ABSTRACT Cysteine thioaldehydes are putative intermediates in sulfatase‐maturing enzyme catalysis and in the biosynthesis of penicillin, coenzyme A and families of ribosomally synthesized and posttranslationally modified peptides (RiPPs). Norrish type‐II photolysis of phenacylsulfides gives cysteine thioaldehydes but can be inefficient in aqueous solution owing to competing β‐scission. We show that irradiation of phenacylsulfides bearing non‐conjugating electron‐withdrawing substituents leads to efficient Norrish type‐II fragmentation. In aqueous buffer, photolysis of cysteine phenacylsulfides leads to high conversion into cysteine enethiolate and isothiazolone, which can be interconverted with an oxidant (Ellman's reagent) or reductant (phosphine). Cysteine enethiolates are relatively stable in aqueous buffer at neutral‐to‐high pH but undergo cyclocondensation to cysteine thiazole at low pH. Cysteine thioaldehydes undergo appreciable levels of hydrolysis to give formylglycine in the absence of buffer and for longer peptides that adopt enabling secondary structure. Nucleophilic (n → π*) participation of the proximal backbone carbonyl group on cysteine thioaldehydes can lead to peptide oxazoles. These results suggest viable oxidation‐before‐cyclocondensation biosynthetic pathways for peptide azoles and that the hydrolysis of cysteine thioaldehydes into formylglycine, as proposed for sulfatase activation, is not trivial and relies on a peptide environment that promotes the desired hydration at the expense of other similarly efficient thiocarbonyl‐quenching processes.

Understanding the growth of needle-shaped molecular crystals and the factors that influence the needle morphology is not only a fundamental research question but is also important in the design of industrial crystallization processes. Needle-like crystals have poor flow properties, are difficult to filter and to dry and - in the case of pharmaceuticals - difficult to formulate. While the morphology can often be controlled by changing the solvent, some compounds are persistent needle-formers that grow from all solvents as highly anisotropic crystals. In this highlight article we discuss the structural properties that lead to (persistent) needle growth. We also review strategies to modify the morphology such as the use of tailor-made additives, polymeric growth modifiers and cocrystallization. In this highlight fundamental research on the growth of needle-like crystals and strategies to control the aspect ratio are reviewed.

Recentstudies toward finding more efficient ruthenium metalloligands for photocatalysis applications have shown that the derivatives of the linear [Ru(dqp)2]2+ (dqp: 2,6-di(quinolin-8-yl)-pyridine) complexes hold significant promise due to their extended emission lifetime in the μs time scale while retaining comparable redox potential, extinction coefficients, and absorption profile in the visible region to [Ru(bpy)3]2+ (bpy: 2,2'-bipyridine) and [Ru(tpy)2]2+ (tpy: 2,2':6',2″-terpyridine) complexes. Nevertheless, its photostability in aqueous solution needs to be improved for its widespread use in photocatalysis. Carbon-based supports have arisen as potential solutions for improving photostability and photocatalytic activity, yet their effect greatly depends on the interaction of the metal complex with the support. Herein, we present a strategy for obtaining Ru-polypyridyl complexes covalently linked to aminated reduced graphene oxide (rGO) to generate novel materials with long-term photostability and increased photoactivity. Specifically, the hybrid Ru(dqp)@rGO system has shown excellent photostable behavior during 24 h of continual irradiation, with an enhancement of 10 and 15% of photocatalytic dye degradation in comparison with [Ru(dqp)2]2+ and Ru(tpy)@rGO, respectively, as well as remarkable recyclability. The presented strategy corroborates the potential of [Ru(dqp)2]2+ as an interesting photoactive molecule to produce more advantageous light-active materials by covalent attachment onto carbon-based supports.

