Development of CuMnxOy (x = 2, and y = 4)-GO heterostructure for the synthesis of pyranoquinoline derivatives.

The pyranoquinoline derivatives are synthetically important due to their biological properties. In this research, these derivatives were produced through an environmentally friendly method. This method includes the use of CuMnxOy (x = 2, and y = 4)-GO as a nanocatalyst, which is easy to produce, has excellent performance, cost-effectiveness, and recyclability among its features, and also the use of water as a green solvent. Pyranoquinolines through the one-pot, the multi-component reaction between different derivatives of aryl glyoxal, ethyl cyanoacetate, and 4-hydroxyquinoline-2(1H)-one were synthesized using nanocatalyst, K2CO3, and H2O. Also, the structure of the CuMnxOy-GO nanocatalyst was evaluated and confirmed via different analyses. The distinguishing features of this work compared to previous works are easy workup, recyclability of nanocatalyst, facile synthesis process, and provide high yields of products.

Zn Complex on Tryptophan-Functionalized MCM-41 as an Efficient and Promising Reusable Nanocatalyst in One-Pot Three-Component Synthesis of Amino Benzyl Quinolinols and Naphthols via a Betti Reaction.

In this research, a Zn transition metallic complex on functionalized mesopore silica MCM-41 has been designed and utilized as an effective, recoverable, and thermally stable heterogeneous nanocatalyst in the formation of the C-C bond. Also, the synthesis of amino benzyl quinolinols and amino benzyl naphthol derivatives was performed by the three-component reaction of Betti from aromatic aldehydes, type II amines, and 8-hydroxyquinoline and 1-naphthol in the presence of the MCM-41-tryptophan-Zn nanocatalyst under reflux conditions. The short reaction times, high efficiency of the products, the easy separation of catalysts due to their heterogeneity, and their reusability are the advantages of this method. Finally, the nature of catalysts was studied by using some techniques such as the Fourier transform infrared spectrum, energy-dispersive spectroscopy, hot filtration test, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, inductively coupled plasma optical emission spectrometry, and N2 adsorption-desorption (BET). The synthesized heterogeneous catalysts showed perfect catalytic activity and also good recyclability in the Betti reaction. They could be reused at least for five consecutive cycles without significant loss of their catalytic activities.

Degradation of ciprofloxacin using hematite/MOF nanocomposite as a heterogeneous Fenton-like catalyst: A comparison of composite and core-shell structures.

A novel strategy was described to fabricate hematite-MOF materials with morphologies (core-shell) and (composite) as an efficient peroxymonosulfate (PMS) activator for degrading ciprofloxacin (CIP) antibiotics. First, α-Fe2O3 nanoparticles (NPs) with a size distribution range of 80 nm were prepared by surfactant-assisted reflux method. Then, cobalt-based metal-organic framework (ZIF-67) was grown onto the α-Fe2O3 NPs with ultrasonic and solvothermal method, which can control the nanostructures morphology. The physicochemical properties of these nanostructures were probed by ATR-IR, WA-XRD, FESEM, VSM, TEM, and EDS spectroscopy. The results showed that all the added CIP (20 ppm) antibiotics were completely degraded in 30 min in the α-Fe2O3/ZIF-67 (0.10 g/L) and PMS (0.20 g/L) system with rate constant of 0.130 min-1. To validate the merits of the α-Fe2O3/ZIF-67, α-Fe2O3@ZIF-67 core-shell nanostructures were also applied under similar conditions. The findings demonstrated that Co/Fe species within α-Fe2O3/ZIF-67 composite catalyzed PMS synergistically to the formation of the OH and SO4- and 1O2 for CIP degradation. Furthermore, α-Fe2O3/ZIF-67 showed good recyclability enabling facile separation of the catalyst from reaction mixtures using an external magnet. The current protocol can be a useful criterion in designing various Magnetic-MOF composites with controlled morphologies for environmental remediation.

Cu-Kojic Acid Complex Anchored to Functionalized Silica-MCM-41: A Promising Regioselective and Reusable Nanocatalyst for Click Reaction.

