One-Pot,Facile, Highly Efficient,and Green Synthesis of Acridinedione Derivatives Using Vitamin B1

An efficient methodology for the synthesis of acridinedione derivatives 4a–o has been achieved by one-pot, multicomponent condensation of dimedone 1, various amines 2a–d, and substitute aromatic aldehydes 3a–k, in the presence of the easily available, inexpensive, and nontoxic catalyst vitamin B₁ (VB₁) as a versatile biodegradable. Synthesis of acridine-type compounds was performed in good yields in water as green solvent. Its high-yield efficiency; clean, ecofriendly, simple workup procedure; and easy purification are regarded as the main advantages of this method besides its green solvent. The synthesized compounds are characterized using spectroscopic analyses (FTIR, ¹H NMR, ¹³C NMR, and high-resolution mass spectrometry) techniques.     

High-Performance Liquid Chromatography of Fat-Soluble Vitamins. I. Determination of Vitamin A-Acetate in Pharmaceutical Preparations and Blood

Abstract

A reversed phase high-performance liquid chromatography (HPLC) has been developed for the quanititive determination of retinol acetate (vitamin A-acetate) in pharmaceutical formulations and biological materials. The extraction of vitamin A-acetate from capsules and dragees and from blood is performed in a fully automated, electronically controlled extraction apparatus within 3–10 minutes. For reversed phase HPLC a column of LiChrosorb RP18 and methanol as eluent were used. Vitamin A-acetate was separated in less than 1 minute. The detection limit was 1-2 ng. The described methods were proved useful for extraction and determination of vitamin A-acetate in pharmaceutical preparations such as capsules and dragees and in blood, and can be well reproduced with a maximum coefficient of variation of <4%.     

Synthesis,characterization, and crystal structure determination of palladacycles of para-substituted 2-thiobenzylazobenzenes

Bichelated neutral palladacycles (1–3), [Pd(L)Cl], were synthesized from reaction of the new potential tridentate (C,N,S) ligands, 2-thiobenzylazobenzene (L₁), 4′-methyl-2-thiobenzylazobenzene (L₂), and 4′-chloro-2-thiobenzylazobenzene (L₃) with sodium tetrachloropalladate(II), Na₂[PdCl₄], in ethanol. The compounds were characterized by elemental analysis, FT-IR, ¹H NMR, UV–visible, and thermogravimetric analysis. The crystal structures of L₂ and 1–3 were determined by single-crystal X-ray diffraction. In 1–3, the geometry around palladium remains almost square planar, coordinated to carbon, nitrogen, and sulfur of the ligand forming a bichelated cyclopalladate complex. The C–H…Cl type intermolecular hydrogen bonds, weak π…π, C–H…π, and van der Waals interactions are believed to be the stabilizing forces for the crystal packing of these palladacycles.     

Complexes of unsymmetric bis-hydrazide ligands: crystal structures and properties

Two unsymmetric bis-aroyl-hydrazines, N′-(2-hydroxybenzoyl)isonicotinohydrazide (L1) and N′-(2-hydroxybenzoyl)nicotinohydrazide (L2), were synthesized through reactions of salicyl hydrazide with isonicotinoyl chloride and nicotinoyl chloride, respectively. Reactions of metal salts with L1 or L2 gave three new complexes, [Cd(L1)₂(SCN)₂] _n (1), [Zn(L1)₂Cl₂]?·?H₂O (2), and [Zn(L2)₂Cl₂] (3). Complex 1 features a 1-D double-chain structure built by SCN^– bridging six-coordinate Cd^II centers while 2 and 3 are mononuclear Zn^II complexes. In 1–3, isomeric ligands L1 and L2 coordinate with metal ions in a terminal coordination mode. Ligands L1 and L2 through O–H···N and N–H···O hydrogen-bonding interactions in 1–3 are crucial for the structure extension into 3-D supramolecular structures of 1 and 2, or 2-D sheet of 3. Complexes 1–3 emit interesting blue-green luminescence. Thermal behaviors of 1–3 as well as the specific rotation of 2 were also investigated.     

