Liquid-state Nuclear Magnetic Resonance Research Articles

Solvent Welding and Imprinting Cellulose Nanofiber Films Using Ionic Liquids.

Cellulose nanofiber films (CNFF) were treated via a welding process using ionic liquids (ILs). Acid-base-conjugated ILs derived from 1,5-diazabicyclo[4.3.0]non-5-ene [DBN] and 1-ethyl-3-methylimidazolium acetate ([emim][OAc]) were utilized. The removal efficiency of ILs from welded CNFF was assessed using liquid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR). The mechanical and physical properties of CNFF indicated surface plasticization of CNFF, which improved transparency. Upon treatment, the average CNFF toughness increased by 27%, and the films reached a Young's modulus of ∼5.8 GPa. These first attempts for IL "welding" show promise to tune the surfaces of biobased films, expanding the scope of properties for the production of new biobased materials in a green chemistry context. The results of this work are highly relevant to the fabrication of CNFFs using ionic liquids and related solvents.

Applications of Dissolution-DNP for NMR Screening.

Experimental screening for protein-ligand interactions is a central task in drug discovery. Nuclear magnetic resonance (NMR) spectroscopy enables the determination of binding affinities, as well as the measurement of structural and dynamic parameters governing the interaction. With traditional liquid-state NMR relying on a nuclear spin polarization on the order of 10-5, hyperpolarization methods such as dissolution dynamic nuclear polarization (D-DNP) can increase signals by several orders of magnitude. The resulting increase in sensitivity has the potential to reduce requirements for the concentration of protein and ligands, improve the accuracy of the detection of interaction by allowing the use of near-stoichiometric conditions, and increase throughput. This chapter introduces a selection of basic techniques for the application of D-DNP to screening. Procedures for hyperpolarization are briefly reviewed, followed by the description of NMR methods for detection of binding through changes in chemical shift and relaxation parameters. Experiments employing competitive binding with a known ligand are shown, which can be used to determine binding affinity or yield structural information on the pharmacophore. The specific challenges of working with nonrenewable hyperpolarization are reviewed, and solutions including the use of multiplexed NMR detection are described. Altogether, the methods summarized in this chapter are intended to allow for the efficient detection of binding affinity, structure, and dynamics facilitated through substantial signal enhancements provided by hyperpolarization.

Structural characterization of aerogels derived from enzymatically oxidized galactomannans of fenugreek, sesbania and guar gums

Aerogels are obtained by laccase/2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidation of galactomannans (GMs) from the leguminous plants fenugreek (Trigonella foenum-graecum), sesbania (Sesbania bispinosa) and guar (Cyamopsis tetragonolobus). GM oxidation in aqueous solutions causes a viscosity increase, resulting in structured and stable hydrogels. Upon lyophilization, water-insoluble aerogels are obtained, capable of water uptake up to several times their own weight.The materials derived from the three gums have been analyzed and compared. Chemical modifications have been studied by electrospray-ionization mass spectrometry (ESI-MS) and Fourier-transform infrared spectroscopy (FTIR). Polymer structure has been determined by liquid-state and semi-quantitative solid-state nuclear magnetic resonance (NMR) spectroscopy and chemical stability by incubation under variable conditions of pH, ionic strength and solvent nature. The results show that hydrogel formation is due to oxidation of primary hydroxyl groups to carbonyl and carboxyl groups and subsequent formation of hemiacetal and ester bonds. Fenugreek displays the highest stability, compared to guar and sesbania rehydrated aerogels. This feature could be interpreted by its higher degree of substitution (Gal:Man = 1:1) and consequently higher amount of galactose primary alcohols, leading to more extensive crosslinking.

One-Step Synthesis, Structure, and Band Gap Properties of SnO2 Nanoparticles Made by a Low Temperature Nonaqueous Sol-Gel Technique.

Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO2) is extremely attractive as a transparent conducting material for applications in low-emission window coatings and solar cells, as well as in lithium-ion batteries and gas sensors. It is also an important catalyst and catalyst support for oxidation reactions. Here, we describe a novel nonaqueous sol–gel synthesis approach to produce tin oxide nanoparticles (NPs) with a low NP size dispersion. The success of this method lies in the nonhydrolytic pathway that involves the reaction between tin chloride and an oxygen donor, 1-hexanol, without the need for a surfactant or subsequent thermal treatment. This one-pot procedure is carried out at relatively low temperatures in the 160–260 °C range, compatible with coating processes on flexible plastic supports. The NP size distribution, shape, and dislocation density were studied by powder X-ray powder diffraction analyzed using the method of whole powder pattern modeling, as well as high-resolution transmission electron microscopy. The SnO2 NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state 13C and 1H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of 13C, 1H, and 119Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The 13C SSNMR, FTIR, and Raman data showed the presence of organic species derived from the 1-hexanol reactant remaining within the samples. The optical absorption, studied using UV–visible spectroscopy, indicated that the band gap (Eg) shifted systematically to lower energy with decreasing NP sizes. This unusual result could be due to mechanical strains present within the smallest NPs perhaps associated with the organic ligands decorating the NP surface. As the size increased, we observed a correlation with an increased density of screw dislocations present within the NPs that could indicate relaxation of the stress. We suggest that this could provide a useful method for band gap control within SnO2 NPs in the absence of chemical dopants.

Demonstration of multiparty quantum clock synchronization

Quantum clock synchronization (QCS) is a kind of method to measure the time difference among spatially separated clocks with the principle of quantum mechanics. The first QCS algorithm proposed by Chuang and Jozsa is merely based on two parties, which is further extended and generalized to multiparty situation by Krco and Paul. They present a multiparty QCS protocol based upon W-state, utilizing shared prior entanglement and broadcasting the classical information to synchronize spatially separated clocks. Shortly afterward, Ben-Av and Exman came up with an optimized multiparty QCS based on Z-state. In this work, we firstly report the demonstrations of these two multiparty QCS protocols in a four-qubit liquid-state nuclear magnetic resonance system. The experimental results show a great agreement with the theoretical predictions and also prove that Ben-AV’s multiparty QCS algorithm is more accurate than Krco’s.

NMR Spectroscopy Unchained: Attaining the Highest Signal Enhancements in Dissolution Dynamic Nuclear Polarization.

Dynamic nuclear polarization (DNP) via the dissolution method is one of the most successful methods for alleviating the inherently low Boltzmann-dictated sensitivity in nuclear magnetic resonance (NMR) spectroscopy. This emerging technology has already begun to positively impact chemical and metabolic research by providing the much-needed enhancement of the liquid-state NMR signals of insensitive nuclei such as 13C by several thousand-fold. In this Perspective, we present our viewpoints regarding the key elements needed to maximize the NMR signal enhancements in dissolution DNP, from the very core of the DNP process at cryogenic temperatures, DNP instrumental conditions, and chemical tuning in sample preparation to current developments in minimizing hyperpolarization losses during the dissolution transfer process. The optimization steps discussed herein could potentially provide important experimental and theoretical considerations in harnessing the best possible sensitivity gains in NMR spectroscopy as afforded by optimized dissolution DNP technology.

Nuclear Magnetic Resonance Spectroscopy for In Situ Monitoring of Porous Materials Formation under Hydrothermal Conditions.

The employment of nuclear magnetic resonance (NMR) spectroscopy for studying crystalline porous materials formation is reviewed in the context of the development of in situ methodologies for the observation of the real synthesis medium, with the aim of unraveling the nucleation and growth processes mechanism. Both liquid and solid state NMR techniques are considered to probe the local environment at molecular level of the precursor species either soluble in the liquid phase or present in the reactive gel. Because the mass transport between the liquid and solid components of the heterogeneous system plays a key role in the synthesis course, the two methods provide unique insights and are complementary. Recent technological advances for hydrothermal conditions NMR are detailed and their applications to zeolite and related materials crystallization are illustrated. Achievements in the field are exemplified with some representative studies of relevance to zeolites, aluminophosphate zeotypes, and metal-organic frameworks.

Dynamic nuclear polarization of carbonyl and methyl 13C spins of acetate using 4-oxo-TEMPO free radical.

