The Effects of the Steroids 5-Androstenediol and Dehydroepiandrosterone and Their Synthetic Derivatives on the Viability of K562, HeLa, and Wi-38 Cells and the Luminol-Stimulated Chemiluminescence of Peripheral Blood Mononuclear Cells from Healthy Volunteers.

In order to evaluate the role of substituents at 3-C and 17-C in the cytotoxic and cytoprotective actions of DHEA and 5-AED molecules, their derivatives were synthesized by esterification using the corresponding acid anhydrides or acid chlorides. As a result, seven compounds were obtained: four DHEA derivatives (DHEA 3-propionate, DHEA 3-butanoate, DHEA 3-acetate, DHEA 3-methylsulfonate) and three 5-AED derivatives (5-AED 3-butanoate, 5-AED 3,17-dipropionate, 5-AED 3,17-dibutanoate). All of these compounds showed micromolar cytotoxic activity toward HeLa and K562 human cancer cells.

Dioxygen-halogen bonding exemplified by crystalline peroxosolvates of ,'-bis(haloacetyl) bispidines.

The halogen bonding in molecular crystals and supramolecular assemblies has been widely investigated. Special attention is given to the molecular structures capable of simultaneously exhibiting different types of non-covalent interactions, including conventional hydrogen bonds and halogen bonds. This paper systematically analyzes crystalline peroxosolvates of bispidine-based bis-amide derivatives, containing haloacetic acid residues, namely previously reported 1,1'-(1,5-dimethyl-3,7-diazabicyclo[3.

Aggregation-induced emission of cyclometalated rhodium(III) and iridium(III) phenylpyridine complexes with ancillary 1,3-diketones.

A joint structural and spectroscopic study of simple bis-cyclometataled rhodium(III) and iridium(III) complexes with 2-phenylpyridine and aromatic β-diketones (dibenzoylmethane, benzoylacetone, benzoyltrifluoroacetone, and 2-thenoyltrifluoroacetone) reveals an interplay between the solid-state emission efficiency and crystal packing peculiarities of the complexes. Although the prepared rhodium(III) cyclometalates are isostructural with iridium(III) analogues, different types of π-π interactions are responsible for the aggregation-induced emission (AIE) of the complexes depending on the metal ion. For iridium(III) complexes, pyridyl-pyridyl contacts are essential for AIE because they lower the energy of the emissive metal-to-ligand charge transfer state below that of the non-emissive state located at the ancillary ligand.

Structural Motifs in Aryl Organogermanium Ge-O Derivatives for Material Design.

The aim of this work was to understand the main structural features and ways of formation of Ge-O bonds in organogermanium compounds under the conditions of ArGeHal (Hal = halide) hydrolysis. The structural types of these compounds were considered, providing 11 blocks (-). The molecular structures of the novel compounds [(-FCH)Ge]O (), [(-FCCH)Ge]O (), and -[(-FCCH)GeO] () were studied through XRD (X-ray diffraction) analysis.

Polymorphism of Carbamazepine Pharmaceutical Cocrystal: Structural Analysis and Solubility Performance.

Polymorphism is a common phenomenon among single- and multicomponent molecular crystals that has a significant impact on the contemporary drug development process. A new polymorphic form of the drug carbamazepine (CBZ) cocrystal with methylparaben (MePRB) in a 1:1 molar ratio as well as the drug's channel-like cocrystal containing highly disordered coformer molecules have been obtained and characterized in this work using various analytical methods, including thermal analysis, Raman spectroscopy, and single-crystal and high-resolution synchrotron powder X-ray diffraction. Structural analysis of the solid forms revealed a close resemblance between novel form II and previously reported form I of the [CBZ + MePRB] (1:1) cocrystal in terms of hydrogen bond networks and overall packing arrangements.

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 [MeSb(OOH), MeSb(OOH)·HO, PhSb(OOH)·0.

Supramolecular Organization in Salts of Riluzole with Dihydroxybenzoic Acids-The Key Role of the Mutual Arrangement of OH Groups.

Intermolecular interactions, in particular hydrogen bonds, play a key role in crystal engineering. The ability to form hydrogen bonds of various types and strengths causes competition between supramolecular synthons in pharmaceutical multicomponent crystals. In this work, we investigate the influence of positional isomerism on the packing arrangements and the network of hydrogen bonds in multicomponent crystals of the drug riluzole with hydroxyl derivatives of salicylic acid.

Virtual Screening, Structural Analysis, and Formation Thermodynamics of Carbamazepine Cocrystals.

In this study, the existing set of carbamazepine (CBZ) cocrystals was extended through the successful combination of the drug with the positional isomers of acetamidobenzoic acid. The structural and energetic features of the CBZ cocrystals with 3- and 4-acetamidobenzoic acids were elucidated via single-crystal X-ray diffraction followed by QTAIMC analysis. The ability of three fundamentally different virtual screening methods to predict the correct cocrystallization outcome for CBZ was assessed based on the new experimental results obtained in this study and data available in the literature.