Qualitative and quantitative analysis of chemical constituents of Ptychopetalum olacoides Benth

Ptychopetalum olacoides is a folk medicinal plant for health care in market, especially in Brazil. Fourteen known compounds were isolated from P. olacoides and their chemical structures were elucidated by extensive spectroscopic data, including 1D NMR, 2D NMR, UV, IR and HR-ESI-MS. The 14 known compounds were identified as N-trans-feruloyl-3,5-dihydroxyindolin-2-one (1), magnoflorine (2), menisperine (3), 4-coumaroylserotonin (4), moschamine (5), luteolin (6), 4′-methoxyluteolin (7), 3-methoxyluteolin (8), 3, 7-dimethoxyluteolin (9), caffeic acid (10), ferulic acid (11), vanillic acid (12), syringic acid (13) and ginsenoside Re (14). To our knowledge, compounds (1–6, 13–14) were isolated from the plant for the first time. Additionally, quantitative analysis results indicated that calibration equations of compounds (1–3, 6, 9, 11–13) exhibited good linear regressions within the test ranges (R² ≥ 0.9990) and magnoflorine and menisperine were the major constituents in the barks of P. olacoides. The contents of magnoflorine and menisperine accounted for 75.96% of all analytes. However, the content of phenolic components was smaller and the highest content was no more than 1.04 mg/g. Collectively, these results suggested that alkaloids are the dominant substances in P. olacoides, which can make a difference for the quality control and further use of P. olacoides.     

The Spectrophotometric Determination of Vitamin a Using Iodine

Abstract

Methods are described for the spectrophotometric determination of vitamin A (0.15–12.5 μg) using iodine as the chromogenic reagent. The reaction is most sensitive in chloroform. Vitamin D₂ and ß-carotene do not interfere if the analysis is carried out in 1, 2 -dichloroethane.     

Determination of B-group vitamins in Turkish honey using ultra-performance liquid chromatography with electrospray ionization coupled to tandem mass spectrometry

A rapid and sensitive ultra-performance liquid chromatography–tandem mass spectrometry method with electrospray ionization (UPLC–ESI–MS/MS) for analysis of B-group vitamins in honey has been presented. Aim of this study is the characterization of different types of Turkish honeys according to B-group vitamins. Vitamins were determined in 17 different types of Turkish honey samples by UPLC–ESI–MS/MS. Heather honey samples were distinguished among the studied honeys with the richest vitamin content with 286.10?mg/kg, and it is followed by sunflower honey and thyme honey with the total vitamin contents of 206.01 and 163.27?mg/kg, respectively. The presence of vitamin B₁ (thiamine), vitamin B₂ (riboflavin), vitamin B₃ (nicotinamide, B₃N and nicotinic acid, B₃H), vitamin B₆ (pyridoxine), and vitamin B₉ (folic acid) was detected in all the honey samples analyzed. Moreover, vitamin B₅ (pantothenic acid) was observed in most of them. Vitamin B₁₂ (cyanocobalamin) and vitamin B₇ (biotine) were not detected in the studied honey samples. Turkish honey samples showed efficacious vitamin content for the consumers.     

Indirect Flow-Injection Analysis of Ascorbic Acid by Photochemical Reduction of Methylene Blue

Abstract

Ascorbic acid was determined indirectly by spectrophotometry at 666 nm based on the photochemical reduction of methylene blue using flow-injection analysis. The carrier stream was 12.7 μgml^?1 methylene blue in phthalate-HCl buffer solution at pH 3.2. The reactor was irradiated with a 500-Watt halogen lamp to facilitate the development of the photochemical reaction. The system allows determination of ascorbic acid in the range 0.18–6.12 μgml^?1 with relative standard deviations of 2.09 and 0.31% for 1.97 and 4.92 μgml^?1 samples, respectively, and a sampling frequency of 50–55 h^?1. The proposed method was applied successfully to the determination of ascorbic acid in vitamin C tablets.     

The first coordination compounds of OP[NC4H8O]3 phosphoric triamide ligand: structural study and Hirshfeld surface analysis of SnIV and MnII complexes

The first X-ray crystal structures of coordination compounds of OP[NC₄H₈O]₃ phosphoric triamide (L) are investigated in Cl₂(CH₃)₂Sn(trans-L)₂ (1) and [Mn(H₂O)₄(trans-L)₂]Cl₂·2H₂O (2) as models of molecular and salt complexes for Hirshfeld surface (HS)-based analysis. The crystal packing of 1 includes weak interactions, while in the salt complex 2, a 2-D aggregate, along the (001) plane, is mediated by normal O–H?Cl and O–H?O hydrogen bonds. In the Hirshfeld study, the crystal cohesions of 1 and 2 are recognized via H?H, O?H/H?O, and Cl?H/H?Cl contacts. Among these interactions, hydrogen bonds O–H?Cl occur in the salt structure of 2, as well as some weaker hydrogen interactions as C–H?O (1 and 2), C–H?Cl (1), and O–H?O (2). The full fingerprint plots have nearly symmetric shapes for two independent molecules of 1, while an asymmetric shape appears for the cationic component of 2. To extract more detailed information on close intermolecular contacts, the molecular surface of the previously reported structure L was also mapped. The structure 2 is the first monomeric octahedral Mn(II)–phosphoric triamide complex reported so far. Furthermore, the HS analysis of 2 is the first such study on a cation–anion complex structure including phosphoric triamide ligand.     