Cu-Kojic acid (KA) complex anchored to functionalized silica-MCM-41 was synthesized via the process of postgrafting and introduced as an effective, new, reusable, and thermally resistant heterogeneous nanocatalyst for the clean synthesis of 1H-1,2,3-triazoles from Click reaction of 2-(azidomethyl)-5-benzyloxy-4-pyrone and azido Kojic acid with a variety of terminal alkynes in excellent yields. The structure of nanocatalyst was analyzed by ICP, BET, XRD, EDS, SEM, TGA, TEM, and FT-IR techniques.

Injectable thermosensitive hybrid hydrogel containing graphene oxide and chitosan as dental pulp stem cells scaffold for bone tissue engineering.

Here, we fabricated thermosensitive injectable hydrogel containing poly (N-isopropylacrylamide) (PNIPAAm)-based copolymer/graphene oxide (GO) composite with different feed ratio to chitosan (CS) as a natural polymer through physical and chemical crosslinking for the proliferation and differentiation of the human dental pulp stem cells (hDPSCs) to the osteoblasts. The PNIPAAm copolymer/GO composite was synthesized by free-radical copolymerization of (N-isopropylacrylamide) (NIPAAm), itaconic acid (IA) and maleic anhydride-modified poly(ethylene glycol) (PEG) in the presence of GO and used for the preparation of the hydrogels. The formulated hydrogels were evaluated for the porous architecture, rheological behavior, compressive strength, swelling property, in vitro degradation, hemocompatibility, biocompatibility, and differentiation. The hydrogel could enhance the deposition of minerals and the activity of alkaline phosphatase (ALP), in large part attributable to the oxygen and amine-containing functional groups of GO and CS. The engineered hydrogel could also upregulate the expression of the Runt-related transcription factor 2 and osteocalcin in the hDPSCs cultivated in both the normal and osteogenic media. It seems to promote the absorption of osteogenic inducer too. Based on our findings, the engineered hydrogel demonstrated the osteogenic potential, upon which it is proposed as a constructing scaffold in bone tissue engineering for the transplantation of hDPSCs.

Isotopic splitting patterns in the (13) C NMR spectra of some partially deuterated 1-aryl-2-(phenyldiazenyl)butane-1,3-dione and 4-hydroxy-3-(phenyldiazenyl)-2H-chromen-2-one: evidence for elucidation of tautomeric forms.

Nuclear magnetic resonance spectra of synthesized azo dyes derived from aniline derivatives in reaction with benzoylacetone and 4-hydroxycoumarin were studied in both CDCl3 and (CD3 )2 SO (two drops of D2 O were added into solutions of dyes). All dyes showed intramolecular hydrogen bonding. Dyes derived from o-nitro aniline in the reaction with benzoylacetone, and 4-hydroxycoumarin showed bifurcated intramolecular hydrogen bonds. The solvent-substrate proton exchange of dyes derived from benzoylacetone and 4-hydroxycoumarin was examined in the presence of two drops of D2 O. Among ten dye samples, two dyes derived from benzoylacetone did not show deuteration, three dyes showed partial deuteration and five dyes showed full deuteration under similar conditions. For the partially deuterated dyes the ß-isotope effect in (13) C splitting was investigated and was used for the determination of the predominant tautomeric form.

Isotopic effect on tautomeric behavior of 5-(2,6-disubstituted-aryloxy)-tetrazoles.

Isotopic effect on tautomeric behaviors of the synthesized 5-phenoxy- (1a), 5-(2,6-dimethylphenoxy)-(1b), 5-(2,6-diisopropylphenoxy)-(1c), 5-(2,6-dimethoxyphenoxy)-(1d) and 5-(4-methylphenoxy)-tetrazole (1e) were investigated in DMSO-d6 by adding one drop of D2O. Among 1a-e, 1a, 1d and 1e show small rotational barrier around C5-O1 and O1-C6 while in 1b and 1c there are distinguishable rotational barrier about that bonds. The (1)H NMR spectra of 1b and 1c show slightly different chemical shifts for two methyl and isopropyl groups on those phenyl ring, respectively, while the chemical shifts difference (Δδ) between two methyl and two isopropyl groups were enhanced by adding D2O. The (13)C NMR spectra of 1b show two overlapped singlets for methyl groups after adding D2O. Representatively, the calculations of compound 1c were performed with GAUSSIAN-03 and the rotational barrier about C5-O1 and between isopropyl group and phenyl ring in 1c was calculated with B3LYP/6-31G(d) basis set.

