Solid-state Density Research Articles

Low-Frequency Raman Spectroscopy of Pure and Cocrystallized Mycophenolic Acid.

The aqueous solubility of solid-state pharmaceuticals can often be enhanced by cocrystallization with a coformer to create a binary cocrystal with preferred physical properties. Greater understanding of the internal and external forces that dictate molecular structure and intermolecular packing arrangements enables more efficient design of new cocrystals. Low-frequency (sub-200 cm-1) Raman spectroscopy experiments and solid-state density functional theory simulations have been utilized together to investigate the crystal lattice vibrations of mycophenolic acid, an immunosuppressive drug, in its pure form and as a cocrystal with 2,2'-dipyridylamine. The lattice vibrations primarily consist of large-amplitude translations and rotations of the crystal components, thereby providing insights into the critical intermolecular forces governing cohesion of the molecular solids. The simulations reveal that despite mycophenolic acid having a significantly unfavorable conformation in the cocrystal as compared to the pure solid, the cocrystal exhibits greater thermodynamic stability over a wide temperature range. The energetic penalty due to the conformational strain is more than compensated for by the strong intermolecular forces between the drug and 2,2'-dipyridylamine. Quantifying the balance of internal and external energy factors in cocrystal formation indicates a path forward in the development of future mycophenolic acid cocrystals.

Carbon Dioxide Sequestration by Triboelectric Charging of Tumbling Quartz Sand

Mechanical activation (i.e., tumbling) of quartz sand in a carbon dioxide (CO2) atmosphere leads to triboelectric charging of the sand grains, driving a process that ultimately sequesters and removes CO2 from the ambient atmosphere. Supported by diffuse reflectance FTIR and 13C solid-state NMR experiments and density functional theory (DFT) calculations, we propose that CO2 is inserted into the quartz lattice to form an anchored CO3 species, a process that otherwise requires high temperature and pressure to proceed synthetically. The products of the reaction are stable for at least 6 months at ambient temperature and pressure, but CO2 is liberated at temperatures above 150 °C. The prospect of using this method to remove CO2 from the atmosphere and, ultimately, to help mitigate the adverse effects of greenhouse gases and global warming is briefly discussed.

Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks.

Despite growing interest in the potential applications of p-block hydroperoxo complexes, the chemistry of inorganic hydroperoxides remains largely unexplored. For instance, single-crystal structures of antimony hydroperoxo complexes have not been reported to date. Herein, we present the synthesis of six triaryl and trialkylantimony dihydroperoxides [Me3Sb(OOH)2, Me3Sb(OOH)2·H2O, Ph3Sb(OOH)2·0.75(C4H8O), Ph3Sb(OOH)2·2CH3OH, pTol3Sb(OOH)2, pTol3Sb(OOH)2·2(C4H8O)], obtained by the reaction of the corresponding dibromide antimony(V) complexes with an excess of highly concentrated hydrogen peroxide in the presence of ammonia. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, Fourier transform infrared and Raman spectroscopies, and thermal analysis. The crystal structures of all six compounds reveal hydrogen-bonded networks formed by hydroperoxo ligands. In addition to the previously reported double hydrogen bonding, new types of hydrogen-bonded motifs formed by hydroperoxo ligands were found, including infinite hydroperoxo chains. Solid-state density functional theory calculation of Me3Sb(OOH)2 revealed reasonably strong hydrogen bonding between OOH ligands with an energy of 35 kJ/mol. Additionally, the potential application of Ph3Sb(OOH)2·0.75(C4H8O) as a two-electron oxidant for the enantioselective epoxidation of olefins was investigated in comparison with Ph3SiOOH, Ph3PbOOH, t-BuOOH, and H2O2.

Electron Trap Depths in Cubic Lutetium Oxide Doped with Pr and Ti, Zr or Hf─From Ab Initio Multiconfigurational Calculations.