Synthesis,spectroscopic characterization,antimicrobial activity and crystal structure of silver and copper complexes of sulfamethazine

Silver(I) and copper(II) complexes of 4-amino-N-(4,6-dimethyl-2-pyrimidinyl) benzenesulfonamide (smz) have been synthesized and characterized by elemental analysis and infrared (IR), ¹H NMR, and UV–vis spectroscopy. [Ag(smz)(pyridine)] (1) crystallizes in monoclinic system with space group P2₁/c and Z = 4, while [Cu(smz)₂(pyridine)₂]·H₂O (2) crystallizes in triclinic system with space group P-1 and Z = 2. X-ray analysis revealed that silver in 1 is four-coordinate exhibiting distorted tetrahedral geometry, while copper in 2 is coordinated to six nitrogens leading to a highly distorted octahedral geometry. The molecular structures of both 1 and 2 are stabilized by N–H?O and C–H?π intermolecular and C–H?O intramolecular interactions. Water plays a significant role in crystal packing by forming strong N–H?O_water intramolecular as well as O_water–H?N intermolecular interactions in 2. The results of IR, UV–vis, ¹H NMR spectral data and thermal analysis for 1 and 2 suggest that the binding of silver and copper to the sulfonamidic nitrogen is in agreement with the crystal structure determination. Antimicrobial activities of silver (1) and copper (2) complexes of sulfamethazine are studied by the dilution method against Staphylococcus aureus and Escherichia coli strains.     

Determination of α-tocopherol and ergocalciferol by thin-layer chromatography

A procedure was developed for determining α-tocopherol (vitamin E) and ergocalciferol (vitamin D₂) in oils. The procedure involved the alkaline hydrolysis of an oil according to GOST (State Standard) 30417 followed by the independent recovery of vitamins by extraction with organic solvents. The extracts were separated on Sorbfil plates with the stationary phase of silica gel with a particle size of 5–12 μm by eluting vitamin E with an octane-diethyl ether mixture (7: 1) and vitamin D₂ with a tetrachloromethane-diethyl ether mixture (4: 1). The zones of α-tocopherol and ergocalciferol were developed with conc. HNO₃ and conc. H₂SO₄, respectively. The plate scanning and image processing were performed with a Sorbfil Videodensitometer software. The calibration plots were linear in the range of 2.5–15 and 15–50 mg/mL for α-tocopherol and 0.08–0.13 mg/mL for ergocalciferol. The procedure was used to determine vitamins in bur marigold oily extract and grape seed oil.     

Experimental and Computational Studies on the 1:1 Complex of Anthranilic Acid with P-Toluenesulfonic Acid

Abstract

The proton-transfer compound (3) was synthesized in good yields by the reaction of anthranilic acid with p-toluenesulfonic acid. It was characterized by elemental analysis, infrared spectroscopy, and X-ray single-crystal determination. The crystal structure analysis of 2-carboxyanilinium p-toulenesulfonate (3) has revealed a one-dimensional hydrogen-bonded network structure, involving the tosylate anion, the carboxyl group, and the ammonium group. The H(N)···O distances range from 1.97 to 2.23 Å. The molecular geometry and vibrational frequencies of 3 were calculated using the ab-initio method (HF) with the 6–31G(d) and 6–31+G(d,p) basis sets. The computed results indicate that the optimized geometry reproduces the crystal structure well, and the assignments of fundamental vibrations also agree well with the theoretical frequencies. The intermolecular proton transfer process between the ionic (3) and nonionic (4) structures was also investigated with the theoretical computations. The nonionic form (4) is energetically more stable than the ionic form (3) and TS(3→4) by 9.76 and 7.01 kcal/mol, respectively, including the zero-point vibrational energy correction at the HF/6–31+G(d,p) level. In addition, the atomic charges, the molecular electrostatic potentials, the nucleus-independent chemical shifts, and the frontier molecular orbitals of 3 were carried out at the HF/6–31+G(d,p) level of theory.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables     