New Solid Forms of Nitrofurantoin and 4-Aminopyridine Salt: Influence of Salt Hydration Level on Crystal Packing and Physicochemical Properties.

The crystallization of the poorly soluble drug nitrofurantoin (NFT) with 4-aminopyridine (4AmPy) resulted in three multicomponent solid forms with different hydration levels: anhydrous salt [NFT+4AmPy] (1:1), salt monohydrate [NFT+4AmPy+HO] (1:1:1), and salt tetrahydrate [NFT+4AmPy+HO] (1:1:4). Each salt was selectively prepared by liquid-assisted grinding in the presence of acetonitrile or ethanol/water mixture at a specific composition. The NFT hydrated salts were characterized using single crystal X-ray diffraction.

Gallium (III) Complexes Based on Aminobisphenolate Ligands: Extremely High Active ROP-Initiators from Well-Known and Easily Accessible Compounds.

We report herein the synthesis and full characterizations of the first examples of gallium complexes based on "privileged" aminobisphenolate ligands which are easily available. These complexes turned out to be extremely active in the ring-opening polymerization of ε-caprolactone even at room temperature and highly active in the ROP of L-lactide. The combination of factors such as the easy availability of these compounds and the supposedly low toxicity, together with the extremely high activity in ROP, allows us to consider these compounds as suitable for use on an industrial scale for the synthesis of biodegradable polymers for biomedical applications.

Coordination Polymers of Polyphenyl-Substituted Potassium Cyclopentadienides.

A series of potassium salts of di- and tri-arylsubstituted cyclopentadienes has been obtained by the metalation of the corresponding cyclopentadienes with benzylpotassium in THF media. Crystals of all compounds, afforded by recrystallization from THF/hexane, diglyme-THF/hexane and toluene/hexane mixtures, have been studied by X-ray diffraction. All studied potassium cyclopentadienides exhibit the luminescence at room temperature and overall quantum yield of photoluminescence for potassium salt of diarylsubstituted cyclopentadiene is 18%.

Formation Thermodynamics of Carbamazepine with Benzamide, Para-Hydroxybenzamide and Isonicotinamide Cocrystals: Experimental and Theoretical Study.

Formation thermodynamic parameters for three cocrystals of carbamazepine (CBZ) with structurally related coformers (benzamide (BZA), para-hydroxybenzamide (4-OH-BZA) and isonicotinamide (INAM)) were determined by experimental (cocrystal solubility and competitive reaction methods) and computational techniques. The experimental solubility values of cocrystal components at eutectic points and solubility product of cocrystals [CBZ + BZA], [CBZ + 4-OH-BZA], and [CBZ + INAM] in acetonitrile at 293.15 K, 298.

Fast Quantum Approach for Evaluating the Energy of Non-Covalent Interactions in Molecular Crystals: The Case Study of Intermolecular H-Bonds in Crystalline Peroxosolvates.

Energy/enthalpy of intermolecular hydrogen bonds (H-bonds) in crystals have been calculated in many papers. Most of the theoretical works used non-periodic models. Their applicability for describing intermolecular H-bonds in solids is not obvious since the crystal environment can strongly change H-bond geometry and energy in comparison with non-periodic models.

A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine.

Though 2-arylperimidines have never been used in iridium(III) chemistry, the present study on structural, electronic and optical properties of -unsubstituted and -methylated 2-(2-thienyl)perimidines, supported by DFT/TDDFT calculations, has shown that these ligands are promising candidates for construction of light-harvesting iridium(III) complexes. In contrast to -H perimidine, the -methylated ligand gave the expected cyclometalated μ-chloro-bridged iridium(III) dimer which was readily converted to a cationic heteroleptic complex with 4,4'-dicarboxy-2,2'-bipyridine. The resulting iridium(III) dye exhibited panchromatic absorption up to 1000 nm and was tested in a dye-sensitized solar cell.

Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis.

The synthesis, transformation, and application in catalysis of triphenyllead hydroperoxide, the first dioxygen lead complex, are described. Triphenyllead hydroperoxide is characterized by Pb nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and single-crystal X-ray diffraction, revealing the first one-dimensional (1D) coordination peroxo polymer. Photolytic isomorphous transformation of PhPbOOH yields a mixed hydroxo/superoxo crystalline structure, the first nonalkali superoxo crystalline metal salt, which is stable up to 100 °C.

Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents.