We propose a universal approach to model intervalence charge transfer (IVCT) and metal-to-metal charge transfer (MMCT) transitions between ions in solids. The approach relies on already well-known and reliable ab initio RASSCF/CASPT2/RASSI-SO calculations for a series of emission center coordination geometries (restricted active space self-consistent field, complete active space second-order perturbation theory, and restricted active space state interaction with spin-orbit coupling). Embedding with ab initio model potentials (AIMPs) is used to represent the crystal lattice. We propose a way to construct the geometries via interpolation of the coordinates obtained using solid-state density functional theory (DFT) calculations for the structures where the activator metal is at specific oxidation (charge) states of interest. The approach thus takes the best of two worlds: the precision of the embedded cluster calculations (including localized excited states) and the geometries from DFT, where the effects of ionic radii mismatch (and eventual nearby defects) can be modeled explicitly. The method is applied to the Pr activator and Ti, Zr, Hf codopants in cubic Lu2O3, in which the said ions are used to obtain energy storage and thermoluminescence properties. Electron trap charging and discharging mechanisms (not involving a conduction band) are discussed in the context of the IVCT and MMCT role in them. Trap depths and trap quenching pathways are analyzed.

Multiscale Dot-Wire-Sheet Heterostructured Nitrogen-Doped Carbon Dots-Ti3 C2 Tx /Silk Nanofibers for High-Performance Fiber-Shaped Supercapacitors.

Fiber-shaped supercapacitors (FSCs) have become one of the significantly strategical flexible energy-storage materials towards future wearable textile electronics and metaverse technologies. Here, we develop the high-performance FSCs based on multiscale dot-wire-sheet heterostructure microfiber of nitrogen-doped carbon dots-Ti3 C2 Tx /silk nanofibers (NCDs-Ti3 C2 Tx /SNFs) hybrids via microfluidic fabrication. Due to the enlarged interlayer spacing, plentiful porous channels, accelerated H+ ion transport dynamics, large electrical conductivity and excellent mechanical strength/flexibility, the NCDs-Ti3 C2 Tx /SNFs possesses high volumetric capacitance (2218.7 F cm-3 ) and reversible charge-discharge stability in 1 M H2 SO4 electrolyte. Furthermore, the solid-state FSCs present high energy density (57.9 mWh cm-3 ), good capacitance (1157 F cm-3 ), long-life cycles (82.3 % capacitance retention after 40000 cycles), which realize the actual energy-supply applications (powering lamp, watch and toy car).

Identifying Ordered OH/F Anions in Hydroxyfluorides by a Terahertz Spectroscopic Approach

Distinguishing the OH–/F– ligands has been one of the vital challenges in X-ray crystallography. Fluorine and oxygen atoms have similar scattering cross sections of X-rays, and the hydrogen atoms are invisible to X-rays, rendering the two functional groups F– and OH– indistinguishable from each other with the X-ray diffraction (XRD) method. We demonstrated that terahertz (THz) spectroscopy is promising for solving this problem. THz spectroscopy probes the optical phonon modes given rise by intermolecular interactions. Different F–/OH– substitutions usually lead to remarkable changes in the intermolecular interactions, which can be reflected in THz spectroscopy. Guanidinium fluorooxoborates represent new-generation nonlinear optical materials used in the short-wavelength ultraviolet region. For such materials, a dispute remains regarding the OH–/F– substitution in the B3O3(F, OH)4 anion units, which suggests 16 possible configurations of the anion units. Employing solid-state density functional theory, we showed that all 16 configurations display fingerprint THz peaks. Against the experimental criterion of high-resolution THz spectroscopy, we proved that only one configuration exists, implying that the anion structure is well-ordered. THz spectroscopy provides an essential complementary tool to the XRD method for retrieving detailed structural information. Furthermore, the terahertz vibrational information reveals that the cationic unit of guanidinium is a rigid building block unit with little external and internal vibration mixing, whereas the anionic unit is not rigid and produces vigorous mixing. This finding leads to a deeper understanding of the role of the constituent units in producing the excellent optical properties of the guanidinium fluorooxoborate compounds.