Syntheses,characterizations, crystal structures,antibacterial and SOD-like activities of nickel(II) and copper(II) complexes with 2-((Z)-(4-methoxyphenylimino)methyl)-4,6-dichlorophenol

Three mononuclear nickel(II) and copper(II) complexes, [Ni(L)₂(py)₂] (1), [Ni(L)₂(DMF)(H₂O)] (2), and [Cu(L)₂] (3), where HL = 2-((Z)-(4-methoxyphenylimino)methyl)-4,6-dichlorophenol, py = pyridine and DMF = N,N-dimethylformamide, have been synthesized and their structures determined by single crystal X-ray analysis. Complexes 1–3 crystallized in the monoclinic system of the space groups C2/c, P2_1/n, and P2_1/c, respectively. The crystal structures of 1 and 2 present an octahedral geometry at the metal center and 3 shows a square-planar geometry. The FT-IR spectra, UV–vis spectra, and magnetic susceptibility measurements agree with the observed crystal structures. EPR spectra indicate a d_x2–y2 ground state (g_|| > g_⊥ > 2.0023 and A_|| > A_⊥) for 3 at RT and LNT. The results of simultaneous TG-DTA analyses of 1 and 3 showed the final degradation products are NiO for 1 and CuO for 3. The Schiff base (HL) behaves as monobasic bidentate ligand possessing N and O donor atoms. Electrochemical properties for the complexes are similar and involve two irreversible redox processes. Complex 3 exhibits the ability to inhibit jack bean urease, although its Schiff base has no ability to inhibit urease. Complex 1 exhibits more active scavenging effects against O₂^? than HL, 2 and 3 under the same conditions. Antibacterial screening activities of these complexes were also investigated.     

Facile synthesis,X-ray analysis,and spectroscopic studies of di-iron propanedithiolate complexes with tris(aromatic)phosphine ligands

Three new propanedithiolate-type iron–sulfur complexes containing tris(aromatic)phosphine ligands, [{(μ-SCH₂)₂CH₂}Fe₂(CO)₅L] (L?=?P(PhOMe-p)₃, 1; P(PhMe-p)₃, 2; P(PhF-p)₃, 3), have been prepared through carbonyl substitution in the presence of Me₃NO. The new complexes 1–3 were characterized by elemental analysis, IR, ¹H, ¹³C{¹H}, and ³¹P{H} NMR spectra. The molecular structures of 1–3 were unequivocally determined by single crystal X-ray diffraction, in which the tris(aromatic)phosphine coordinated to Fe resides in an apical position of the pseudo-square-pyramidal geometry. IR spectroscopy and X-ray crystallographic analysis for 1–3 have indicated that the highly electron rich tris(aromatic)phosphine ligands (where the corresponding electron-donating abilities display the following order of P(PhOMe-p)₃?>?P(PhMe-p)₃?>?P(PhF-p)₃) result in a considerable red shift of the CO-stretching frequencies and a clear change of the Fe–Fe bond distances in 1–3.     

Fluohinetric Determination of Iron and Tpalliur with 1,4-Diami No-2,3-Dihyoroanthraquinone

Abstract

Fluorimetric methods for the determination of iron(III) (0.28–0.6 ppm) and thallium(III) (0.1–3 ppm) are described. Methods are based on the formation of a fluorescent product (δ_ex = 400 nm, δ_em= 470 nm) resulting of the transformation of the reagent. The interferences of foreign ions in each determination are also determined.     

Syntheses,crystal structures,electrochemical studies,and antioxidant activities of zinc(II) and copper(II) complexes with bis(2-benzimidazolyl) aniline derivatives

Two ligands, bis(benzimidazol-2-ylmethyl) aniline (bba) and bis(N-methyl-benzimidazol-2-ylmethyl) aniline (Mebba), and their transition metal complexes [Zn(bba)(Br)₂]·2DMF (1) and [Cu(Mebba)(Br)₂]·2DMF (2) have been synthesized and characterized by elemental analyses, molar conductivities, UV–vis spectra, IR spectra, NMR spectroscopy, and X-ray crystallography. The structure around Zn(II) can be described as distorted tetrahedral. Complex 2 can be described as distorted trigonal bipyramidal. Cyclic voltammograms of 2 indicate a quasireversible Cu²⁺/Cu⁺ couple. Additionally, the antioxidant activities of the free ligands and their complexes were determined by the superoxide and hydroxyl radical scavenging methods in vitro. Complexes 1 and 2 possess potent hydroxyl radical scavenging activity and better than standard antioxidants such as vitamin C and mannitol. Complex 2 possesses excellent superoxide radical activity.     