Hyperpolarization of 13C-enriched biomolecules via dissolution dynamic nuclear polarization (DNP) has enabled real-time metabolic imaging of a variety of diseases with superb specificity and sensitivity. The source of the unprecedented liquid-state nuclear magnetic resonance spectroscopic or imaging signal enhancements of >10 000-fold is the microwave-driven DNP process that occurs at a relatively high magnetic field and cryogenic temperature. Herein, we have methodically investigated the relative efficiencies of 13C DNP of single or double 13C-labeled sodium acetate with or without 2H-enrichment of the methyl group and using a 4-oxo-TEMPO free radical as the polarizing agent at 3.35 T and 1.4 K. The main finding of this work is that not all 13C spins in acetate are polarized with equal DNP efficiency using this relatively wide electron spin resonance linewidth free radical. In fact, the carbonyl 13C spins have about twice the solid-state 13C polarization level of methyl 13C spins. Deuteration of the methyl group provides a DNP signal improvement of methyl 13C spins on a par with that of carbonyl 13C spins. On the other hand, both the double 13C-labeled [1,2-13C2] acetate and [1,2-13C2, 2H3] acetate have a relative solid-state 13C polarization at the level of [2-13C] acetate. Meanwhile, the solid-state 13C T1 relaxation times at 3.35 T and 1.4 K were essentially the same for all six isotopomers of 13C acetate. These results suggest that the intramolecular environment of 13C spins plays a prominent role in determining the 13C DNP efficiency, while the solid phase 13C T1 relaxation of these samples is dominated by the paramagnetic effect due to the relatively high concentration of free radicals.

Role of soluble aluminum species in the activating solution for synthesis of silico-aluminophosphate geopolymers

An aluminosilicate precursor, such as metakaolin, can be transformed into a cement-like geopolymer binder via a phosphate activation approach. This paper identifies the effect of the addition of aluminum species into the phosphate activating solution on the formation of such geopolymers, from the fresh to the hardened state. Activating solutions with Al/P molar ratios of 0, 0.1, and 0.3 were prepared by blending monoaluminum phosphate (MAP) and orthophosphoric acid (OPA). The rheological properties, fluidity, and setting times of the fresh geopolymer pastes and the compressive strength of the hardened geopolymer matrices were studied. Liquid-state 27Al and 31P nuclear magnetic resonance (NMR) measurements for the chemical environments of Al and P, and spectroscopic, thermal, and microscopic analyses revealed that the soluble aluminum in the phosphate activating solution played an important role during the geopolymerization process. Seeding of aluminum species through inclusion in the activating solution allowed a rapid sol/gel transition that improved the rheological properties and setting time of the fresh geopolymer pastes at ambient temperature. However, although the increased concentration of aluminum phosphate oligomers promoted by the soluble aluminum addition contributed to the formation of a compact matrix with high early strength, it hinders the ongoing reaction of metakaolin in the later period, which has a detrimental influence on ongoing strength development beyond 7 days of curing.

Semi-preparative high-resolution recycling liquid chromatography

A semi-preparative high-resolution system based on twin column recycling liquid chromatography was built. The integrated system includes a binary pump mixer, a sample manager, a two-column oven compartment, two low-dispersion detection cells, and a fraction manager (analytical). It addresses challenges in drug/impurity purification, which involve several constraints simultaneously: (1) small selectivity factors (α < 1.2, poor resolution), (2) mismatch of elution strength between the sample diluent and the eluent causing severe band fronting or tailing, (3) diluent-to-eluent mismatch of viscosity causing viscous fingering and unpredictable band deformation, (4) low abundance of the impurity relative to the active pharmaceutical ingredient (API) (<1/100), and (5) yield and purity levels to be larger than 99% and 90%, respectively.The prototype system was tested for the preparation of a trace impurity present in a concentrated solution of an API, estradiol. The ultimate goal was to collect ∼1 mg of impurity (>90% purity) for unambiguous structure elucidation by liquid state nuclear magnetic resonance (NMR 600 MHz and above). First, the particle size (3.5 μm) used to pack the 4.6 mm × 150 mm long twin columns is selected so that the speed-resolution of the recycling process is maximized at 4000 psi pressure drop. Next, the production rate of the process is also maximized by determining the optimum number (7) of cycles and the corresponding largest sample volume (160 μL) to be injected. Finally, the process is fully automated by programming the time events related to (1) sample cleaning, (2) transfer of the targeted impurity from one to the second twin column, and (3) impurity collection. The process was tested without interruption during one week for the collection of a trace impurity (α = 1.166, strong acetonitrile-methanol sample diluent, concentration ∼2 mg/L) from a concentrated (10 g/L) stock solution (60 mL total) of estradiol. The process enriches the impurity content relative to the API by about a factor ∼5000. For the lack of a sufficient collected amount (∼120 μg only) of the pure impurity (purity 50% only), NMR experiments could not provide reliable results. Instead, the combination of LC–MS (single ion monitoring) and UV absorption spectra (λmax shift) revealed that the targeted impurity was likely the low-abundant enol tautomeric form of the ketone estrone, a possible intermediate or by-product of the synthesis reaction of estradiol.