Derivatives of main group elements containing element-element bonds are characterized by unique properties due to σ-conjugation, which is an attractive subject for investigation. A novel series of digermanes, ArGe-Ge(SiMe), containing aryl (Ar = -CHMe (), -CHF (), CF ()) and trimethylsilyl substituents, was synthesized by the reaction of germyl potassium salt, [(MeSi)GeK*THF], with triarylchlorogermanes, ArGeCl. The optical and electronic properties of such substituted oligoorganogermanes were investigated spectroscopically by UV/vis absorption spectroscopy and theoretically by DFT calculations.

Comparison of Proton Acceptor and Proton Donor Properties of HO and HO in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates.

Two new peroxosolvates of drug-like compounds were synthesized and studied by a combination of X-ray crystallographic, Raman spectroscopic methods, and periodic DFT computations. The enthalpies of H-bonds formed by hydrogen peroxide (HO) as a donor and an acceptor of protons were compared with the enthalpies of analogous H-bonds formed by water (HO) in isomorphic (isostructural) hydrates. The enthalpies of H-bonds formed by HO as a proton donor turned out to be higher than the values of the corresponding H-bonds formed by HO.

Bispidine Platform as a Tool for Studying Amide Configuration Stability.

In this work, the solution conformations of seventeen 3,7-diacyl bispidines were studied by means of NMR spectroscopy including VT NMR experiments. The acyl groups included alkyl, alkenyl, aryl, hetaryl, and ferrocene moieties. The presence of syn/anti-isomers and their ratios were estimated, and some reasons explaining experimental facts were formulated.

A Combined Experimental and Theoretical Study of Nitrofuran Antibiotics: Crystal Structures, DFT Computations, Sublimation and Solution Thermodynamics.

Single crystal of furazolidone (FZL) has been successfully obtained, and its crystal structure has been determined. Common and distinctive features of furazolidone and nitrofurantoin (NFT) crystal packing have been discussed. Combined use of QTAIMC and Hirshfeld surface analysis allowed characterizing the non-covalent interactions in both crystals.

Crystalline Peroxosolvates: Nature of the Coformer, Hydrogen-Bonded Networks and Clusters, Intermolecular Interactions.

Despite the technological importance of urea perhydrate (percarbamide) and sodium percarbonate, and the growing technological attention to solid forms of peroxide, fewer than 45 peroxosolvates were known by 2000. However, recent advances in X-ray diffractometers more than tripled the number of structurally characterized peroxosolvates over the last 20 years, and even more so, allowed energetic interpretation and gleaning deeper insight into peroxosolvate stability. To date, 134 crystalline peroxosolvates have been structurally resolved providing sufficient insight to justify a first review article on the subject.

Identification of Barium Hydroxo-Hydroperoxostannate Precursor for Low-Temperature Formation of Perovskite Barium Stannate.

A breakthrough "superoxide colloidal solution route" for low-temperature synthesis of barium and strontium stannate perovskites and their doped analogues was recently introduced. The synthesis starts from hydrogen peroxide-rich stannate solutions and yields a so-called "crystalline superoxide molecular cluster" that is converted by low temperature (<300 °C) to the respective perovskites. In this paper, the so-called "crystalline superoxide molecular cluster" is identified as a superoxide-free, barium trihydroxo(hydroperoxo)peroxostannate, BaSn(OH)(OOH)(OO) phase (BHHPS).

Effects of Concentration on Aggregation of BODIPY-Based Fluorescent Dyes Solution.

Despite significant progress in understanding of dye aggregation, there are still processes that need to be further explored and which can significantly affect aggregation. In this work it was shown that the aggregation of dyes is influenced not only by dye concentration, but also by solvent polarity. It was found that nature, positions and number of fluorescent peaks may be controlled by simultaneous varying of both water fraction and dye concentration.

Identification of a previously unreported co-crystal form of acetazolamide: a combination of multiple experimental and virtual screening methods.

In the search for new co-crystal forms, many studies only consider one method of co-crystallisation which may lead to incorrect results. In this work, we demonstrate the efficiency of applying multiple experimental and virtual screening methods for a more comprehensive search for co-crystals of acetazolamide. A new co-crystal of acetazolamide with 4-aminobenzoic acid ([ACZ + PABA] (1 : 1)) was discovered, although previously, it had been found in the blind spot of the liquid-assisted grinding (LAG) screening method.

dl-Piperidinium-2-carboxyl-ate bis-(hydrogen peroxide): unusual hydrogen-bonded peroxide chains.

The title compound, CHNO·2HO, is the richest (by molar ratio) in hydrogen peroxide among the peroxosolvates of aliphatic α-amino acids. The asymmetric unit contains a zwitterionic pipecolinic acid mol-ecule and two hydrogen peroxide mol-ecules. The two crystallographically independent hydrogen peroxide mol-ecules form a different number of hydrogen bonds: one forms two as donor and two as acceptor ([2,2] mode) and the other forms two as donor and one as acceptor ([2,1] mode).