The solvent-free elimination of sulfinic acid and aromatization of 1,6-trans-substituted bis(arylsulfone) trienes is reported. It is shown that sublimation can be used as a 'green' method to combine the thermal transformation of six trienes and the crystal growth of the resulting 4-(phenylsulfonyl)biphenyls. When the sublimation conditions are carefully controlled, high quality single crystals of the 4-(phenylsulfonyl)biphenyls are obtained. Theoretical modelling of the reaction using the simplified triene Ph-(CH)6-SO2H showed that the cyclization is energetically feasible and that the complete conversion is possible during the timescale of the sublimation. At temperatures slightly higher than the optimum sublimation temperature two of the trienes transformed into 1,4-cyclohexadienes that did not eliminate phenylsulfinic acid. A reaction mechanism involving a 1,3-hydrogen shift induced by free PhS center dot radicals is proposed for the formation of the 1,4-cyclohexadienes. 1,6-trans-substituted bis(arylsulfone) trienes undergo aromatization and elimination of phenylsulfinic acid during sublimation leading to the growth of high quality, pure single crystals of the resulting (4-phenylsulfonyl)biphenyls in the desublimation area. image

The combination of 2-pyridyl oximes or 2-pyridinemethanol and a hydroxo-functionalized dicarboxylic acid has provided access to a family of coordination polymers.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH2) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (H3pdc) has provided access to three new compounds, [Ni4(INA)2(pyaox)2(pyaoxH)2(DMF)2] (1), [Co5(mpko)6(mpkoH)2(OMe)2(H2O)](ClO4)6 (2), and [Co5(OH)(Hpdc)5(H2pdc)] (3). 1 displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH2 in their neutral or ionic form. The neighbouring Ni4 units in 1 are held together through strong intermolecular hydrogen bonding interactions, forming a three-dimensional supramolecular framework. 2 and 3 are mixed-valent Co4IIICoII and Co2IIICoII3 compounds with a bowtie and trigonal bipyramidal metal topology, accordingly. Direct current and alternate current magnetic susceptibility studies revealed that the exchange interactions between the NiII ions in 1 are ferromagnetic (J = 1.79(4) cm−1), while 2 exhibits weak AC signals in the presence of a magnetic field. The syntheses, crystal structures, and magnetic properties of 1–3 are discussed in detail.

The development of synthetic approaches towards new mixed-ligand metal organic frameworks (MOFs) has been attracting considerable attention recently as they display fascinating properties due to the synergistic effect between the different ligands. Herein, the initial combination of pyridine-2,6-dimethanol (H(2)pdm) with benzene-1,4-dicarboxylic acid (H(2)bdc) has provided access to three new mixed-ligand MOFs, [M-3(bdc)(2)(Hpdm)(2)](n) (M-II=Zn-II, 1; Mn-II, 2) and [Mn-3(bdc)(3)(H(2)pdm)(2)](n) (3). 1-3 are the first MOFs containing H(2)pdm in its neutral or anionic form. 1 and 2 are isostructural 2D MOFs with a square lattice (sql) framework topology, while 3 is a 3D MOF possessing a primitive cubic (pcu) topology. Dc magnetic susceptibility measurements for 3 demonstrate antiferromagnetic interactions between the Mn-II ions which is a combination of intra- and intertrimer exchange pathways.

A new Schiff base complex, Cu(H2L)2 (H3L: 6,6 ′ -((1E,1 ′ E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol)), through the reaction of ligand H3L with Cu(NO3)2 3H2O, in the ratio of 2 : 1 in methanol solvent was prepared. The obtained ligand (H3L) was characterized by FT-IR, 13C NMR, 1H NMR and elemental analyses. Then its copper(II) complex was prepared and characterized by FT-IR spectroscopy, thermal studies, elemental analyses and single crystal X-ray diffraction. The X-ray crystallography revealed that the two H3L ligands in bidentate fashion coordinated to one copper center for producing Cu(H2L)2 complex. We used copper(II) Schiff base complex, Cu(H2L)2, for the preparation of CuO nanoparticles via solid-state thermal decomposition. The crystalline structure of the product was studied by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). XRD indicated that the new product was copper oxide. SEM image showed that the size of CuO nanoparticles was between 46 and 53 nm, and they had uniform shape. The antibacterial properties of the complex and ligand were also investigated. The results revealed that Schiff base complex showed higher biological activity than Schiff base ligand.

