Synthesis of one-pot pyrazolo[4′,3′:5,6]pyrano[2,3-c]phenazin-15-yl) methanone derivatives via a multi-component using Fe3O4@TiO2-SO3H as a recoverable magnetic catalyst under microwave irradiation

ABSTRACT

A new one-pot method for the synthesis four-component of pyrazolo[4′,3′:5,6]pyrano[2,3-c]phenazin-15-yl)methanone derivatives has been developed in the presence of nano Fe₃O₄@TiO₂-SO₃H catalysts (heterogeneous acid) under microwave conditions and in a solvent-free environment at 180?W. One of the benefits of using this catalyst was its re-use in subsequent stages of its reaction without much loss in its activity, which was carried out by an external magnet and recovered. The catalyst was synthesized and characterized by XRD, EDX, TEM, FESEM, TGA-DTA, BET, VSM and AFM. The productivity of the products obtained from this protocol (MAOS) is significantly high and the shorter reaction time in the synthesis process over the reflux method. These results showed advantages for synthesis, such as mild reaction conditions, no use of toxic catalysts in the laboratory, solvent-free environment, low energy consumption and Economically Affordable.     

Strong,Self‐Healable,and Recyclable Visible‐Light‐Responsive Hydrogel Actuators

The most pressing challenges for light‐driven hydrogel actuators include reliance on UV light, slow response, poor mechanical properties, and limited functionalities. Now, a supramolecular design strategy is used to address these issues. Key is the use of a benzylimine‐functionalized anthracene group, which red‐shifts the absorption into the visible region and also stabilizes the supramolecular network through π–π interactions. Acid–ether hydrogen bonds are incorporated for energy dissipation under mechanical deformation and maintaining hydrophilicity of the network. This double‐crosslinked supramolecular hydrogel developed via a simple synthesis exhibits a unique combination of high strength, rapid self‐healing, and fast visible‐light‐driven shape morphing both in the wet and dry state. As all of the interactions are dynamic, the design enables the structures to be recycled and reprogrammed into different 3D objects.     

Fe(III) @g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanocomposite-catalyzed green synthesis of di-indolyloxindole derivatives

A Fe(III)/g-C₃N₄ nanocomposite was simply synthesized by impregnation of FeCl₃ with g-C₃N₄, and the heterogeneous nanocomposite was characterized by various techniques; including X-ray diffraction, Fourier-transform infrared spectroscopy, and transmission electron microscopy. Then, the 3-indolylation reaction of isatin with indole derivatives was carried out in the presence of the Fe(III)/g-C₃N₄ nanocomposite in water in reflux conditions. The results showed that the corresponding products were synthesized in excellent yields (up to 96%) in a short time (30 min). The significant features of this protocol are the non-toxic solvent, green media, short reaction time and high yields.     

Water Expandable Polystyrene-Organoclay Nanocomposites: Role of Clay and Its Dispersion State

A published process for preparing expandable polystyrene containing water as a blowing agent was applied to synthesize water expandable polystyrene-organoclay nanocomposites (WEPS-OCN). Organoclay was uniformly dispersed in styrene monomer. During suspension polymerization, water was trapped in the polystyrene (PS) matrix through the use of starch, ending up with spherical PS-organoclay beads. By selecting organoclays with various surfactants and modifier concentrations, different distribution states of nanoclay in the PS matrix, from cluster (poor dispersion) to either intercalated (limited dispersion) or exfoliated (full dispersion) were obtained. The incorporation of organoclay led to higher water content in the expandable beads. However, as expected, the flammability of the expanded product was increased with organoclay content. Furthermore, the results showed that the average unexpanded bead size, density of preexpanded beads, foam cell morphology, and flammability were directly influenced by the dispersion status of the organoclay. The best results were obtained when full dispersion (exfoliation) of nanoclay in PS matrix occurred.     

Segmental Dynamics in net -poly(methyl methacrylate)- co -poly(n-butyl acrylate) Copolymer Networks

Dynamic mechanical spectroscopy and differential scanning calorimetry investigations of segmental dynamics are reported for net-poly(methyl methacrylate)-co-poly(n-butyl acrylate) copolymer networks. Three characteristic temperatures, namely, Vogel (T_∞), glass transition (T _g ), and crossover (T _c ), were used to define cooperativity range and a new reduced temperature parameter (Solidness, S). The results showed that broadness of the α -dispersion (glass transition) and cooperativity length scale at the glass transition temperature decreased with increasing butyl acrylate content and T _g -scaled temperature dependence of the relaxation time (fragility). However, the cooperativity range (T _c –T_∞), decreased with increasing fragility index. Furthermore, the solidness at T _g (S(T _g )) was nearly independent of chemical structure of the samples. Finally, a correlation was found between two measures of cooperativity length scale in the glass transition region, namely, average volume of cooperatively rearranging regions, V _CRR , and the number of basic units in an act of rearrangement in the glass transition region, Z(T _g ), determined from two completely independent experimental techniques.     

