharmacokinetics and drug-likeness properties.

Carboxylated pillar[5]arene cavity accommodates organic cations in the host-guest complexes

The electron-rich cavity of carboxylated pillar[5]arene efficiently encapsulates cationic guest molecules within supramolecular assemblies. In this study we provide evidence of the host-guest complexation between carboxylated pillar[5]arene and benzamidine, a competitive inhibitor of serine proteases. We show the unexpected inclusion of the polar amidinium functionality within the central cavity of the macrocyclic host sustained by N+-H···π and cation···π interactions. In addition to the in-cavity complexation, simultaneous external binding of bipyridinium guests with varying stoichiometries has been observed. The interesting aspect is the inclusion of a hydrogen bonded pair of 1,2-bis(4-pyridyl)ethylene guests into pillar[5]arene cavity. Additional insights into inclusion characteristics are provided by NMR and ion mobility mass spectrometry (IM-MS) studies, offering information for the solution/gas phase and enabling a comprehensive description of the complexation process across different phases. This work expands the portfolio of cationic guest molecules capable of being encapsulated by carboxylated pillar[5]arene, showing new promises and directions for their inclusion and self-assembly behavior.

MRI and PFG NMR studies of percolation effects in advanced melting during a cryoporometry characterisation of disordered mesoporous alumina

Cryoporometry (or thermoporometry) offers a way of pore structural characterisation for mesoporous materials that often needs little sample preparation, is relatively quick, and is statistically-representative for macroscopic samples. While it is well-known that freezing is controlled by pore-blocking, and is thus an invasion percolation process, the percolative nature of pore-to-pore co-operative advanced melting effects has been much less studied. In this work, PFG NMR studies, of diffusivity within the molten phase, have shown that the early melting process follows the scaling law, expected from percolation theory, below the percolation threshold. The percolation threshold thereby obtained was that for a 3D isotropic Poisson polyhedral lattice, consistent with the observation of patchwise macroscopic heterogeneities in the spatial distribution of local average pore size seen in MR relaxation time-weighted images. MRI has shown that once advanced melting effects kicked-in, around the percolation threshold, they occurred to different degrees in different slices along the length of the extrudate pellet. The macroscopic banding in pore-blocking, during freezing, and advanced melting effects, along the axis of the extrudate was consistent with anisotropic diffusional properties observed with MRI. Hence, it has been shown how the pore-pore co-operative effects can be utilised to improve structural characterisation of mesoporous solids.