High Performance Liquid Chromatogrphy of Fat-Soluble Vitamins. III. Determination of Vitamin D3 in Pharmaceutical Preparations and in Blood

Abstract

A reversed phase high-performance liquid chromatographic method (HPLC) is described for separation and determination of colecalciferol (Vitamin D₃) in Vitamin preparations and in biological materials. Vitamin D₃ is extracted from the formulations and from the blood in a fully automated electronically controlled extraction apparatus. For HPLC a column of lichrosorb RP18 and methanol as eluent are used. The extraction, separation and determination of vitamin D₃ needs about 10–20 minutes. The described extraction and HPLC methods allow the detection of 1–2 ng per injection and are well reproduced with a maximum coefficient of variation of < 3,5%. Vitamin A-acetate is used as internal standard.     

Synthesis and characterization of Pr(III), Nd(III) and Er(III) complexes with 2,6-pyridinedimethanol

The reactions of Ln(NO₃)₃?6H₂O (Ln=Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H₂pydm) in a 1:2 M ratio were investigated, and complexes with the formula [Ln(H₂pydm)₂(NO₃)₂](NO₃) (Ln=Pr or Nd) (1 and 2) and [Er(H₂pydm)₃](NO₃)₃ (3) were isolated. The compounds contain 10-coordinate Pr(III) and Nd(III) ions that crystallize in the triclinic space group P-1 while the 9-coordinate Er(III) complex crystallizes in the monoclinic system (P2₁/n). A new lanthanide complex, [Pr(H₂pydm)₃](Cl)₃?DMF (4), has been synthesized by reaction of PrCl₃?6H₂O and H₂pydm. The nine-coordinate Pr(III) is bound to three H₂pydm ligands. X-ray crystal structures of 1–4 reveal that the ligand coordinates tridentate via the pyridyl nitrogen and the two hydroxyl oxygens. The electronic absorption spectra of 1–4 show 4f–4f transitions.     

Determination of Vitamin D3 and 25-Hydroxyvitamin D3 Using Liquid Chromatography with Amperometric Detection

Abstract

The electrochemical behaviour of vitamin D₃ and 25-hydroxyvitamin D₃ (25-OH D₃) in a high performance liquid chromatography system using amperometric detection is described. Separation is carried out using a C18 reversed-phase column and the optimum mobile phase was a 0.1 M LiClO₄ solution in methanol-water (97:3, v/v) at a flow rate of 1.25 ml/min. 25-OH D₃ and vitamin D₃ were eluted with good resolution at retention times of 3 and 6 minutes respectively, and determined by amperometric detection with a glassy carbon electrode at + 1.050 V (vs Ag/AgCl). Calibration graphs for both substances showed good linearity when amounts of vitamin D₃ between 18 and 312 ng and 27 and 412 ng of 25-OH D₃ were injected. Detection limits of 8 ng (vitamin D₃) and 25 ng (25-OH D₃); relative standard deviations of 3.2% (vitamin D₃) and 5.8% (25-OH D₃) were obtained.     

SYNTHESES OF SOME 35S-LABELLED ORGANIC COMPOUNDS AT BORIS KIDRIČ INSTITUTE - VINČA

Abstract

³⁵-labelled organic compounds are widely used in different fields: medicine, chemistry, biochemistry, biology, etc. Some of these compounds are known as chemoprotectors and ³⁵S-labelled forms are used in the investigation of such protective mechanism. Details of the chemical and biochemical syntheses of some ³⁵S-labelled organic compounds are given in the paper: DL-cysteine hydrochloride-³⁵S (1-amino-2-mercaptopropionic acid), vitamin B₁-³⁵S (thiamin hydrochloride), thiourea-³⁵S, carbon disulphide-³⁵S and L-methionine-³⁵S (1-amino-4-methyl- thiobutyric acid). Products of high specific activities are obtained: 5–10 mCi/mM DL-cysteine hydrochloride-³⁵S; 60–120 mCi/mM vitamin B₁-³⁵S; 100–200 mCi/mM thiourea-³⁵S; 20–100 mCi/mM carbon disulphide- ³⁵S and 1–10 Ci/mM L-methionine-³⁵S. All the products are of high chemical and radiochemical purity, which were determined by thin layer chromatography.