Feasibility of Using Poisons to Suppress the Positive Temperature Reactivity Coefficient in Hydride-Moderated Reactors

Metal hydrides are being seriously considered for advanced nuclear reactor or microreactor applications due to their solid physical state and high hydrogen density. Using hydrides for autonomous applications poses several research and development challenges, one of which relates to neutron upscattering in the thermal energy regime. These hydrides, including zirconium hydride and yttrium hydride, result in a positive temperature coefficient of reactivity for several advanced reactor designs. In this study, we consider one such design that exhibits positive feedback from metal hydrides and thoroughly investigate the neutronic aspects of the core. Temperature reactivity coefficients for four fuels and two hydride moderator configurations are studied, and the total temperature coefficients are found to be positive for all designs, showing that this issue cannot be resolved simply by material variations. Accordingly, five epi-thermal absorbers were evaluated to demonstrate the feasibility of the excess positive feedback suppression in the core instigating from neutron energy spectrum shift. Following which, two promising burnable poison candidates are selected to investigate further throughout the core discharge. Promising results are shown for this core design, which can be extended to other hydride-moderated remote special-purpose reactor designs.

Direct Transformation of SiH4 to a Molecular L(H)2Co═Si═Co(H)2L Silicide Complex.

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si-H bond activations in SiH4 at the metal centers of 14-electron LCoI fragments (L = Tp″, HB(3,5-diisopropylpyrazolyl)3-; [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)). Upon exposure of (Tp″Co)2(μ-N2) (1) to SiH4, a mixture of (Tp″Co)2(μ-H) (2) and (Tp″Co)2(μ-H)2 (3) was formed and no evidence for Si-H oxidative addition products was observed. In contrast, [BP2tBuPz]-supported Co complexes led to Si-H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP2tBuPz]Co)2(μ-N2) (5) with SiH4 gave the dicobalt silicide complex [BP2tBuPz](H)2Co═Si═Co(H)2[BP2tBuPz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. The effect of the [BP2tBuPz] ligand on Co-Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP2tBuPz]Co(L)x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH4, despite the lack of significant Si-H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of MexSiH4-x (x = 1-3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

Tailoring and Identifying Brønsted Acid Sites on Metal Oxo-Clusters of Metal-Organic Frameworks for Catalytic Transformation.

Metal-organic frameworks (MOFs) with Brønsted acidity are an alternative solid acid catalyst for many important chemical and fuel processes. However, the nature of the Brønsted acidity on the MOF's metal cluster or center is underexplored. To design and optimize the acid strength and density in these MOFs, it is important to understand the origin of their acidity at the molecular level. In the present work, isoreticular MOFs, ZrNDI and HfNDI (NDI = N,N'-bis(5-isophthalate)naphthalenediimide), were prepared as a prototypical system to unravel and compare their Brønsted and Lewis acid sites through an array of spectroscopic, computational, and catalytic characterization techniques. With the aid of solid-state nuclear magnetic resonance and density functional calculations, Hf6 oxo-clusters on HfNDI are quantitatively proved to possess a higher density Brønsted acid site, while ZrNDI-based MOFs display stronger and higher-population Lewis acidity. HfNDI-based MOFs exhibit a superior catalytic performance in activating dihydroxyacetone (DHA) and converting DHA to ethyl lactate, with 71.1% selectivity at 54.7% conversion after 6 h. The turnover frequency of BAS-dominated Hf-MOF in DHA conversion is over 50 times higher than that of ZSM-5, a strong BAS-based zeolite. It is worth noting that HfNDI is reported for the first time in the literature, which is an alternative platform catalyst for biorefining and green chemistry. The present study furthermore highlights the uniqueness of Hf-based MOFs in this important biomass-to-chemical transformation.

