Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)

O,O′-Ditolylphosphorodithioates of phosphorus(III), [(o-, m-, or p-CH₃C₆H₄O)₂PS₂] _n PCl_3−n , and phosphorus(V), [(o-, m-, or p-CH₃C₆H₄O)₂-PS₂] _n POCl_3−n , (n = 1, 2, and 3) were isolated as colorless viscous liquids by the reaction of PCl₃ and POCl₃ with sodium ditolylphosphorodithioate, (o-, m-, or p-CH₃C₆H₄O)₂PS₂Na, in 1:1, 1:2, and 1:3 molar ratios in toluene. These compounds were characterized by elemental analyses, molecular weight measurements, IR, and NMR (¹H, ³¹P, and ¹³C) spectroscopic studies, which indicated a less common monodentate linkage of dithiophosphate moieties in both phosphorus(III) and phosphorus(V) derivatives leading to a tetrahedral geometry around the phosphorus atom.     

Phosphosulfonic acid‐catalyzed green synthesis and bioassay of α‐aryl‐α′‐1,3,4‐thiadiazolyl aminophosphonates

A series of new α‐aminophosphonates containing 1,3,4‐thiadiazole moiety (4a–l) were synthesized via a simple, efficient, and one‐pot three‐component Kabachnik–Fields reaction of 2‐amino‐5‐ethyl‐1,3,4‐thiadiazole with various aryl/heteroaryl aldehydes and diethylphosphite under solvent‐free microwave irradiation conditions using phosphosulfonic acid, as a reusable and heterogeneous solid acid catalyst. All the title compounds were screened for radical scavenging activity by DPPH and H₂O₂ methods, and antimicrobial activity against bacteria (Gram‐positive and Gram‐negative) and fungi using the disc diffusion technique. They exhibited potent in vitro antioxidant and moderate antimicrobial activity.     

Stereodivergent approach to Alzheimer's therapeutic agent (R)-(−) and (S)-(+)-arundic acid employing chiral 4-pentenol derivatives as building blocks

An efficient stereodivergent total synthesis of anti-Alzheimer agent (R)-(?) and (S)-(+)-arundic acid has been achieved from both chiral and nonchiral materials. This strategy features an efficient approach to separable diastereomeric C-2 chiral 4-pentenol intermediates employing proline catalysed asymmetric α-aminooxylation and [3,3] sigmatropic Claisen rearrangement are the highlights of present synthesis.     

A convenient new and efficient commercial synthetic route for dasatinib (Sprycel®)

A new and efficient synthetic route for dual-Src/Abl kinase inhibitor dasatinib (Sprycel®), an anticancer drug, is described. This commercially viable process yields dasatinib monohydrate free of potential impurities with consistent yield of 68% in route A and 61% in route B with HPLC purity >99.80% over four stages.     

High resolution detection of high mass proteins up to 80,000 Da via multifunctional CdS quantum dots in laser desorption/ionization mass spectrometry

CdS quantum dots (∼5 nm) are used as multifunctional nanoprobes as an effective matrix for large proteins, peptides and as affinity probes for the enrichment of tryptic digest proteins (lysozyme, myoglobin and cytochrome c) in laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). The use of CdS quantum dots (CdS QDs) as the matrix allows acquisition of high resolution LDI mass spectra for large proteins (5000-80,000 Da). The enhancement of mass resolution is especially notable for large proteins such as BSA, HSA and transferrin (34-49 times) when compared with those obtained by using SA as the matrix. This technique demonstrates the potentiality of LDI-TOF-MS as an appropriate analytical tool for the analysis of high-molecular-weight biomolecules with high mass resolution. In addition, CdS QDs are also used as matrices for background-free detection of small biomolecules (peptides) and as affinity probes for the enrichment of tryptic digest proteins in LDI-TOF-MS.     

