Diastereoselective synthesis of pyrrolo[1, 2-c]imidazoles using chiral thiohydantoins,malononitrile, and aldehydes and evaluation of their antioxidant and antibacterial activities

Diastereoselective synthesis of pyrrolo[1,2-c]imidazoles is reported from three-component reaction of chiral thiohydantoins, aldehydes, and malononitrile in the presence of NEt₃. The antioxidant properties of the obtained products were evaluated by 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay. Among the products, compound 4l possessing NH₂ and NH groups and bromine atom at 4-position of the aromatic ring displayed the highest antioxidant activity (90%). Also, their antibacterial activities were explored against gram-positive and gram-negative bacteria using disc diffusion method. Among the synthesized compounds, 4a with chlorine atom at para position of the aromatic ring, and methyl group (the smallest alkyl group) at 7-position, displayed the best antibacterial activity against the tested gram-positive bacteria.     

Modification of an implicit approach based on nonstandard rules for structural dynamics analysis

The present study aims to modify a recently suggested implicit approach consisted of the approximate Euler method and closed-form exponential mapping (herein referred to as the Liu scheme) for the dynamic analysis of structures. Such modification has been developed based upon nonstandard rules. The equation of motion is formulated in the augmented dynamic space to apply the exponential mapping as a group preserving scheme. The formulation of the proposed method involves the hyperbolic sine and cosine functions. The method is therefore prone to divergence due to the behavior of the hyperbolic functions in structures with a high ratio of stiffness to mass. In the present study, to consider the properties of the structural equation into the formulation of the time step size and thereby avoid the divergence, a parameter, known as stability parameter, is thus derived from the exact solution of the equation of motion based on nonstandard rules. Embedding this parameter into the proposed method improves its stability. Afterward, for evaluating the performance of the proposed method, it is applied to several structures with different loading patterns while implemented in programing environment of the Matlab software. The results are compared to those of several commonly used numerical methods in structural applications. It is found that the proposed method has acceptable convergence and accuracy, and low time consumption compared to several commonly used methods. Furthermore, its stability is guaranteed by embedding the stability parameter into the proposed method.     

Synthesis of bicyclic lactones via I2-mediated intramolecular tandem C–C/C–O bond formation

The iodine/DMAP-mediated intramolecular tandem C–C/C–O bond forming reaction of malonate bearing alkene moiety proceeded to give bicyclic lactones with good diastereoselectivity in good yield. The mechanistic investigation was also discussed on the basis of various control experimental results.     

Fabrication of graphene‐silver/polyurethane nanofibrous scaffolds for cardiac tissue engineering

The graphene‐based nanocomposites are considered as great candidates for enhancing electrical and mechanical properties of nonconductive scaffolds in cardiac tissue engineering. In this study, reduced graphene oxide‐silver (rGO‐Ag) nanocomposites (1 and 2 wt%) were synthesized and incorporated into polyurethane (PU) nanofibers via electrospinning technique. Next, the human cardiac progenitor cells (hCPCs) were seed on these scaffolds for in vitro studies. The rGO‐Ag nanocomposites were studied by X‐ray diffraction (XRD), Raman spectroscopy, and transmission electron microscope (TEM). After incorporation of rGO‐Ag into PU nanofibers, the related characterizations were carried out including scanning electron microscope (SEM), TEM, water contact angle, and mechanical properties. Furthermore, PU and PU/nanocomposites scaffolds were used for in vitro studies, wherein hCPCs showed good cytocompatibility via 3‐(4, 5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) assay and considerable attachment on the scaffold using SEM studies. Real‐time polymerase chain reaction (PCR) and immunostaining studies confirmed the upregulation of cardiac specific genes including GATA‐4, T‐box 18 (TBX 18), cardiac troponin T (cTnT), and alpha‐myosin heavy chain (α‐MHC) in the PU/rGO‐Ag scaffolds in comparison with neat PU ones. Therefore, these nanofibrous rGO‐Ag–reinforced PU scaffolds can be considered as suitable candidates in cardiac tissue engineering.     

Disulfide‐Unit Conjugation Enables Ultrafast Cytosolic Internalization of Antisense DNA and siRNA

Development of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA.     

MCM-41 Catalyzed Efficient Regioselective Synthesis of β-Aminoalcohol under Solvent-free Conditions

β‐Aminoalcohols were synthesized in high yields by reaction of epoxides with amines in the presence of MCM‐41 as a green and reusable catalyst under solvent‐free conditions.     

Spectral,crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

The reaction of α‐keto‐stabilized diphosphine ylides [Ph₂P(CH₂)_nPPh₂═C(H)C(O)C₆H₄‐p‐CN] (n = 1 (Y¹); n = 2 (Y²)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr₂(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br₂Pd(κ²‐Y¹)] ( 1 ), [Br₂Pt(κ²‐Y¹)] ( 2 ), [Br₂Pd(κ²‐Y²)] ( 3 ) and [Br₂Pt(κ²‐Y²)] ( 4 ). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1 – 4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔE_int, about 57–58%, in the complexes are allocated to ΔE_elstat.     

Solvent‐Free Chemoselective Synthesis of 1,1‐Diacetates Catalyzed by Cu(NO3)2 · 3H2O

1,1‐Diacetates have been synthesized by the reaction of a variety of aldehydes with acetic anhydride in the presence of cupric nitrate as catalyst under solvent‐free conditions. Ketones were not converted to the corresponding diacetates under these conditions.     

Montmorillonite as a Heterogeneous Catalyst in the Efficient,Mild and One Pot Synthesis of Schiff Bases under Solvent‐Free Conditions

A mild and efficient method has been reported for preparation of Schiff base ligands through condensation reaction of various aromatic aldehydes and ketones with different aromatic amines in the presence of montmorillonite as a heterogeneous catalyst under solvent free conditions. The advantages of this friendly, economically, environmentally and mild method are such as; simplicity of the reaction procedure, reusability of catalyst, simple work‐up, high product yields and very short reaction times.