Statistically disordered short hydrogen bonds in (pipzH2)(cdoH)2 and a comparison with (pipzH2)(cdo)·H2O (pipz is piperazine and cdoH2 is chelidonic acid)

Two related proton‐transfer compounds, namely piperazine‐1,4‐diium 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate monohydrate, C₄H₁₂N₂²⁺·C₇H₂O₆²⁻·H₂O or (pipzH₂)(cdo)·H₂O, (I), and piperazine‐1,4‐diium bis(6‐carboxy‐4‐oxo‐4H‐pyran‐2‐carboxylate), C₄H₁₂N₂²⁺·2C₇H₃O₆⁻ or (pipzH₂)(cdoH)₂, (II), were obtained by the reaction of 4‐oxo‐4H‐pyran‐2,6‐dicarboxylic acid (chelidonic acid, cdoH₂) and piperazine (pipz). In (I), both carboxyl H atoms of chelidonic acid have been transferred to piperazine to form the piperazine‐1,4‐diium ion. The structure is a monohydrate. All potential N—H donors are involved in N—H...O hydrogen bonds. The water molecule spans two anions via the 4‐oxo group of the pyranose ring and a carboxylate O atom. The hydrogen‐bonding motif is essentially two‐dimensional. The structure is a pseudomerohedral twin. In the asymmetric unit of (II), the anion consists of monodeprotonated chelidonic acid, while the piperazine‐1,4‐diium cation is located on an inversion centre. The single carboxyl H atom is disordered in two respects. Firstly, the disordered H atom is shared equally by both carboxylic acid groups. Secondly, the H atom is statistically disordered between two positions on either side of a centre of symmetry and is engaged in a very short hydrogen‐bonding interaction; the relevant O...O distances are 2.4549 (11) and 2.4395 (11) Å, and the O—H...O angles are 177 (6) and 177 (5)°, respectively. Further hydrogen bonding of the type N—H...O places the (pipzH₂)²⁺ cations in pockets formed by the chains of (cdoH)⁻ anions. In contrast with (I), the (pipzH₂)²⁺ cations form hydrogen‐bonding arrays that are perpendicular to the anions, yielding a three‐dimensional hydrogen‐bonding motif. The structures of both (I) and (II) also feature π–π stacking interactions between aromatic rings.     

Enantioselective Diethylzinc Addition to Aromatic Aldehydes Catalyzed by Novel Ti(IV) Complex of Three-Dentate Chiral Sulfonamide Ligands

The synthesis of several novel three-dentate sulfonamide alcohol ligands is described, starting from camphorsulfonyl chloride. The influence of temperature and ligand structure on the asymmetric addition of dietylzinc to aromatic aldehydes has been studied. Enantioselectivities up to 76% have been obtained.     

ZnO Nanoparticles as an Efficient,Heterogeneous, Reusable,and Ecofriendly Catalyst for One-Pot,Three-Component Synthesis of 3,4-Dihydropyrimidin-2(1H)-(thio)one Derivatives in Water

An extremely efficient heterogeneous protocol is reported for the one-pot, three-component synthesis of a series of dihydropyrimidinones (DHPMs) in the presence of ZnO nanoparticles in water as a green solvent. The ZnO nanoparticles exhibited excellent catalytic activity and the proposed methodology is capable of providing the desired products in good yields (65–94%) within short reaction times. After the reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity, which makes this ecofriendly process cost-effective.     

Targeted Delivery of Anticancer Drug Loaded Charged PLGA Polymeric Nanoparticles Using Electrostatic Field

Pure positive electrostatic charges (PPECs) show suppressive effect on the proliferation and metabolism of invasive cancer cells without affecting normal tissues. PPECs are used for the delivery of drug-loaded polymeric nanoparticles (DLNs) capped with negatively charged poly(lactide-co-glycolide) (PLGA) and Poly(vinyl-alcohol) PVA into the tumor site of mouse models. The charged patch is installed on top of the skin in the mouse models' tumor region, and the controlled selective release of the drug is assayed by biochemical, radiological, and histological experiments on both tumorized models and normal rats' livers. It is found that DLNs synthesized by PLGA show great attraction to PPECs due to their stable negative charges, which would not degrade immediately in blood. The burst and drug release after less than 48h of this synthesized DLNs are 10% and 50%, respectively. These compounds can deliver the loaded-drug into the tumor site with the assistance of PPECs, and the targeted-retarded release will take place. Hence, local therapy can be achieved with much lower drug concentration (conventional chemotherapy [2 mg kg⁻¹] versus DLNs-based chemotherapy [0.75 mg kg⁻¹]) with negligible side effects in non-targeted organs. PPECs have many potential clinical applications for advanced-targeted chemotherapy with the lowest discernible side effects.     