New one-pot synthesis of spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]pentaones and their sulfur analogues.

Reaction of barbituric acid (BA), 1,3-dimethyl barbituric acid (DMBA) and 2-thiobarbituric acid (TBA) with cyanogen bromide and various aldehydes in presence of triethylamine afforded a new class of heterocyclic stable 5-alkyl and/or 5-aryl-1H, 1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]2,2',4,4',6'(3H,3'H,5H)-pentaones which are dimeric forms of barbiturate (uracil and thiouracil derivatives) at 0 °C to ambient temperatures. Structure elucidation is proved by X-ray crystallography, (1)H NMR, (13)C NMR, FT-IR, CHN and mass analyses techniques. Mechanisms of the formations are discussed.

Tautomerism and isotopic multiplets in the 13C NMR spectra of partially deuterated 3-arylpyrimido[4,5-c]pyridazine-5,7(6H,8H)-diones and their sulfur analogs--evidence for elucidation of the structure backbone and tautomeric forms.

The tautomerism of the synthesized 3-arylpyrimido[4,5-c]pyridazine-5,7(6H,8H)-diones (1a-d) and 3-aryl-7-thioxo-7,8-dihydro-6H-pyrimido[4,5-c]pyridazine-5-ones (2a-d) was studied in dimethyl sulfoxide (DMSO)-d(6). (1)H NMR spectra of 1a-d showed a clustered water molecule in the structure backbone that is attached by strong intermolecular H bonding. The relation between the temperature and H bonding of the clustered water molecule with 1a was also studied as representative. The relation between the electronegativity (chi) of the substituent on phenyl ring and the chemical shifts of clustered water protons in 1a-d was also studied. All of 1a-d and also 2d compounds existed in lactam (I) form, whereas 2a-c compounds have two distinguished tautomers in DMSO-d(6) [lactam (I) and lactim (II) forms]. The solvent-substrate proton exchange was examined in compounds 1a-d and 2a-d by adding one drop of D(2)O. All compounds (except 1d) showed proton/deuterium exchange of the clustered water protons in DMSO by adding one drop of D(2)O. Some compounds (but not all of them) that are easily soluble in DMSO-d(6) containing D(2)O showed isotopic splitting (beta-isotope effect) in their (13)C NMR spectra. Among them, compound 1a was the best evidence to help the spectral assignments and structure determination of predominant tautomer by carbon-13 splitting (beta-isotope effect).

5-(2,6-Dimethoxy-phen-oxy)-2-methyl-sulfanylmethyl-2H-tetra-zole.

In the title mol-ecule, C(11)H(14)N(4)O(3)S, the tetra-zole and benzene rings are nearly perpendicular to each other, forming a dihedral angle of 104.93 (14)°. The crystal packing exhibits weak inter-molecular C-H⋯O hydrogen bonds.

1,1',3,3',5,5'-Hexamethyl-spiro-[furo[2,3-d]pyrimidine-6(5H),5'-pyrimidine]-2,2',4,4',6'(1H,3H,1'H,3'H,5'H)-penta-one.

In the title mol-ecule, C(15)H(18)N(4)O(6), the fused 2,3-dihydro-furan ring has an envelope conformation and the spiro pyrimidine ring has a half-chair conformation. In the crystal, short inter-molecular O⋯C contacts of 2.835 (4) and 2.868 (4) Šbetween the carbonyl groups indicate the existence of electrostatic inter-actions, which link the mol-ecules into corrugated sheets parallel to the ab plane.

NMR investigation of methyl-2,4-dimethoxysalicylate: effect of solvent and temperature.

(1)H NMR and (13)C NMR of methyl-2,4-dimethoxysalicylate 2 was measured in chloroform-d at the temperature range of 220-330 K, in dimethyl sulfoxide-d(6) at the temperature range of 300-400 K and in a polar protic solvent (CD(3)OD) at 300 K. The structure of 2 in liquid phase (solvent) is compared with those in solid phase (X-ray) and in the gas phase (quantum mechanical calculations). The relationship between molecular geometry, (1)H NMR chemical shift and W coupling of involved protons has a complex nature, but hydrogen bonds [C=O...H-O and C=O...H-CH(2)O] strength is the principle factor.