Molecular composition of the Humeome extracted from different green composts and their biostimulation on early growth of maize

The use of composted agricultural wastes as source of biostimulant compounds provides an added value to the recycling of biomasses. This study aims to expand the knowledge on the relationship between molecular composition and bioactivity of the Humeome extracted from green composts. Humic acids (HA) were isolated from the following green composts: 1. artichoke (HA-CYN), 2. artichoke/fennel (HA-CYNF), 3. tomato (HA-TOM), 4. cauliflower (HA-CAV). The compost-extracted Humeome was characterized by solid- and liquid-state Nuclear Magnetic Resonance (NMR) Spectroscopy, Infrared Spectrometry, pyrolysis-gas chromatography/mass spectrometry (Pyr-GC/MS), elemental and thermal analyses (TGA, DSC), and the effects on maize (Zea mays L.) seedling growth (roots and shoots) and leaves chlorophyll content, investigated at three different concentration rates (25, 50 and 100 mg L−1 C). All Humeomes from green composts generally favored plant growth, with HA-CYN and HA-CAV being active at small concentrations, while HA-TOM and HA-CYNF at greater application rates. The response of HA-CYN and HA-CAV was attributed to their large hydrophobicity that may favor adhesion to roots surfaces and concomitant release of bioactive molecules, whereas the toxicity of phenolic moieties in HA-TOM and HA-CYNF could only be mitigated by tighter intermolecular aggregation at greater concentrations. Bioactivity of Humeomes from green composts appeared to be related to their composition and consequent conformational structure in solution, whose flexibility determines the potential release of bioactive molecules that directly or indirectly influence plants development.

Intrinsic bounds of a two-qudit random evolution

We investigate entangled qudits evolving under random, local $SU(d)$ operations and demonstrate that this evolution is constrained by intrinsic bounds, showing robust features of two-qudit entangled states that can be useful for fault tolerant implementations of phase gates. Our analytical results are supported by numerical simulations and confirmed by experiments on liquid-state nuclear magnetic resonance qubits.

Corrosion behaviour and chemical stability of transparent hybrid sol-gel coatings deposited on aluminium in acidic and alkaline solutions

The aim of this study was to prepare transparent hybrid sol-gel coatings to serve as a barrier for corrosion protection of aluminium. The coatings were synthesised using silicon precursors tetraethyl orthosilicate (TEOS) and organically modified silicon precursor 3-methacryloxypropyltrimethoxysilane (MAPTMS) which were then mixed with different amounts of zirconium(IV) propoxide (ZTP) chelated using methacrylic acid (MAA). The synthesis process was followed using in-situ Fourier transform infrared spectroscopy and liquid-state 1H, 13C and 29Si nuclear magnetic resonance spectroscopy.The coating properties, such as transparency, topography, chemical composition, morphology and wettability were evaluated. Corrosion properties were analysed using electrochemical methods in ∼0.1 N NaCl in a pH range between 3 and 10. The chemical stability was evaluated in strongly alkaline solution.Homogeneous composition of the coatings was achieved through condensation reactions between Si- and Zr-based precursors. Obtained coatings were highly transparent, increased the contact water angle for polar and non-polar liquids compared to bare substrate, and improved the cleaning properties. The electrochemical measurements confirmed remarkable barrier protection in NaCl solutions of various pHs, especially for coatings with high Zr/Si ratios. In harsh media such as 0.1 N NaOH, the coating with low Zr/Si ratio was more stable. The results were interpreted in terms of different degrees of polycondensation of Si species as a function of Zr content in the coating. The importance of chemical speciation of the sol during synthesis were emphasised as this affects the subsequent coating properties.

