Synthesis and in vitro cytotoxicity of novel dinuclear platinum(II) complexes containing a chiral tetradentate ligand

A series of novel dinuclear platinum(II) complexes with a chiral tetradentate ligand, (1R,1′R,2R,2′R)-N¹,N¹′-(1,2-phenylenebis(methylene))dicyclohexane-1,2-diamine (HL), and mono-carboxylic acid derivatives as ligands have been designed, synthesized, and characterized. In vitro cytotoxicity evaluation of synthesized complexes against human HepG-2, A549, HCT-116, and MCF-7 cancer cell lines has been conducted by MTT assays. All compounds showed antitumor activity to HepG-2 and HCT-116 cell lines. Compound L2 exhibited better cytotoxicity than that of carboplatin against HepG-2 and A549 cell lines and also showed comparable activity against HCT-116 cell line.     

New reagent for the introduction of Boc protecting group to amines: Boc-OASUD

A new reagent, tert-butyl (2,4-dioxo-3-azaspiro [5,5] undecan-3-yl) carbonate (Boc-OASUD) for the preparation of N-Boc-amino acids is described. The Boc-OASUD reacts with amino acids and their esters at room temperature in the presence of a base and gives N-Boc-amino acids and their esters in good yields and purity. Introduction of the Boc group takes place without racemization. The Boc-OASUD, being a solid and more stable, is a better alternative to di-tert-butyl dicarbonate which is low melting and has to be dispensed in plastic containers than glass because of its poor stability.     

Pd(II)-catalyzed cascade Heck/intramolecular C(sp2)–H amidation reaction: An efficient route to 4-aryl-2-quinolinones

A Pd(II)-catalyzed cascade Heck/intramolecular C(sp²)–H amidation reaction is described for the synthesis of 4-aryl-2-quinolinone derivatives. Substituted cinnamamide containing 2-(pyridin-2-yl)ethanamine unit reacts with aryl iodide to form intermediate by Heck reaction. Then, the intermediate takes place intramolecular amidation via C(sp²)–H activated process promoted by orientation group.     

Efficient synthesis of N-nosyl-protected 3-azabicyclo[4.3.0]nonen-8-one by an aniline- and nitrobenzene-mediated Pauson–Khand cyclization

The intramolecular Pauson–Khand cyclization in the presence of both aniline and nitrobenzene was used to improve the construction of N-nitrobenzenesulfonyl-protected 3-azabicyclo[4.3.0]nonane skeletons. We found that aniline enhanced the cyclization and that nitrobenzene prevents the concurrent reduction in this process. This combination of mediators allows for the efficient synthesis of bioactive azabicyclic nonane-type alkaloids and the use of milder deprotection conditions in the synthetic route.     

New phosphorylating reagents for deoxyribonucleosides and oligonucleotides

New phosphorylating reagents 1 and 2 were prepared in three steps from 4-hydroxybenzaldehyde. They showed good efficiency in the solid phase synthesis of 5′-phosphate monoester nucleosides. End-phosphate DNA sequence synthesis demonstrated the efficiency of the new reagents (1 and 2) according to the general procedure of automated DNA synthesis. The oxidation of P(III) to P(V) and the removal of benzyl protecting groups were achieved in a single step by treatment with a 0.02 M I₂/pyridine/H₂O solution. Due to this one-pot treatment, it is possible to use the phosphorylating reagents (1 and 2) for the synthesis of base-sensitive ODNs. The reagents 1 and 2 are unique among phosphorylating reagents.     

Syntheses of N-aryl-protected glucosamines and their stereoselectivity in chemical glycosylations

N-Aryl-protecting groups were introduced in glucosamines to achieve β-selective glycosylation. Various N-aryl aminosugars were synthesized via Buchwald–Hartwig reaction. Glycosylation using glycosyl trichloroacetimidates of N-aryl aminosugars smoothly proceeded in the presence of trimethylsilyl trifluoromethanesulfonate. Use of a glycosyl donor comprising an electron-donating 2,4-dimethoxyphenyl (DMP) group led to the glycosylation proceeding with high β selectivity. This stereoselectivity seemed to be derived from the formation of an aziridine intermediate. The DMP-protecting group can be removed immediately by using ammonium hexanitratocerate (IV).     

