Silver nanoparticles immobilized onto poly(4‐vinylpyridine)‐functionalized magnetic nanoparticles: A robust magnetically recyclable catalyst for oxidant‐free alcohol dehydrogenation

A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4‐vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques.     

Structural basis of pyrazolopyrimidine derivatives as CAMKIIδ kinase inhibitors: insights from 3D QSAR,docking studies and in silico ADMET evaluation

Ca²⁺/calmodulin-dependent protein kinase II (CAMKIIδ) belongs to the serine/threonine kinase family, which is involved in a broad range of cellular events in cell survival and proliferation as well as a number of other signal transduction pathways. Thus, it is regarded a promising target for treatment of cancers. In the present paper, a three-dimensional quantitative structure–activity relationship and molecular docking were applied to investigate a series of new CAMKIIδ inhibitors of pyrazolopyrimidine derivatives. The determination coefficient (R²) and leave-one-out cross-validation coefficient (Q²) of CoMSIA model are 0.676 and 0.956, respectively. The predictive ability of this model was evaluated by the external validation using a test set of eight compounds with a predicted determination coefficient \(R^{ 2}_{\text{test}}\) of 0.80, besides the mean absolute error of the test set was 0.328 log units. Docking results are in concordance with CoMSIA contour maps, gave the information for interactive mode exploration. Based on those satisfactory results, newly designed molecules were predicted with highly potent CAMKIIδ inhibitory activity, additionally, they have showed promising results in the preliminary in silico ADMET evaluations. This study could expand our understanding of pyrazolopyrimidine derivatives as inhibitors of CAMKIIδ and would be of great help in lead optimization for early drug discovery of highly potent CAMKIIδ inhibitors.     

Antioxidant and anticancer activities of α-aminophosphonates containing thiadiazole moiety

In the current study, α-aminophosphonates containing thiadiazole moiety (1–4) was synthesized, characterized and their antioxidant and anticancer activities were carried out. The compounds (1–4) were synthesized from the reaction of 2-amino-5-methyl-1,3,4-thiadiazole with various aldehydes, triphenylphosphite and mixed valence Cu(I)/Cu(II) inorganic coordination polymer as a catalyst. The elucidation of compounds structures were carried out using different spectroscopic techniques. The antioxidant properties were carried out using radical scavenging methods (DPPH) which exhibited excellent scavenging activity particularly with compound 3. The cytotoxic effects of the five compounds on the human hepato cellular carcinoma (HepG2) and breast adeno carcinoma (MCF7) cell lines were evaluated using MTT assay which revealed the presence of cytotoxic effect with highest activity for compound 3 on HepG2 and compound 1 on MCF7. This suggests that these five compounds, particularly compounds 1 and 3, have antioxidant and anticancer effect and could be used as novel chemotherapeutic compounds but this needs further in vivo investigation to confirm our in vitro results.     

Synthesis of novel 3-phenyl-2-oxido/sulfido-1,3,4,2-benzoxadiazaphosphepines

An efficient and facile synthetic approach towards a series of novel 3-phenyl-2-oxido/sulfido-2,3-dihydro-1,3,4,2-benzoxadiazaphosphepines 2–7 was described. The method depended on the cyclocondensation of equimolar ratios of salicylaldehyde phenylhydrazone (1) with different examples of phosphorus halides and phosphorus sulfides in toluene containing triethylamine as a catalyst. In the same manner, the fusion of salicylaldehyde phenylhydrazone (1) with triethyl phosphate in the presence of DBU afforded the 2-ethoxy-1,3,4,2-benzoxa-diazaphosphepine 8, while a fusion of compound 1 with diethyl phosphite and tris(2-chloroethyl)phosphite led to the formation of new examples of 1,2-benzoxaphospholes 9 and 10, respectively. Interestingly, the reaction of compound 1 with diethyl ethoxycarbonyl phosphonate in ethanol containing DBU as a catalyst furnished the chromeno[3,4-d][1,2,3]diazaphosphole derivative 12 as a regioselective product.     

Synthesis,spectroscopic characterization,crystal structure,and anti-bacterial activity of diorganotin(IV) complexes with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone

Three new diorganotin(IV) complexes, [Me₂Sn(BDET] (2), [Bu₂Sn(BDET)] (3), and [Ph₂Sn(BDET)] (4), were synthesized by reacting R₂SnCl₂ (R = Me, Bu, and Ph) with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone [H₂BDET, (1)] in the presence of KOH in absolute methanol. The newly synthesized complexes were characterized by elemental analysis, molar conductivity, UV–vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopies. The molecular structure of 4 was confirmed by X-ray crystallography. X-ray crystallography revealed that the doubly deprotonated O,N,S-tridentate thiosemicarbazone coordinates to tin(IV), resulting in a distorted trigonal bipyramidal geometry. Their ¹H, ¹³C, and ¹¹⁹Sn NMR spectra support a five-coordinate tin(IV) in solution for all complexes, in accord with the solid-state X-ray structure determined for 4. Compounds 1–4 were evaluated for their antibacterial activities against Staphylococcus aureus, Enterobacter aerogenes, Escherichia coli, and Salmonella typhi. The results exhibited that 2–4 were active with comparable potency compared to the standard drug. Antibacterial studies also indicated that the complexes have potential for biological evaluation.     