Deciphering the potassium storage phase conversion mechanism of phosphorus by combined solid-state NMR spectroscopy and density functional theory calculations

Phosphorus is the potential anode material for emerging potassium-ion batteries (PIBs) owing to the highest specific capacity and relatively low operation plateau. However, the reversible delivered capacities of phosphorus-based anodes, in reality, are far from the theoretical capacity corresponding to the formation of K3P alloy. And, their underlying potassium storage mechanisms remain poorly understood. To address this issue, for the first time, we perform high-resolution solid-state 31P NMR combined with XRD measurements, and density functional theory calculations to yield a systemic quantitative understanding of (de)potassiation reaction mechanism of phosphorus anode. We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP ↔ (K3P11, K3P7, beta-K4P6) ↔ (alpha-K4P6) ↔ (K1−xP, KP, K4−xP3, K1+xP) ↔ (amorphous K4P3, amorphous K3P) that are proceed along with the electrochemical potassiation/depotassiation processes. Additionally, the corresponding K-P alloys intermediates, such as the amorphous phases of K4P3, K3P, and the nonstoichiometric phases of “K1−xP”, “K1+xP”, “K4−xP3” are experimentally detected, which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics, resulting in lower capacity of phosphorus-based anodes. Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.

Terahertz spectroscopy for quantitatively elucidating the crystal transformation of chiral histidine enantiomers to racemic compounds

d-Histidine (d-His), l-Histidine (l-His), and their racemic compound dl-Histidine (dl-His) have different stereo chirality, making them intrinsic diverse functionalities to the living system. Identifying the configuration and crystal structures of enantiomers and the racemic compound is always the foremost requirement in processing protein foods. Although these features can be analyzed by spectroscopic technologies individually, it remains challenging to incorporate these complex methods into a facile analytical strategy. Herein, we propose a terahertz spectroscopy with solid-state density functional theory to both distinguish the configurational difference and quantify the crystal transformation from l-His and d-His to dl-His. By comparison with X-ray diffraction analysis, the validity of the crystal transformation evaluation based on terahertz spectroscopy is verified. A normalized fitting line regarding the terahertz absorption frequency and intensity is calculated to quantitatively elucidate the crystal transformation from enantiomers to dl-His. Our findings provide a new analytical approach to the research on food chemistry.

Constructing robust cathode/Li interfaces and intensifying ion transport kinetics for PEO-based solid-state lithium-sulfur batteries

Solid-state lithium-sulfur batteries (SSLSBs) are attractive due to their potential to provide high energy densities. However, the battery chemistry of SSLSBs still faces significant challenges, such as sluggish ion transport and prominent interface failures. Here, a high-performance cell is demonstrated by designing a composite electrolyte (CPE) consisting of polyethylene glycol azobenzamide (PGA) and poly (ethylene oxide) (PEO). Meanwhile, 7Li solid-state NMR spectroscopy and density functional theory (DFT) results show that PGA promotes the dissociation of lithium salts and generate more free lithium ions, thereby improving the ion migration kinetics. Moreover, ex-situ XPS and DFT confirm that PGA has a significant confined effect on polysulfides and effectively suppresses the shuttle effect. Subsequently, the interfacial layer consisted of abundant LiF&Li3N, which could achieve rapid lithium-ion transport and uniform deposition. Therefore, a stable ultra-long cycle time of over 2800 h can be achieved for the Li/Li symmetric cells at 0.2 mA cm−2. The prepared CPE exhibits a high ionic conductivity of 4.9 × 10-4 S cm−1 and a lithium-ion transference number of 0.53 at 50 °C. The assembled SSLSBs show an excellent cycling performance, which accomplishes 100 cycles at 0.2C with the reversible discharge capacity of 541 mAh/g. The superior performance of the SSLSBs rationalizes the CPE construction concept and leads to considerations for the innovative design of PEO-based SSLSBs.

An investigation on 3-hydroxybenzaldehyde for exploring terahertz low-frequency vibration modes with quasi-harmonic approximation method