Synthesis of Novel 1H‐Imidazol[1,2‐a]Indeno[2,1‐e]Pyridine‐6(5H)‐Ones Derivatives via a One‐Pot Four‐Component Condensation Reaction

1H‐imidazol[1,2‐a]indeno[2,1‐e]pyridine‐6(5H)‐ones derivatives were synthesized in a one‐pot four‐component condensation of corresponding aldehydes, 1,3‐indandione, diamine, and nitro ketene dithioacetal using KAl(SO₄)₂·12H₂O (alum) as nontoxic, reusable, inexpensive and easily available catalyst in good to excellent yields. This green protocol provides a powerful entry into fused polycyclic structures related to bioactive heterocycles.     

Partial Regularity of Strong Local Minimizers in the Multi-Dimensional Calculus of Variations

Let ⁿ be a bounded domain and F: a given strongly quasiconvex integrand of class C ² satisfying the growth condition for some c>0 and 2p<. Consider the multiple integral where uW ^1,p (, ^N ). The main result of the paper is the proof that any strong local minimizer of I[·] is of class C ^1, _loc for any (0,1) on an open set of full n-dimensional measure. In the case of weak local minimizers we establish the same result under the extra assumption that the oscillations in the gradient of the minimizer are not too large. Without such an assumption weak local minimizers need not be partially regular as we show by a class of examples. We also briefly discuss the question of existence of strong local minimizers for I[·] and connections of our results to extensions of Weierstrass sufficiency theorem to the multi-dimensional setting.     

Copper‐Catalyzed Synthesis of Pentasubstituted Pyridines from N‐Sulfonyl Ketenimines, 1,1,3,3‐Tetramethylguanidine,and Acetylene Dicarboxylates

Regioselective synthesis of pentasubstituted pyridines has been developed in moderate‐to‐good yields by the reaction of sulfonyl azides, alkynes, and a dialkyl acetylenedicarboxylate? tetramethylguanidine adduct catalyzed by CuI in MeCN at room temperature.     

Gelatin/montmorillonite biohybrid films prepared via a novel photocrosslinking method: structure–properties investigations

Gelatin/sodium montmorillonite (Na⁺MMT) hybrid nanocomposite films were prepared by a new photocrosslinking method using 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone (Irgacure 2959) as a photoactive radical initiator and N,N′-Methylenebisacrylamide (MBA) as a crosslinking agent. The prepared samples were characterized by X-ray diffraction (XRD), differential scanning calorimetry, stress–strain measurements and UV–Vis spectrophotometry. XRD patterns showed the formation of exfoliation structure resulting in considerable improves in mechanical properties of the nanocomposite. Retaining of transparency also suggested that Na⁺MMT nanosheets were uniformly distributed in the gelatin matrix. The tensile strength and Elastic’s modulus of nanocomposites were also improved notably by enhancing amount of Na⁺MMT. Furthermore, gelatin/Na⁺MMT nanocomposites showed a second T _g at a higher temperature in presence of Na⁺MMT.     

Sensitive determination of methadone in human serum and urine by dispersive liquid–liquid microextraction based on the solidification of a floating organic droplet followed by HPLC–UV

Dispersive liquid–liquid microextraction based on solidification of floating organic droplet was developed for the extraction of methadone and determination by high‐performance liquid chromatography with UV detection. In this method, no microsyringe or fiber is required to support the organic microdrop due to the usage of an organic solvent with a low density and appropriate melting point. Furthermore, the extractant droplet can be collected easily by solidifying it at low temperature. 1‐Undecanol and methanol were chosen as extraction and disperser solvents, respectively. Parameters that influence extraction efficiency, i.e. volumes of extracting and dispersing solvents, pH, and salt effect, were optimized by using response surface methodology. Under optimal conditions, enrichment factor for methadone was 134 and 160 in serum and urine samples, respectively. The limit of detection was 3.34 ng/mmL in serum and 1.67 ng/mL in urine samples. Compared with the traditional dispersive liquid–liquid microextraction, the proposed method obtained lower limit of detection. Moreover, the solidification of floating organic solvent facilitated the phase transfer. And most importantly, it avoided using high‐density and toxic solvents of traditional dispersive liquid–liquid microextraction method. The proposed method was successfully applied to the determination of methadone in serum and urine samples of an addicted individual under methadone therapy.