The identification and study of supramolecular synthons is a fundamental task in the design of pharmaceutical cocrystals. The malaria drug pyrimethamine (pyr) and the antibiotic trimethoprim (tmp) are both 2,4-diaminopyrimidine derivatives, providing the same C–NH2/N=C/C–NH2 and C–NH2/N=C interaction sites. In this article, we analyze and compare the synthons observed in the crystal structures of tmp and pyr cocrystals and molecular salts with sulfamethazine (smz), α-ketoglutaric acid (keto), oxalic acid (ox), sebacic acid (seb), and azeliac acid (az). We show that the same coformer interacts with different binding sites of the 2,4-diaminopyrimidine ring in the respective tmp and pyr cocrystals or binds at the same site but gives H bonding patterns with different graph set notions. Pyr·smz·CH3OH is the first crystal structure in which the interaction of the sulfa drug at the C–NH2/N=C/C–NH2 site with three parallel NH2···N, N···NHsulfonamide, and NH2···O=S H bonds is observed. The main synthon in (tmp+)(keto–).0.5H2O and (tmp+)2(ox2–)·2CH3OH is the motif of fused R21(6) and R12(5) rings instead of the R22(8) motif typically observed in tmp+ and pyr+ carboxylates. Tmp/az is a rare example of cocrystal-salt polymorphism where the two solid-state forms have the same composition, stoichiometry, and main synthon. Theoretical calculations were performed to understand the order of stability, which is tmp·az cocrystal > (tmp+)(az–) salt. Finally, two three-component tmp/sulfa drug/carboxylate cocrystals with a unique ternary synthon are described.

The cocrystallization of the fluoroquinolones ciprofloxacin (cip), norfloxacin (nor), and enrofloxacin (enro) with the α,ω-dicarboxylic acids glutaric acid (glu), adipic acid (adi), pimelic acid (pim), suberic acid (sub), azeliac acid (az), and sebacic acid (seb) resulted in 27 new molecular salts and ternary molecular ionic cocrystals of compositions A+B-, A2+B2-, A2+B2-B, and A+B-A. Depending on the solvent, different stoichiomorphs, solvates, or polymorphs were obtained. All salts and cocrystals contain the robust R2NH2+...-OOC or R3NH+...-OOC synthon but have different supramolecular ring motifs. Moderate solubility enhancements over the parent fluoroquinolones were observed. Salts in the ratio of 1:1 and 2:1 were also prepared by ball-milling. The milled sample nor/az (1:1) was shown to gel the GRAS (generally recognized as safe) solvent propylene glycol, and enro/sub (1:1) was shown to gel both propylene glycol and water. Dynamic rheology measurements confirmed that nor/az and enro/sub behave like viscoelastic materials and supramolecular gels.

Metal-organic hybrid complexes often exhibit large surface area, pore volume, fascinating structures and potential applications including catalytic applications. Hence a new metal-organic hybrid complex [Diaquo{bis(p-hydroxybenzoato-kappa O-1(1))}(1-methylimidazole-kappa N-1(1))}copper(II)] was synthesized using conventional method. Physico-chemical characterization of the complex was performed with FTIR spectroscopy, single crystal X-ray diffraction, TGA, EPR and FESEM. Single crystal X-ray diffraction study suggests it to be three dimensional with space group P2(1)2(1)2(1) (orthorhombic). The crystal achieves its three-dimensional structure and stability through extensive intermolecular hydrogen bonding. Hirshfeld surface analysis, catalytic activity and DFT study of the complex was also performed. The synthesized complex acts as good catalyst in benzimidazole synthesis with good recyclability as catalyst up to 5th run. (C) 2021 Elsevier B.V. All rights reserved.