3-Hydroxybenzaldehyde (3-HBA) was investigated in the range of 0.6–2.8 THz by terahertz time-domain spectroscopy (THz-TDS) and solid-state density functional theory (ss-DFT) with first-principles calculation. Four distinct peaks were found respectively, and among them, the intensity disparity between experiment and simulation spectra at 2.04 THz was recognized as the biggest inconsistency. Considering thermal behavior can be responsible for this, quasi-harmonic approximation (QHA) method was introduced to mimic the unit cell volume expansion. According to vibrational modes analysis, it was ascertained that the biggest vibrational modes discrepancy was also located at 2.04 THz. Molecules in 0% and 4% unit cell expansion exhibit an opposite rotational direction in a-b plane compared with 2% unit cell expansion. Noncovalent intermolecular interactions were investigated with independent gradient model (IGM), and the result indicates that hydrogen bonding is the dominating noncovalent interaction of 3-HBA. While calculating systematic potential energy to the displaced bonds stretching involving hydrogen atoms, it was found the anomalous potential energy variation to the bond stretching provides a possible explanation for the rotation direction divergence, that is, the rotation direction divergence can be related to some hydrogen atoms seeking lower overall potential energy around their equilibrium positions during bond stretching in response to the variational intermolecular van der Waals force. This research combined THz-TDS with the quasi-harmonic approximation method, elucidating the principle of vibrational characteristics in different volumes, which is beneficial to the investigation of the terahertz low-frequency vibration to thermal behavior as a reference in biochemistry and other fields.

Evaluation of the Stability of Diamine-Appended Mg2(dobpdc) Frameworks to Sulfur Dioxide.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are a promising class of CO2 adsorbents, although their stability to SO2─a trace component of industrially relevant exhaust streams─remains largely untested. Here, we investigate the impact of SO2 on the stability and CO2 capture performance of dmpn-Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-propanediamine), a candidate material for carbon capture from coal flue gas. Using SO2 breakthrough experiments and CO2 isobar measurements, we find that the material retains 91% of its CO2 capacity after saturation with a wet simulated flue gas containing representative levels of CO2 and SO2, highlighting the robustness of this framework to SO2 under realistic CO2 capture conditions. Initial SO2 cycling experiments suggest dmpn-Mg2(dobpdc) may achieve a stable operating capacity in the presence of SO2 after initial passivation. Evaluation of several other diamine-Mg2(dobpdc) variants reveals that those with primary,primary (1°,1°) diamines, including dmpn-Mg2(dobpdc), are more robust to humid SO2 than those featuring primary,secondary (1°,2°) or primary,tertiary (1°,3°) diamines. Based on the solid-state 15N NMR spectra and density functional theory calculations, we find that under humid conditions, SO2 reacts with the metal-bound primary amine in 1°,2° and 1°,3° diamine-appended Mg2(dobpdc) to form a metal-bound bisulfite species that is charge balanced by a primary ammonium cation, thereby facilitating material degradation. In contrast, humid SO2 reacts with the free end of 1°,1° diamines to form ammonium bisulfite, leaving the metal-diamine bond intact. This structure-property relationship can be used to guide further optimization of these materials for CO2 capture applications.

First-principles study of elastic and thermodynamic properties of UO2, γ-UO3 and α-U3O8

A detailed solid-state density functional theory study of uranium dioxide (UO2), gamma uranium trioxide (γ-UO3), and alpha triuranium octoxide (α-U3O8), which are very common materials throughout the nuclear fuel cycle, was carried out. DFT simulations of these three oxides were presented using both PBE+U and LDA+U functionals to examine their mechanical and thermodynamic properties. The computed lattice parameters were found to be in very good agreement with previous experimental results. The values of elastic properties like bulk, shear, and Young's modulus, as well as Poisson's ratio, were predicted, and the calculated Debye temperature was reported. The elastic anisotropy of UO2, γ-UO3, and α-U3O8 was calculated for the first time, from which the anisotropic degrees of these oxides were revealed by the values of anisotropic parameters and three-dimensional surface constructions of elastic properties. In addition, thermodynamic properties of UO2, γ-UO3, and α-U3O8, including heat capacity, entropy, enthalpy, phonon free energy, and Gibbs free energy, were determined as a function of temperature in the range of 0 - 2000 K. The computed thermodynamic values show an overall good agreement with available experiments, especially at low temperatures. The obtained physical parameters can provide meaningful data for further experimental investigations and promote the development of nuclear fuel cycles.

Tunable Solid Acid Catalyst Thin Films Prepared by Atomic Layer Deposition.