Superhydrophobic Paper from Nanostructured Fluorinated Cellulose Esters.

The development of economically and ecologically viable strategies for superhydrophobization offers a vast variety of interesting applications in self-cleaning surfaces. Examples include packaging materials, textiles, outdoor clothing, and microfluidic devices. In this work, we produced superhydrophobic paper by spin-coating a dispersion of nanostructured fluorinated cellulose esters. Modification of cellulose nanocrystals was accomplished using 2H,2H,3H,3H-perfluorononanoyl chloride and 2H,2H,3H,3H-perfluoroundecanoyl chloride, which are well-known for their ability to reduce surface energy. A stable dispersion of nanospherical fluorinated cellulose ester was obtained by using the nanoprecipitation technique. The hydrophobized fluorinated cellulose esters were characterized by both solid- and liquid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and contact angle measurements. Further, we investigated the size, shape, and structure morphology of nanostructured fluorinated cellulose esters by dynamic light scattering, scanning electron microscopy, and X-ray diffraction measurements.

Computations of the chirality-sensitive effect induced by an antisymmetric indirect spin–spin coupling

ABSTRACTResults of quantum mechanical computations of the antisymmetric part of the indirect spin–spin coupling tensor, , performed using the coupled-cluster method, the second-order polarisation propagator approximation, and the density functional theory for 25 molecules and nearly 100 spin–spin couplings are reported. These results are used for an estimation of the magnitude of the recently proposed liquid-state nuclear magnetic resonance chirality-sensitive effect, which allows to determine the molecular chirality directly, i.e. without the need for the application of any chiral agent. The following were found: (i) the antisymmetry J⋆ is usually larger for the coupling between spins separated by two chemical bonds in comparison with the coupling through one bond, (ii) promising samples are those which contain fluorine, and (iii) the antisymmetry of the spin–spin coupling tensor is of the order of a few hertz for commercially available chemical compounds. Therefore, the relevant property of the experiment, the pseudoscalar Jc, for them is of the order of 1 nHz m/V.

Degradation of the Formamidinium Cation and the Quantification of the Formamidinium–Methylammonium Ratio in Lead Iodide Hybrid Perovskites by Nuclear Magnetic Resonance Spectroscopy

The highest efficiency in perovskite solar cells is currently achieved with mixed-cation hybrid perovskites. The ratio in which the cations are present in the perovskite structure has an important effect on the optical properties and the stability of these materials. At present, the formamidinium cation is an integral part of many of the highest efficiency perovskite systems. In this work, we introduce a nuclear magnetic resonance (NMR) spectroscopy protocol for the identification and differentiation of mixed perovskite phases and of a secondary phase due to formamidinium degradation. The influence of the cooling rate used in a precipitation method on the FA/MA ratio in formamidinium–methylammonium lead iodide perovskites (FAxMA1–xPbI3) was investigated and compared to the FA/MA ratio in thin films. In order to obtain the FA/MA ratio from fast and accessible liquid-state 1H NMR spectra, the influence of the acidity of the solution on the line width of the resonances was elucidated. The ratio of the organi...

Automatic differential analysis of NMR experiments in complex samples.

Liquid state nuclear magnetic resonance (NMR) is a powerful tool for the analysis of complex mixtures of unknown molecules. This capacity has been used in many analytical approaches: metabolomics, identification of active compounds in natural extracts, and characterization of species, and such studies require the acquisition of many diverse NMR measurements on series of samples. Although acquisition can easily be performed automatically, the number of NMR experiments involved in these studies increases very rapidly, and this data avalanche requires to resort to automatic processing and analysis. We present here a program that allows the autonomous, unsupervised processing of a large corpus of 1D, 2D, and diffusion-ordered spectroscopy experiments from a series of samples acquired in different conditions. The program provides all the signal processing steps, as well as peak-picking and bucketing of 1D and 2D spectra, the program and its components are fully available. In an experiment mimicking the search of a bioactive species in a natural extract, we use it for the automatic detection of small amounts of artemisinin added to a series of plant extracts and for the generation of the spectral fingerprint of this molecule. This program called Plasmodesma is a novel tool that should be useful to decipher complex mixtures, particularly in the discovery of biologically active natural products from plants extracts but can also in drug discovery or metabolomics studies.

