Journal of the Iranian Chemical Society最新文献

Sulfamerazine (4-Amino-N-(4-methylpyrimidin-2-yl) benzenesulfonamide) is a polymorphic molecule crystallizing in three forms: Form I: Pn2₁a polymorph (with three entries in the Cambridge Structural Database CSD), Form II: Pbca polymorph (with two entries in the CSD) and Form III: P2₁/c polymorph with only one entry in the CSD). We have experimentally prepared a novel monoclinic P2₁/c polymorph (Form IV) of the sulfadrug and also obtained crystals of Form II (Pbca polymorph) by following a different synthesis procedure. Both crystals were structurally characterized by single-crystal X-ray diffraction XRD and geometrically optimized by density functional theory DFT. The five crystal structures (1), (3)–(6) of the four mentioned polymorphs were analyzed and discussed in terms of crystal packing, Hirshfeld surface analysis HSA of the intermolecular interactions, voids’ distribution in the crystal packing, their related energies and the resulting underlying topologies. The energy and activity relations of the compounds were also investigated by DFT.

A series of 21 novel compounds based on noscapine were synthesized and investigated as potential anticancer therapeutics. These new compounds were prepared from the N-demethylation of noscapine followed by the three-component A³-coupling of N-nornoscapine as a secondary amine, an aldehyde and a terminal alkyne catalyzed by copper iodide (CuI). Two classes of derivatives were synthesized by applying phenylacetylene and propargyl alcohol as the alkyne moiety. Chemical structures of the products were confirmed by ¹HNMR, ¹³CNMR, and HR-MS. In vitro cytotoxicity of the synthesized derivatives was studied on MCF-7 breast cancer cell line treated with different doses of compounds for 48 h. Compounds 6l, 6n and 6h (IC₅₀ = 18.94, 19.29 and 32.11 µM, respectively) displayed the highest potency compared to that of noscapine (IC₅₀ = 36.38 µM).

Complexes of first row transition metals are a promising class of inexpensive catalysts for oxidation reactions. In this work, we studied the influence of covalent immobilization of Mn-porphyrin onto the surface of activated carbon in the green oxidation of various olefins. meso-tetrakis(4-carboxyphenyl)porphyrinatomanganese(III) acetate (MnTCPP) immobilized onto hydroxylated activated carbon (AC-OH). The anchored catalyst was characterized using FTIR, UV–VIS, atomic absorption and EDX spectroscopies. TGA analysis and BET-BJH method were employed to determine thermal behavior and surface properties of complex respectively. Then, catalytic performance of MnTCPP@AC-OH was investigated in the green oxidation of olefins with molecular oxygen and hydrogen peroxide. A comparison between two green oxidants (molecular oxygen and hydrogen peroxide) shows that although more product is obtained with hydrogen peroxide, more recyclability is obtained with molecular oxygen. The separation and recovery of the nanocatalyst was simple, effective and economical in this green oxidation method and the supported catalyst can be reused at least five times without significant loss of activity.

Nanoparticles particularly titanium dioxide (TiO₂) have demonstrated remarkable potential in both photocatalytic degradation of the toxic compounds and development of the effective photodynamic therapy (PDT) by harnessing light-induced reactive oxygen species (ROS) generation. In PDT, the choice of appropriate photosensitizers (PSs) and optimal light sources is crucial for the therapeutic efficacy. Pure titanium dioxide has the drawbacks of limited tissue penetration and high cytotoxicity due to the triggered traditional ultraviolet light sources, rapid recombination rate of the electron (e⁻)/hole (h⁺) pairs attributed to their broader band gap energy, and low solubility with high tendency to aggregation in water. Reproducible synthesis and efficiency optimization in ROS generation are also among the challenges. Addressing these challenges, this study focuses on the construction of a novel PDT nanoplatform: design and synthesis of the biocompatible N-doped-TiO₂/FeTCPP (PFNT) by modifying TiO₂ nanoparticles with urea as a safe nitrogen source (NT) to create an efficient type I PS, which expands the optical absorption capacity between 400 and 800 nm due to the facilitated localized nitrogen states within the titanium dioxide band gap, as well as by incorporating iron metalloporphyrin FeTCPP (tetra(4-carboxyphenyl) porphyrin) as an effective type II PS. Upon visible-light irradiation, FeTCPP not only sensitizes singlet oxygen, but also transfers electrons from excited FeTCPP* species to Ti⁴⁺-based N-TiO₂ to afford FeTCPP^•+ ligands and Ti³⁺ centers, thus propagating the production of hydrogen peroxide, superoxide, and hydroxyl radicals. By generating the substantial distinct ROS, significant tumor cell killing was obtained under LED irradiation, particularly in addressing melanoma. This research underscores substantial promise of the designed N‐TiO₂/FeTCPP nanocomposites in advancing the field of PDT-based cancer therapy, paving the way for efficient and targeted treatments.

In the current study, we synthesized copper oxide nanostructures (CuO NSs) via a facile hydrothermal procedure. We characterized them with the help of scanning electron microscopy (SEM) and X-ray diffractometry (XRD). SEM study revealed that CuO NSs inherited nanoneedles-based flowering geometry with a porous nature, while XRD proved the crystalline nature of these NSs. When deposited on a glassy carbon electrode (GCE), these nanostructures are displayed as a sensitive sulfite detection tool in the sample matrix. The results showed that sodium hydroxide, with pH 10.0, was the best-supporting electrolyte among all electrolytes studied. The as-prepared sulfite sensor performed well in a linear working range of 10–100 µM sulfite with the low detection limit (LOD) of the amperometry technique used to evaluate the analytical performance of the electrode, such as a limit of 1.12 µM. The developed sensor was highly stable and reproducible, showing a relative standard deviation of 2.17% for 10 cycles. The sensor also exhibited more selectivity for sulfite in the presence of probable interfering species, including cyanide, sulfate, chloride, and nitrate. The findings further proved the CuO/GCE-Nafion-based sensor as a sensitive diagnostic tool for quantifying or monitoring health-hazardous sulfite in the environmental sample matrices.