Surface modified silver selinide nanoparticles as extracting probes to improve peptide/protein detection via nanoparticles-based liquid phase microextraction coupled with MALDI mass spectrometry

We report the first use of functionalized Ag₂Se nanoparticles (NPs) as effective extracting probes for NPs-based liquid-phase microextraction (NPs-LPME) to analyze hydrophobic peptides and proteins from biological samples (urine and plasma) and soybean in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Surface modified functional groups such as octadecanethiol (ODT) and 11-mercaptoundecanoic acid (MUA) on Ag₂Se NPs were found to play an important role for efficient extraction of peptides and proteins from test samples through hydrophobic interactions. The peptides can be efficiently extracted using functionalized Ag₂Se NPs as extracting probes in the presence of high concentration of matrix interferences such as 4 M urea, 0.5% Triton X-100 and 3% NaCl. Ag₂Se@ODT NPs have shown better extraction efficiency and detection sensitivity for peptides than Ag₂Se@MUA NPs, bare Ag₂Se NPs and conventional MALDI-MS. The LODs are 20-68 nM for valinomycin and 100-180 nM for gramicidin D using Ag₂Se@ODT NPs-LPME in the MALDI-MS. The current approach is highly sensitive and the target analytes can be effectively isolated without sample loss and efficiently analyzed in MALDI-MS.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.     

Multifunctional ZrO2 nanoparticles and ZrO2-SiO2 nanorods for improved MALDI-MS analysis of cyclodextrins, peptides, and phosphoproteins

Multifunctional ZrO₂ nanoparticles (NPs) and ZrO₂-SiO₂ nanorods (NRs) have been successfully applied as the matrices for cyclodextrins and as affinity probes for enrichment of peptides (leucine-enkephalin, methionine-enkephalin and thiopeptide), phosphopeptides (from tryptic digestion products of β-casein) and phosphoproteins from complex samples (urine and milk) in atmospheric pressure matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) and MALDI time-of-flight (TOF) MS. The results show that the ZrO₂ NPs and ZrO₂-SiO₂ NRs can interact with target molecules (cyclodextrins, peptides, and proteins), and the signal intensities of the analytes were significantly improved in MALDI-MS. The maximum signal intensities of the peptides were obtained at pH 4.5 using ZrO₂ NPs and ZrO₂-SiO₂ NRs as affinity probes. The limits of detection of the peptides were found to be 75-105 fmol for atmospheric pressure MALDI-MS and those of the cyclodextrins and β-casein were found to be 7.5-20 and 115-125 fmol, respectively, for MALDI-TOF-MS. In addition, these nanomaterials can be applied as the matrices for the analysis of cyclodextrins in urine samples by MALDI-TOF-MS. ZrO₂ NPs and ZrO₂-SiO₂ NRs efficiently served as electrostatic probes for peptide mixtures and milk proteins because 2–11 times signal enhancement can be achieved compared with use of conventional organic matrices. Moreover, we have successfully demonstrated that the ZrO₂ NPs can be effectively applied for enrichment of phosphopeptides from tryptic digestion of β-casein. Comparing ZrO₂ NPs with ZrO₂-SiO₂ NRs, we found that ZrO₂ NPs exhibited better affinity towards phosphopeptides than ZrO₂-SiO₂ NRs. Furthermore, the ZrO₂ and ZrO₂-SiO₂ nanomaterials could be used to concentrate trace amounts of peptides/proteins from aqueous solutions without tedious washing procedures. This approach is a simple, straightforward, separation-and washing-free approach for MALDI-MS analysis of cyclodextrins, peptides, proteins, and tryptic digestion products of phosphoproteins.      

Conformational control in a bipyridine linked π-conjugated oligomer: cation mediated helix unfolding and refolding

A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained.     

Benzopentalenonaphthalenones from the intramolecular capture of a merocyanine derived from a naphthopyran

Novel, highly coloured benzopentalenonaphthalenones result from a cascade process initiated by the thermally-induced ring-opening of diarylmethanol substituted 2H-naphtho[1,2-b]pyrans in the presence of acid.