Mild and Efficient Chemoselective Tetrahydropyranylation of Alcohols Using Brønsted Acidic Ionic Liquid as Catalyst Under Solvent-Free Conditions

A straightforward and efficient method for preparation of morpholinium bisulfate ([mroH]HSO₄) as a novel acidic ionic liquid is reported. The application of this efficient and inexpensive acidic ionic liquid catalyst for tetrahydropyranylation of alcohols under mild and solvent-free conditions at room was investigated.     

Structural,Electronic, Reactivity,and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide,and Its Derivatives: DFT,MEP, and NBO Calculations

In this study, we used density functional theory (DFT) and natural bond orbital (NBO) analysis to determine the structural, electronic, reactivity, and conformational features of 2,5,5-trimethyl-1,3,2-di-heteroatom (X) phosphinane-2-sulfide derivatives (X = O (compound 1), S (compound 2), and Se (compound 3)). We discovered that the features improve dramatically at 6-31G** and B3LYP/6-311+G** levels. The level of theory for the molecular structure was optimized first, followed by the frontier molecular orbital theory development to assess molecular stability and reactivity. Molecular orbital calculations, such as the HOMO–LUMO energy gap and the mapping of molecular electrostatic potential surfaces (MEP), were performed similarly to DFT calculations. In addition, the electrostatic potential of the molecule was used to map the electron density on a surface. In addition to revealing molecules’ size and shape distribution, this study also shows the sites on the surface where molecules are most chemically reactive.     

Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

Abstract  

New phosphoramidates with formula 3-NC₅H₄C(O)NHP(O)XY (X=Y=Cl (1), X=Y=NH–C(CH₃)₃ (2a,2b), X=Y=N(C₄H₉)₂ (3), X=Cl, Y=N(C₂H₅)₂ (4) were synthesized and characterized by IR, ¹H-, ¹³C-, ³¹P-NMR spectroscopy and CHN elemental analysis. Surprisingly, the reaction of compound 2a with LaCl₃, 7H₂O in 3:1 M ratio leads to a polymorph of this compound (2b). NMR spectra indicate that ² J(PNH_amide) in 2b (7.0 Hz) is very much greater than in 2a (4.1 Hz), while δ(³¹P) values are identical for both of them. In IR spectra, υ(P=O) is weaker but υ(C=O) is stronger in 2a than in 2b. The structures of 2a, 2b were determined by X-ray crystallography. These compounds form centrosymmetric dimers via two intermolecular P=O……H–N hydrogen bonds. Strong intermolecular N–H…N, N–H…O and weak C–H…O hydrogen bonds lead to a three-dimensional polymeric cluster in the 2a while intermolecular strong N–H……N and weak C–H……O hydrogen bonds form a two-dimensional polymeric chain in 2b.     

A Review on Bioengineering Approaches to Insulin Delivery: A Pharmaceutical and Engineering Perspective

Diabetes mellitus (DM) is the most prevalent non‐contagious disease, which has affected a large number of people all over the world. Among all treatments known to have a positive influence in the control of DM, insulin therapy is the most common and effective one. Nowadays, various methods of insulin delivery are under investigation, which are able to reach a plausible bioavailability with ignorable side effects instead of insulin injection. This article presents a comprehensive review of the insulin therapy approach with a focus on modified methods in insulin delivery strategies and current advances in engineered insulin delivery systems.     

Bismuth-containing layered double hydroxide as a novel efficient photocatalyst for degradation of methylene blue under visible light

Layered double hydroxide (LDH)-based photocatalysts have emerged as a very promising candidate to replace TiO₂, owing to their unique layered structure, tunable band gaps, low cost, ease of scale-up, and good photocatalytic activity. Bismuth-doped ZnCr-LDH was studied as photocatalyst in the photodegradation of methylene blue (MB). The structure and morphology of ZnCr-LDH and ZnCrBi-LDH were characterized using a different mode of delegated tools, e.g., FTIR, XRD, UV–Vis, FESEM–EDX, and TEM measurements. FESEM and TEM image of the synthesized LDHs showed that the synthesized LDH is smooth overlapping crystals, and they are approximately in hexagonal form. The material was found to be a good photocatalyst for degradation of methylene blue in visible light, and the results showed that the photocatalytic activity of ZnCrBi-LDH sample is higher than of ZnCr-LDH sample. According to the kinetic data, the reaction rate constant of ZnCrBi-LDH is approximately four times higher than the apparent reaction rate constant of ZnCr-LDH. The catalytic activity was retained even after four methylene blue degradation cycles, indicating that the LDH could be an important addition to the field of wastewater treatment.     

