Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.     

Some results on the annihilators and attached primes of local cohomology modules

Let \((R, \mathfrak {m})\) be a local ring and M a finitely generated R-module. It is shown that if M is relative Cohen–Macaulay with respect to an ideal \(\mathfrak {a}\) of R, then \({\text {Ann}}_R(H_{\mathfrak {a}}^{{\text {cd}}(\mathfrak {a}, M)}(M))={\text {Ann}}_RM/L={\text {Ann}}_RM\) and \({\text {Ass}}_R (R/{\text {Ann}}_RM)\subseteq \{\mathfrak {p}\in {\text {Ass}}_R M|\,\mathrm{cd}(\mathfrak {a}, R/\mathfrak {p})={\text {cd}}(\mathfrak {a}, M)\},\) where L is the largest submodule of M such that \(\mathrm{cd}(\mathfrak {a}, L)< \mathrm{cd}(\mathfrak {a}, M)\). We also show that if \(H^{\dim M}_{\mathfrak {a}}(M)=0\), then \({\text {Att}}_R(H^{\dim M-1}_{\mathfrak {a}}(M))= \{\mathfrak {p}\in {\text {Supp}}(M)|\mathrm{cd}(\mathfrak {a}, R/\mathfrak {p})=\dim M-1\},\) and so the attached primes of \(H^{\dim M-1}_{\mathfrak {a}}(M)\) depend only on \({\text {Supp}}(M)\). Finally, we prove that if M is an arbitrary module (not necessarily finitely generated) over a Noetherian ring R with \(\mathrm{cd}(\mathfrak {a}, M)=\mathrm{cd}(\mathfrak {a}, R/{\text {Ann}}_RM)\), then \({\text {Att}}_R(H^{\mathrm{cd}(\mathfrak {a}, M)}_{\mathfrak {a}}(M))\subseteq \{\mathfrak {p}\in {\text {V}}({\text {Ann}}_RM)|\,\mathrm{cd}(\mathfrak {a}, R/\mathfrak {p})=\mathrm{cd}(\mathfrak {a}, M)\}.\) As a consequence of this, it is shown that if \(\dim M=\dim R\), then \({\text {Att}}_R(H^{\dim M}_{\mathfrak {a}}(M))\subseteq \{\mathfrak {p}\in {\text {Ass}}_R M|\mathrm{cd}(\mathfrak {a}, R/\mathfrak {p})=\dim M\}\).     

电氧化异丙肾上腺素的纳米复合电催化剂：用作传感器

在金纳米粒子(AuNPs)上经苯硫酚衍生物(3,4二羟基苯基-偶氮-苯硫酚, DAT)自组装制得了一种新型纳米复合物,用于修饰玻璃碳电极(GCE/AuNP-DAT).采用循环伏安法研究了该新型电极的性质,并将其用作异丙肾上腺素(IP)电催化剂,考察了该纳米复合物的电催化活性,从而得到反应机理和催化反应速率常数.由于GCE/AuNP-DAT电极对尿酸氧化没有电催化活性,因此可将IP的氧化信号从该改进电极中分离出来,从而排除了尿酸对IP测定的干扰.该电极可作为传感器,当用于差动脉冲伏安法测定IP时,线性动态范围为1.0–1500.0μmol/L,检测极限为0.46μmol/L.     

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.     

One Pot Synthesis of Octahydroquinazolinone Derivatives Using (Me (Im)<Superscript>12</Superscript>) H<Subscript>4</Subscript>CuPW<Subscript>11</Subscript>O<Subscript>39</Subscript> as a Surfactant Type Catalyst

This study is aimed at proposing a practical green procedure for the synthesis of octahydroquinazolinone derivatives using benzaldehyde, dimedone and urea under microwave irradiation in water. A surfactant type polyoxometalate-based organic–inorganic hybrid was able to efficiently catalyze this synthesis. The catalyst was prepared and characterized by Fourier transform infrared, UV–Vis, X-ray diffraction, and thermogravimetric analysis. The employed catalyst exerted a synergistic effect; the anion part acted as a catalyst while the cation part acted as a surfactant in order to increase the concentration of organic reactants in water. The main advantage of this method is its remarkable yield in short reaction periods, which results in the rendering of products with high purity. Moreover, this heterocatalyst is capable of being easily recovered and reused several times. The influences of reaction conditions were studied systematically, and a possible catalysis mechanism was proposed for understanding the highly efficient heterogeneous catalytic behavior.     

A New Reaction of Isatin,Cyclic 1,3‐Diketone,and 2‐Cyanoacetamide: A Four‐Component Synthesis of Spirooxindoles

A novel reaction of isatins, 2‐cyanoacetamide, and cyclic 1,3‐diketones in ethanol was reported. The reaction gave the unexpected spirooxindole ethyl carboxylates in excellent yields and the spirooxindole carboxamide was not observed.     

Comparison of the role of new ethers and conventional alkoxysilanes as external donors in the polymerization of propylene using the industrial Ziegler-Natta catalyst

Two new ethers were synthesized using the Williamson reaction from related alcohols and were used as external donors in propylene polymerization in the presence of the industrial diisobutyl phthalate-based MgCl₂-supported Ziegler-Natta catalyst. For comparison the propylene polymerization was carried out in the presence of silane and in the absence of external donors. The produced polymers were characterized by differential scanning calorimetry, xylene extraction, melt flow index, scanning electron microscopy and gel permeation chromatography. The isotacticity, molecular weight and molecular weight distribution, melt flow index, crystallinity degree and thermal properties of polypropylenes were influenced by the type of external donors.     

Isocyanide‐Based Three‐Component Synthesis of Pyrano‐pyrido‐quinoxalines

Pyrano‐pyrido‐quinoxaline derivatives were synthesized in good yields by a three‐component reaction of isocyanides, dialkyl acetylenedicarboxylates, and pyrido[1,2‐a]quinoxaline‐triones in DMF at 100°.     

Acetone extracted propolis as a novel membrane and its application in phenol biosensors: the case of catechol

A novel biosensor for catechol has been constructed by immobilizing polyphenol oxidase (PPO) into acetone-extracted propolis (AEP) composite modified with gold nanoparticles (GNPs) and attached to multiwalled carbon nanotube (MWCNTs) on a gold electrode surface. The propolis for AEP was obtained from honeybee colonies. Under the optimum conditions, this method could be successfully used for the amperometric determination of catechol within a concentration range of 1 × 10^?6 to 5 × 10^?4?M, with a detection limit of 8 × 10^?7?M (S/N = 3). The effects of pH and operating potential are also explored to optimize the measurement conditions. The best response was obtained at pH?5, while an optimum ratio of signal-to-noise (S/N) was obtained at ?20?mV (versus Ag/AgCl), which was selected as the applied potential for the amperometric measurements. All subsequent experiments were performed at pH?5. Cyclic voltammetry and electrochemical impedance spectroscopy was used to characterize the PPO/CNTs/GNPs/AEP/Au biosensor. The biosensor also exhibited good selectivity, stability, and reproducibility.