Solid acid catalysts, including zeolites and amorphous silica-aluminas (ASAs), are industrially important materials widely used in the fuel and petrochemical industries. The versatility of zeolites is due to the Brønsted acidity of the bridging hydroxyl and shape selectivity that can be tailored during and after synthesis. This is in contrast to amorphous silica-alumina, where tailoring acidity is a major challenge as the Brønsted acid structure in ASA is still debated. In both cases, however, the pore size and acidity cannot be tuned independently, and this is particularly limiting in the application of biomass conversion, where zeolite pores are too small for the molecules of interest. Herein, we present a method using atomic layer deposition (ALD) to prepare thin films of solid acid materials where the ratio of Brønsted to Lewis acid sites can be tuned precisely. This capability, combined with the sub-nm pore size control afforded by ALD yields a powerful and flexible method for synthesizing solid acid catalysts inside virtually any mesoporous host. We demonstrate the utility of these materials in two acid-catalyzed reactions relevant to biomass conversion: (1) Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction and dehydration of fructose and (2) cascade reaction of glucose to 5-hydroxymethylfurfural. Finally, we propose a plausible structure for the Brønsted acid sites in our materials based on infrared spectroscopy and solid-state nuclear magnetic resonance measurements and density functional theory calculations and argue that this same structure might apply to conventional ASAs as well.

Assembling Au4 Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model.

Thiolate-protected gold nanoclusters (denoted as Aum(SR)n or AunLm) have received extensive attention both experimentally and theoretically. Understanding the growth mode of the Au4 unit in Aum(SR)n is of great significance for experimental synthesis and the search for new gold clusters. In this work, we first build six clusters of Au7(AuCl2)3, Au12(AuCl2)4, Au16(AuCl2)6, Au22(AuCl2)6, and Au30(AuCl2)6 with the Au4 unit as the basic building blocks. Density functional theory (DFT) calculations show that these newly designed clusters have high structural and electronic stabilities. Based on chemical bonding analysis, the electronic structures of these clusters follow the superatom network (SAN) model. Inspired by the cluster structures, we further predicted an Au4 two-dimensional (2D) monolayer and a three-dimensional (3D) crystal using graphene and diamond as templates, respectively. The computational results demonstrate that the two structures have high dynamic, thermal, and mechanical stabilities, and both structures exhibit metallic properties according to the band structures calculated at the HSE06 level. The chemical bonding analysis by the solid-state natural density partitioning (SSAdNDP) method indicates that they are superatomic crystals assembled by two electron Au4– superatoms. With this construction strategy, the new bonding pattern and properties of AunLm are studied and the structure types of gold are enriched.

Increased CO2 Affinity and Adsorption Selectivity in MOF-801 Fluorinated Analogues.

The novel ZrIV-based perfluorinated metal–organic framework (PF-MOF) [Zr6O4(OH)4(TFS)6] (ZrTFS) was prepared under solvent-free conditions using the commercially available tetrafluorosuccinic acid (H2TFS) as a bridging ditopic linker. Since H2TFS can be seen as the fully aliphatic and perfluorinated C4 analogue of fumaric acid, ZrTFS was found to be isoreticular to zirconium fumarate (MOF-801). The structure of ZrTFS was solved and refined from X-ray powder diffraction data. Despite this analogy, the gas adsorption capacity of ZrTFS is much lower than that of MOF-801; in the former, the presence of bulky fluorine atoms causes a considerable window size reduction. To have PF-MOFs with more accessible porosity, postsynthetic exchange (PSE) reactions on (defective) MOF-801 suspended in H2TFS aqueous solutions were carried out. Despite the different H2TFS concentrations used in the PSE process, the exchanges yielded two mixed-linker materials of similar minimal formulae [Zr6O4(μ3-OH)4(μ1-OH)2.08(H2O)2.08(FUM)4.04(HTFS)1.84] (PF-MOF1) and [Zr6O4(μ3-OH)4(μ1-OH)1.83(H2O)1.83(FUM)4.04(HTFS)2.09] (PF-MOF2) (FUM2– = fumarate), where the perfluorinated linker was found to fully replace the capping acetate in the defective sites of pristine MOF-801. CO2 and N2 adsorption isotherms collected on all samples reveal that both CO2 thermodynamic affinity (isosteric heat of adsorption at zero coverage, Qst) and CO2/N2 adsorption selectivity increase with the amount of incorporated TFS2–, reaching the maximum values of 30 kJ mol–1 and 41 (IAST), respectively, in PF-MOF2. This confirms the beneficial effect coming from the introduction of fluorinated linkers in MOFs on their CO2 adsorption ability. Finally, solid-state density functional theory calculations were carried out to cast light on the structural features and on the thermodynamics of CO2 adsorption in MOF-801 and ZrTFS. Due to the difficulties in modeling a defective MOF, an intermediate structure containing both linkers in the framework was also designed. In this structure, the preferential CO2 adsorption site is the tetrahedral pore in the “UiO-66-like” structure. The extra energy stabilization stems from a hydrogen bond interaction between CO2 and a hydroxyl group on the inorganic cluster.