Nickel−Copper bimetallic mesoporous nanoparticles: As an efficient heterogeneous catalyst for N‐alkylation of amines with alcohols

A bimetallic catalyst (Ni/Cu‐MCM‐41) is prepared via co‐condensation method. The latter is characterized by Fourier transform infrared (FT‐IR), X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX), diffuse reflectance spectroscopy (DRS), and nitrogen adsorption–desorption analysis. Catalytic performance of Ni/Cu‐MCM‐41 is probed in N‐alkylation of amines with alcohols through a hydrogen autotransfer process. Noteworthy, this catalytic system appears very efficient for synthesis of a range of secondary and tertiary amines in good to excellent isolated yields. Moreover, the catalyst is successfully recovered and reused four times without notable decrease in its activity.     

A New Four‐Component Reaction for the Synthesis of Spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles]

A new four‐component synthesis of spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles] and spiro[acenaphthylene‐1(2H),4′‐[4H‐indeno[1,2‐b]pyridines] by the reaction of indane‐1,3‐dione, 1,3‐dicarbonyl compounds, isatins (=1H‐indole‐2,3‐diones) or acenaphthylene‐1,2‐dione, and AcONH₄ in refluxing toluene in the presence of a catalytic amount of pyridine is reported.     

Analysis of testosterone in human urine using molecularly imprinted solid-phase extraction and corona discharge ion mobility spectrometry

Analysis of testosterone was accomplished using corona discharge ion mobility spectrometry. Molecular imprinted polymer was used for the extraction and pre-concentration of testosterone. Analytical parameters including precision, dynamic range and detection limit were obtained. The linear dynamic range was from 10 to 250 ng/mL and the limit of detection was 0.9 ng/mL. The proposed method was used for analysis of testosterone in urine samples. A urine sample from a 3-year-old girl was used as the blank. The RSD was below 10%. The obtained results from the method were also compared with the standard method for analysis of testosterone using SPE-HPLC analysis. The results demonstrate the accuracy of the method.     

Surface Charge‐Transfer Doping of Graphene Nanoflakes Containing Double‐Vacancy (5‐8‐5) and Stone–Wales (55‐77) Defects through Molecular Adsorption

The adsorption of six electron donor–acceptor (D/A) organic molecules on various sizes of graphene nanoflakes (GNFs) containing two common defects, double‐vacancy (5‐8‐5) and Stone–Wales (55‐77), are investigated by means of ab initio DFT [M06‐2X(‐D3)/cc‐pVDZ]. Different D/A molecules adsorb on a defect graphene (DG) surface with binding energies (ΔE_b) of about ?12 to ?28 kcal mol^?1. The ΔE_b values for adsorption of molecules on the Stone–Wales GNF surface are higher than those on the double vacancy GNF surface. Moreover, binding energies increase by about 10 % with an increase in surface size. The nature of cooperative weak interactions is analyzed based on quantum theory of atoms in molecules, noncovalent interactions plot, and natural bond order analyses, and the dominant interaction is compared for different molecules. Electron density population analysis is used to explain the n‐ and p‐type character of defect graphene nanoflakes (DGNFs) and also the change in electronic properties and reactivity parameters of DGNFs upon adsorption of different molecules and with increasing DGNF size. Results indicate that the HOMO–LUMO energy gap (E_g) of DGNFs decreases upon adsorption of molecules. However, by increasing the size of DGNFs, the E_g and chemical hardness of all complexes decrease and the electrophilicity index increases. Furthermore, the values of the chemical potential of acceptor–DGNF complexes decrease with increasing size, whereas those of donor–DGNF complexes increase.     

One-Pot Synthesis of Dihydropyrimidine-Thione Derivatives Using Tungstate Sulfuric Acid (TSA) as a Recyclable Catalyst

Abstract

An efficient, simple, and environmentally benign procedure for the one-pot synthesis of 3,4-dihydropyrimidine-2-(1H) thione derivatives that entails the three-component condensation of appropriate aryl aldehydes, β-dicarbonyls, and thiourea in the presence of catalytic amount of tungstate sulfuric acid under solvent-free conditions was reported. This method has many advantages including excellent yields, short reaction time, and simple work-up procedure.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: 1H, 13C NMR and Mass Spectra for 5b, 5g, 5j, 5i, 5l (S2-S16). Additional Characterization Data (S17-18).