We have designed a series of 17 new 2-(trifluoromethyl)-1H-benzimidazoles based on alkylation with ethyl chloroacetate. The corresponding ester underwent saponification and hydrazinolysis to afford the corresponding acid and hydrazide, respectively. Hydrazide reacted with aromatic aldehydes and isothiocyanates and gave the corresponding hydrazones and thiosemicarbazide, respectively. The hydrazide and acid derivatives were used to attach an amine; primary and secondary amines via “DCC and azide coupling” methods to finally give a series of N-alkyl-2-(2-(trifluoromethyl)-1H-benzimidazol-1-yl)acetamides with a wide range of lipophilic and hydrophilic features. The most active compound was tested for cytotoxicity against MCF-7 cells using the MTT assay. Some compounds demonstrated activity against two proteins, interacting with key amino acids like the co-crystallized ligands such as compound 7d. Compound 7d exhibited potent cytotoxicity with an IC₅₀ value of 0.51 μM compared to Doxorubicin (IC₅₀ = 2.12 μM).

Among the new complexes, metal N-heterocyclic carbene (NHC) complexes have recently gained remarkable attention as they are entirely appropriate prerequisites for effective drug design and quick optimization. Furthermore, N-heterocyclic carbenes (NHCs) like phosphines contain strong σ-donating properties, which can bind to metals and create stable complexes. This article reports a general theoretical discussion on the structures and nature of C_{(carbene/alkenyl)} → M, P → M and C≡C bonds. Also, the influence of changing L and Rʹ groups in some adducts of [RʹC≡C → ML], (M=Cu (I), Ag (I), Au (I); R'=C₁₀H₇, C₉NH₁₂SO₂; L=NHC (R), P (R)₃; and R=F, Cl, Br, H, CH₃, SiH₃, Ph) has been studied. In this context, DFT calculations by PBE-D3/def2-TZVP level of theory have been used. The nature of C_{(carbene/alkenyl)} → M bonds in [RʹC≡C → MNHCR] and also P → M and C_(alkenyl) → M bonds in [RʹC≡C → MPR₃] complexes was surveyed. This was done using natural bond orbital (NBO), atoms in molecules (AIM), energy decomposition analysis (EDA), and energy decomposition analysis natural orbital for chemical valence (EDA-NOCV). The data have shown that σ donation from C_(alkenyl) to M atom in [RʹC≡C → MPR₃] complexes was greater than corresponding [RʹC≡C → MNHCR] complexes. Also, the C_(alkenyl) → M bonds in corresponding complexes were predominantly electrostatic. In addition, the C≡C bond has been also investigated by applying AIM, EDA, and ETS-NOCV analysis. The outcomes indicate that the highest percentage of interaction energy for C≡C bond is related to covalent interaction.

Dihydropyrimidinone skeleton (DHMP) plays a vital part in medicinal and pharmaceutical chemistry as its derivatives exhibit a broad spectrum of anti-microbial, anti-fungal, anti-bacterial, anti-inflammatory and anti-cancer activities. Taking into account the biological significance of DHPMs, organic chemists have developed different methodologies to synthesize these biologically active target molecules. Our review focuses on the one-pot synthesis of dihydropyrimidinones via Biginelli reaction by using the efficient catalysts and reaction conditions, thereby covering the literature published since 2021.

The present work described the one-pot multicomponent green and novel protocol for the synthesis of dihydrothiazolo [3,2-a] purine-2(1H)-one derivatives from novel purines and substituted 2-amino-thiazoles using BEC (pH 12.5, 10% by weight) as a recyclable heterogeneous catalyst in environmentally sustainable reaction medium PEG-400. The antibacterial potency was studied using a disc diffusion assay against two bacterial strains such as Staphylococci aureus (MTCC 1430) and Escherichia coli (MTCC 1573). The results of biological tests of newly synthesized derivatives 4a, 4b, 4d, 4g, and 4h display marked antibacterial potency against tested pathogens. The biological relevance of these synthesized derivatives is due to the presence of thiazole nucleus in combination with a purine ring. Further, structure conformation of synthesized titled compounds was presented with different spectroscopic methods such as ¹H-NMR, ¹³C-NMR, IR, and GCMS. Numerous benefits of the current method include the catalyst's recyclability, clean reaction conditions, a quick reaction rate, increased product yield, and the lack of dangerous reagents.

We study the effect of high Mg impurity in ZnO film grown by spray pyrolisis for photocatalytic applications. The films were grown on the glass substrate for a very short time (10 min). As a result, pure ZnO film has a nanorice structure with a length of ~ 207 nm, as observed by scanning electron microscopy. By inserting the Mg impurity of ~ 32 at.%, the length of the particle decreased to 90 nm. However, this sample with the high Mg content still exhibits a hexagonal wurtzite structure, as shown by the X-ray diffraction pattern. It was also found that the impurity widens the optical band from 3.20 eV to 3.22 eV, possibly due to the alloying effect. Furthermore, the photocatalytic studies reveal that the ZnO exhibits high degradation efficiency under UV light. By adding Mg impurity, the degradation rate decreases by about 2.93% compared to pure ZnO. After 3 days of exposure, the ZnO and ZnO:Mg demonstrated photocatalytic activity, with a degradation efficiency of 95.33% and 94.17%, respectively. So this result is vital in developing low-cost photocatalytic materials by carefully choosing the type and concentration of doping.