Monitoring of CaCO3 Nanoscale Structuration through Real-Time Liquid Phase Transmission Electron Microscopy and Hyperpolarized NMR.

Calcium carbonate (CaCO3) is one of the most significant biominerals in nature. Living organisms are able to control its biomineralization by means of an organic matrix to tailor a myriad of hybrid functional materials. The soluble organic components are often proteins rich in acidic amino-acids such as l-aspartic acid. While several studies have demonstrated the influence of amino acids on the crystallization of calcium carbonate, nanoscopic insight of their impact on CaCO3 mineralization, in particular at the early stages, is still lacking. Herein, we implement liquid phase-transmission electron microscopy (LP-TEM) in order to visualize in real-time and at the nanoscale the prenucleation stages of CaCO3 formation. We observe that l-aspartic acid favors the formation of individual and aggregated prenucleation clusters which are found stable for several minutes before the transformation into amorphous nanoparticles. Combination with hyperpolarized solid state nuclear magnetic resonance (DNP NMR) and density functional theory (DFT) calculations allow shedding light on the underlying mechanism at the prenucleation stage. The promoting nature of l-aspartic acid with respect to prenucleation clusters is explained by specific interactions with both Ca2+ and carbonates and the stabilization of the Ca2+-CO32-/HCO3- ion pairs favoring the formation and stabilization of the CaCO3 transient precursors. The study of prenucleation stages of mineral formation by the combination of in situ LP-TEM, advanced analytical techniques (including hyperpolarized solid-state NMR), and numerical modeling allows the real-time monitoring of prenucleation species formation and evolution and the comprehension of their relative stability.

Low-Frequency Vibrational Spectroscopy and Quantum Mechanical Simulations of the Crystalline Polymorphs of the Antiviral Drug Ribavirin.

Crystal polymorphism is a common phenomenon in pharmaceutical solids and a critical issue when considering the formulation of therapeutics since multiple polymorphs may form during drug manufacturing. Low-frequency vibrational spectroscopy is sensitive to polymorphic content, and in this work, terahertz time-domain spectroscopy and low-frequency Raman spectroscopy were utilized in the study of crystalline ribavirin, a widely applicable antiviral. Characteristic spectra with numerous peaks in the sub-200 cm–1 region were obtained of the more common polymorph of ribavirin (Form II). Solid-state density functional theory (ss-DFT) simulations were then used to optimize the crystal structure of this polymorph and calculate the frequencies and spectral intensities of the lattice vibrations in the low-frequency region. The near-harmonic thermal behavior of the sample with cooling enabled excellent agreement between experiment and theory to be achieved, emphasizing the quality of the applied model, and the observed spectral peaks could be assigned to specific atomic motions in the solid. Form I and Form II polymorphs of ribavirin were both investigated with ss-DFT to understand the different aspects governing the relative stabilities of these solids. The ss-DFT simulations of the polymorph energies revealed that Form II is more stable at all temperatures due to a stronger cohesive energy than Form I; however, ribavirin in Form I has a significantly lower conformational energy. The finding of monotropism appears to conflict with the reported enantiotropism of the ribavirin polymorphs but ultimately confirms that crystal defects in the real samples greatly affect the thermodynamic relationship of the crystals.