The simultaneous use of 2-pyridyl oximes (pyridine-2 amidoxime, H2pyaox; 2-methyl pyridyl ketoxime, Hmpko) and 1,3,5-benzenetricarboxylic acid (H3btc) provided access to five new compounds, namely [Zn(H2btc)2(H2pyaox)2]•2H2O (1•2H2O), [Zn(Hbtc)(H2pyaox)2]n (2), [Cu(Hbtc)(H2pyaox)]n (3), [Cu(Hbtc)(HmpKo)]n (4) and [Cu2(Hbtc)2(Hmpko)2(H2O)2]•4H2O (5•4H2O). Among them, 3 is the first example of a metal-organic framework (MOF) containing H2pyaox. Its framework can be described as a 3-c uninodal net of hcb topology with the layers being parallel to the (1,0,1) plane. Furthermore, 3 is the third reported MOF based on a 2-pyridyl oxime in general. 2 and 4 are new members of a small family of coordination polymers containing an oximic ligand. 1–5 form 3D networks through strong intermolecular interactions. Dc magnetic susceptibility studies were carried out in a crystalline sample of 3 and revealed the presence of weak exchange interactions between the metal centres; the experimental data were fitted to a theoretical model with the fitting parameters being J = −0.16(1) cm−1 and g = 2.085(1). The isotropic g value was also confirmed by electronic paramagnetic resonance (EPR) spectroscopy. Reactivity studies were performed for 3 in the presence of metal ions; the reaction progress was studied and discussed for Fe(NO3)3 by the use of several characterization techniques, including single crystal X-ray crystallography and IR spectroscopy.

A cooling crystallization of benzoic acid and isonicotinamide in ethanol yields the 1:1 cocrystal with an extreme needle-like morphology with an initial mean aspect ratio of similar to 10 and a size of similar to 64 mu m. We demonstrate that the use of suspension temperature cycling in combination with tailor-made additives alleviates such extreme needle-like morphologies and increases the average particle size of this cocrystal material. Temperature cycling of the cocrystal suspensions in ethanol alone reduces the mean aspect ratio from 10 to 3.3 while it increases the average crystal size from 64 to 450 mu m. The further addition of low concentrations of benzamide or nicotinamide suppresses the growth rate at the tip of the needle even more, resulting in a more favorable equant morphology. An iterative mechanism in which additives are incorporated in the lattice structure and released during the temperature increase in each cycle is proposed. Thus, the incorporation of an additive at the normally fast growing and potential needle tips and its release during the temperature increase part of the cycle effectively makes an additive action catalytic. The simultaneous use of temperature cycling and tailor-made additives offers a new and effective approach for the elimination of unsatisfactory needle-like crystal morphologies and a small crystal size during the production of a pharmaceutical cocrystal material.

Metal organic frameworks (MOFs) have attracted considerable attention in recent years due to their use in a wide range of environmental, industrial and biomedical applications. The employment of benzophenone-4,4'-dicarboxylic acid (bphdcH2) in MOF chemistry provided access to the 3D mixed metal MOFs [CoNa2(bphdc)2(DMF)2]n (NUIG2) and [ZnK2(bphdc)2(DMF)2]n (NUIG3), and the 2D homometallic MOF [Co2(OH)(bphdcH)2(DMF)2(H2O)2]n(OH)·DMF (1·DMF). 1·DMF is based on a dinuclear SBU and consists of interpenetrating networks with an sql topology. Dc magnetic susceptibility studies were carried out in 1·DMF and revealed the presence of weak antiferomagnetic exchange interactions between the metal centres. NUIG2 and NUIG3 are structural analogues of [ZnNa2(bphdc)2(DMF)2]n (NUIG1), which has shown an exceptionally high encapsulation for ibuprophen (Ibu), NO and metal ions. Both NUIG2 and NUIG3 display high metal ion (CoII, NiII, CuII) adsorption capacity, comparable to that of NUIG1, with NUIG2 exhibiting good performance in Ibu uptake (780 mg Ibu per g NUIG2). Monte Carlo simulations were conducted in NUIG1 in order to assess its adsorption capacity for other guest molecules, and revealed that it possesses an outstanding CO2 uptake at ambient pressure, which is larger than that of the previously reported best functioning species (104 vs. 100 cm3 (stp) per cm3). Furthermore, NUIG1 exhibits high selectivity for CO2 over CH4.

Salt formation with proton transfer is observed in crystals grown by cosublimation of the salt coformers. Diflunisal salts were obtained with 4-[3-(pyridin-4-yl)propyl]pyridine, piperazine, and 4-dimethylaminopyridine. Modeling studies indicate that proton transfer does not take place for an acid-base H-bonded adduct in the gas phase. However, modeling larger molecular clusters shows that proton transfer can take place spontaneously within a molecular cluster in the absence of a solvent.