Enhanced process development using automated continuous reactors by self-optimisation algorithms and statistical empirical modelling

Reaction optimisation and understanding is fundamental for process development and is achieved using a variety of techniques. This paper explores the use of self-optimisation and experimental design as a tandem approach to reaction optimisation. A Claisen-Schmidt condensation was optimised using a branch and fit minimising algorithm, with the resulting data being used to fit a response surface model. The model was then applied to find new responses for different metrics, highlighting the most important for process development purposes.     

GC-MS analysis of the bioactive phytoconstituents of various organic crude extracts from the seed kernels of Manilkara bidentata (balata) collected in Trinidad,W.I.

The present study reports the first phytochemical investigation of the seed kernels of Manilkara bidentata (Balata) harvested in Trinidad, W.I. Gas chromatography–mass spectrometry (GC-MS) analysis of the n-hexane, chloroform, ethyl acetate, ethanol and methanol extracts showed a total of 39 components. 2,6,10,14,18-pentamethyl-2,6,10,14,18-eicosapentaene (74.93%), 9-octadecenoic acid, (Z)- 2,3-dihydroxypropyl ester (79.98%), (Z)-ethyl oleate (92.75%), Z,E-2-methyl-3,13-octadecadien-1-ol (80.51%) and 5-(hydroxymethyl)-2-furancarboxyaldehyde (50.32%) were the major constituents identified in the n-hexane, chloroform, ethyl acetate, ethanol and methanol extracts, respectively. The extracts showed the presence of several bioactive components and provides reference data for further research of its active constituents.     

Ternary complexes in gels from agarose and from chemically‐modified agarose

Thermodynamic data and mechanical measurements are shown for gels prepared in aqueous binary solvents (water/DMSO, water/DMF, water/methyl formamide and water/formamide). When electrostatic interactions, as opposed to hydrogen bonding, can be established with the cosolvent (DMSO, DMF, methyl formamide) we come to the conclusion that ternary complexes are formed (agarose/water/cosolvent). In the case of chemically‐modified agarose (OH groups replaced by OCH₃ groups) we suggest that these cosolvents are directly involved in the formation of the gel.     

Determining concentration depth profiles in fluorinated networks by means of electric force microscopy

By means of electric force microscopy, composition depth profiles were measured with nanometric resolution for a series of fluorinated networks. By mapping the dielectric permittivity along a line going from the surface to the bulk, we were able to experimentally access to the fluorine concentration profile. Obtained data show composition gradient lengths ranging from 30 nm to 80 nm in the near surface area for samples containing from 0.5 to 5 wt. % F, respectively. In contrast, no gradients of concentration were detected in bulk. This method has several advantages over other techniques because it allows profiling directly on a sectional cut of the sample. By combining the obtained results with x-ray photoelectron spectroscopy measurements, we were also able to quantify F/C ratio as a function of depth with nanoscale resolution.     

Targeted quantitative bioanalysis in plasma using liquid chromatography/high-resolution accurate mass spectrometry: an evaluation of global selectivity as a function of mass resolving power and extraction window, with comparison of centroid and profile modes

There is a growing interest in exploring the use of liquid chromatography coupled with full-scan high resolution accurate mass spectrometry (LC/HRMS) in bioanalytical laboratories as an alternative to the current practice of using LC coupled with tandem mass spectrometry (LC/MS/MS). Therefore, we have investigated the theoretical and practical aspects of LC/HRMS as it relates to the quantitation of drugs in plasma, which is the most commonly used matrix in pharmacokinetics studies. In order to assess the overall selectivity of HRMS, we evaluated the potential interferences from endogenous plasma components by analyzing acetonitrile-precipitated blank human plasma extract using an LC/HRMS system under chromatographic conditions typically used for LC/MS/MS bioanalysis with the acquisition of total ion chromatograms (TICs) using 10 k and 20 k resolving power in both profile and centroid modes. From each TIC, we generated extracted ion chromatograms (EICs) of the exact masses of the [M + H](+) ions of 153 model drugs using different mass extraction windows (MEWs) and determined the number of plasma endogenous peaks detected in each EIC. Fewer endogenous peaks are detected using higher resolving power, narrower MEW, and centroid mode. A 20 k resolving power can be considered adequate for the selective determination of drugs in plasma. To achieve desired analyte EIC selectivity and simultaneously avoid missing data points in the analyte EIC peak, the MEW used should not be too wide or too narrow and should be a small fraction of the full width at half maximum (FWHM) of the profile mass peak. It is recommended that the optimum MEW be established during method development under the specified chromatographic and sample preparation conditions. In general, the optimum MEW, typically ≤ ±20 ppm for 20 k resolving power, is smaller for the profile mode when compared with the centroid mode.