CuI/Fe3O4 NPs@Biimidazole IL‐KCC‐1 as a leach proof nanocatalyst for the synthesis of imidazo[1,2‐a]pyridines in aqueous medium

In the present work, an innovative leach proof nanocatalyst based on dendritic fibrous nanosilica (DFNS) modified with ionic liquid loaded Fe₃O₄ NPs and CuI salts was designed and applied for the rapid synthesis of imidazo[1,2‐a]pyridines from the reaction of phenyl acetylene, 2‐aminopyridine, and aldehydes in aqueous medium. The structure of the synthesized nanocatalyst was studied by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR), flame atomic absorption spectroscopy (FAAS), energy‐dispersive X‐ray (EDX), and X‐ray diffraction (XRD), vapor–liquid–solid (VLS), and adsorption/desorption analysis (Brunauer–Emmett–Teller [BET] equation) instrumental techniques. CuI/Fe₃O₄NPs@IL‐KCC‐1 with high surface area (225 m² g^?1) and porous structure not only exhibited excellent catalytic activity in aqueous media but also, with its good stability, simply recovered by an external magnet and recycled for eight cycles without significant loss in its intrinsic activity. Higher catalytic activity of CuI/Fe₃O₄NPs@IL‐KCC‐1 is due to exceptional dendritic fibrous structure of KCC‐1 and the ionic liquid groups that perform as strong anchors to the loaded magnetic nanoparticles (MNPs) and avoid leaching them from the pore of the nanocatalyst. Green reaction media, shorter reaction times, higher yields (71–97%), easy workup, and no need to use the chromatographic column are the advantages of the reported synthetic method.     

Novel (4-oxothiazolidine-2-ylidene)benzamide derivatives: synthesis,characterization and crystal structures

Research on Chemical Intermediates - A convenient, one-pot, multicomponent synthesis of new (4-oxothiazolidine-2-ylidene)benzamide derivatives by unsymmetrical thioureas, various amines and methyl...     

SBA-15-SO3H-assisted preparation of 4-aza-phenanthrene-3,10-dione derivatives via a one-pot,four-component reaction

Research on Chemical Intermediates - A novel four-component approach for the synthesis of 1-phenyl-1,4-dihydro-2H-9-oxa-4-aza-phenanthrene-3,10-dione derivatives has been presented via the reaction...     

Formation of PdNiZn thin film at oil‐water interface: XPS study and application as Suzuki‐Miyaura catalyst

Nanosheet of PdNiZn and nanosphere of PdNiZn/reduced‐graphene oxide (RGO) with sub‐3 nm spheres have been successfully synthesized through a facile oil‐water interfacial strategy. The morphology and composition of the films were determined by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive analysis of X‐ray (EDAX) and elemental mapping. In the present study, we have developed a method to minimize the usage of precious Pd element. Due to the special structure and intermetallic synergies, the PdNiZn and PdNiZn/RGO nanoalloys exhibited enhanced catalytic activity and durability relative to Pd nanoparticles in Suzuki‐Miyaura C‐C cross‐coupling reaction. Compared to classical cross‐coupling reactions, this method has the advantages of a green solvent, short reaction times, low catalyst loading, high yields and reusability of the catalysts.     

Simultaneous formation of platinum‐based nanocatalysts and degradation of dyes at oil/water interface: Comparative morphological and kinetic studies

To decrease the water pollution of textile industries with a large amount of toxic and non‐biodegradable colored dye effluents, an efficient technique is required to safely remove harmful pollutants. In this paper, the reaction between azo dyes and NaBH₄ catalyzed by nanoparticles (NPs) thin films has been studied. We report insitu degradation of methyl orange (MO) and methyl red (MR) by using Pt‐based thin films monitored by UV–Vis spectroscopy. We have synthesized different thin films such as Pt, PtPd, PtFeFe₂O₃, PtNi and PtAu films from Pt organometallic precursor in the MO and MR medium (dye degradation and NPs formation is happened simultaneously) and activity of these films were compared in the complete degradation of MO and MR dyes. Rate constants for the catalyzed reactions have been determined. PtPd NPs thin film has shown the highest rate constant for the degradation of MO and MR within only a few seconds due to its well‐ordered structure. Furthermore, the effect of presence of MO on the morphology of NPs was investigated.