New research progress of nuclear magnetic resonance quantum information processing

In the last 20 years, there have been lots of novel developments and remarkable achievements in quantum information processing theoretically and experimentally. Among them, the coherent control of nuclear spin dynamics is a powerful tool for the experimental implementation of quantum schemes in liquid and solid nuclear magnetic resonance (NMR) system, especially in liquid-state NMR. Compared with other quantum information processing systems, NMR platform has many advantages such as the long coherence time, the precise manipulation and well-developed quantum control techniques, which make it possible to accurately control a quantum system with up to 12-qubits. Extensive applications of liquid-state NMR spectroscopy in quantum information processing such as quantum communication, quantum computing and quantum simulation have been thoroughly studied over half a century. There are also many outstanding researches in the recent several years. So we focus on the recent researches in this review article. First, we introduce the basic principle of the liquid-state NMR quantum computing and two new methods reported in the pseudo-pure state preparation which has more advantages than the traditional methods. The quantum noise-injection methods and the quantum tomography technology in liquid-state NMR are also mentioned. Then we overview Horrow-Hassidim-Lioyd algorithm, quantum support vector machine algorithm, duality quantum computing and their implementations in liquid-state NMR system. Also, we report recent researches about quantum simulations, including quantum tunneling, high-energy physics and topological sequences. Then we display the quantum cloud platform of our group. In order to let more people, either amateurs or professionals, embrace and more importantly participate in the tidal wave of quantum science, we launch our NMR quantum cloud computing (NMRCloudQ) service. Through NMRCloudQ, we offer a direct access to a real, physical spectrometer in our laboratory and encourage users to explore quantum phenomena and demonstrate quantum algorithms. Finally, we discuss the development prospects and development bottlenecks of NMR, and point out the prospects for the future development direction.

Qualitative and Quantitative NMR Approaches in Blood Serum Lipidomics.

Nuclear magnetic resonance (NMR) spectroscopy in combination with chemometrics can be applied in the analysis of complex biological samples in many ways. For example, we can analyze lipids, elucidate their structures, determine their nutritional values, and determine their distribution in blood serum. As lipids are not soluble in water, they are transported in blood as lipid-rich self-assembled particles, divided into different density assemblies from high- to very-low-density lipoproteins (HDL to VLDL), or by combining with serum proteins, such as albumins (human serum albumins (HSA)). Therefore, serum lipids can be analyzed as they are using only a 1:1 (v/v) dilution with a buffer or deuterated water prior to analysis by applying 1H NMR or 1H NMR edited-by-diffusion techniques. Alternatively, lipids can be extracted from the serum using liquid partition equilibrium and then analyzed using liquid-state NMR techniques. Our chapter describes protocols that are used for extraction of blood serum lipids and their quantitative 1H NMR (1H qNMR) analysis in lipid extracts as well as 1H NMR edited by diffusion for direct blood serum lipid analysis.

Synthesis, Crystal Structure, and Supramolecular Understanding of 1,3,5-Tris(1-phenyl-1H-pyrazol-5-yl)benzenes.

Understanding the supramolecular environment of crystal structures is necessary to facilitate designing molecules with desirable properties. A series of 12 novel 1,3,5-tris(1-phenyl-1H-pyrazol-5-yl)benzenes was used to assess the existence of planar stacking columns in supramolecular structures of pyrazoles. This class of molecules with different substituents may assist in understanding how small structural changes affect the supramolecular environment. The obtained compounds did not present the formation of planar stacking interactions between benzenes in solid or liquid states. This supposition was indicated by single crystal diffraction, Density Functional Theory (DFT) and quantum theory of atoms in molecules (QTAIM) calculations, and concentration-dependent liquid-state 1H nuclear magnetic resonance (NMR). NMR showed that chemical shifts of benzene and pyrazole hydrogens confirm that planar stacking interactions are not formed in solution. The crystalline structures presented different molecular conformations. The molecular structures of 5 and 9b are in a twisted conformation, while compound 7 showed a conformation analogous to a calyx form.