X‐ray induced degradation of surface bound azido groups during XPS analysis

Mesoporous silica SBA‐15 was synthesized and silanized with azidopropyl triethoxysilane in order to design a clickable material. Fourier transform infrared analysis permitted to prove the attachment of the azidopropylene groups to SBA‐15 resulting in the reactive and functional material N₃‐SBA‐15. X‐ray photoelectron spectroscopy was used to determine the surface composition of SBA‐15. However, we unexpectedly found that the surface bound azido groups undergo X‐ray induced decomposition during the X‐ray photoelectron spectroscopy analysis resulting in the formation of nitrenes. These are very reactive groups able to intercalate C―C and C―H bonds of the propylene chains as judged from the N1s peak shape. Possible mechanisms of intercalation are suggested. C1s and N1s peaks were recorded at different exposure time. N/C, N⁺/N and N⁺/C undergo exponential decay. N⁺/N reaches the value of zero in less than 80 min of exposure to the X‐ray source. The N⁺/C decay plot was fitted with first‐order kinetics, and the decomposition kinetic constant (k_dec) was found to equal to 516.4 s^?1. This is a fast X‐ray induced degradation which must be considered with care when examining clickable materials with surface bound alkyl azido groups. Copyright © 2016 John Wiley & Sons, Ltd.     

Adsorbing behavior of polycarboxylate superplasticizer in the presence of the ester group in side chain

The effect of the ester group in side chain on adsorbing behavior and dispersion of polycarboxylate superplasticizer (PC) was studied by comparing the performance of two types of PC. The fluidity of cement paste was tested to discuss the dispersing ability and dispersing retention ability of PC. The total organic carbon analyzer was used to measure the adsorption amount, and the adsorption layer was obtained by x-ray photoelectron spectroscopy. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and pH value were used to verify the stability of the ester group, and the electrokinetic properties of cement particle were confirmed using the zeta potential measurement. The results show that the ester group in side chain reduces the initial dispersing ability while it increases the dispersing retention ability. The dispersing retention ability depends on the increase of adsorption amount and adsorption layer in 5–60 minutes, and the greater increase leads to the better dispersing retention ability. The ester group can be decomposed to release carboxyl group to enhance the adsorbing ability of PC under the condition of cement hydration, which is the main reason for the greater increase of adsorption amount and adsorption layer and the improvement in dispersing retention ability. It suggests that grafting the ester group is a good way to enhance the dispersing retention ability.     

Unusual electro-optical behaviour of the nematic polyacrylate

ABSTRACT

High sensitivity of liquid crystals to the electric field makes them highly demanded and widely used in different applications. Despite the large number of the electro-optical research on the low-molar-mass liquid crystals electro-optics of the liquid crystalline (LC) polymers is much less studied. Herein, the comparative electro-optical behaviour of two nematic comb-shaped polyacrylates with phenylbenzoate mesogenic side groups was studied in detail. These two polyacrylates have completely the same structure of polymer backbone and spacer length but different in the direction of the ester group in the phenylbenzoate fragments. It was found that this difference predetermines their completely opposite electro-optical properties.

The influence of the electric field of different strength and frequency on the orientation of the mesogenic groups of these polymers is studied. It is shown that application of the electric field at temperatures above the glass transition temperature (~25°C) induces reorientation of the mesogenic groups along or perpendicular to the electric field direction depending in its turn on the ester group direction. For one of the polyacrylates an unusual textural transition is found; during cooling of the polymer sample under applied field at definite temperature a sharp change in the mesogen’s orientation from homeotropic to planar one is found. This electro-optical phenomenon is observed for the first time and probably associated with sharp change in sign of anisotropy of dielectric permittivity from positive (at high temperatures) to negative one (at lower temperatures). Kinetics of the electro-optical switching at different temperatures, influence of the molar masses of the polymer and frequency of the applied AC field on electro-optical behaviour of the polymers are studied. The possibility of the fixation of the electroinduced homeotropic alignment of the mesogenic groups by photopolymerisation of the diacrylate dissolved in the polymer is demonstrated.     

Synthesis and properties of allyloxy-based tolane liquid crystals with high negative dielectric anisotropy

A series of tolane liquid crystals (LCs) containing 2,3-difluorophenyl and allyloxy terminal groups have been synthesised via multi-step reactions. Their thermotropic mesophases, birefringences and dielectric anisotropy properties are discussed by comparison with the non-fluorinated analog. The results show that the allyloxy-based tolane LC 3TOV reveals a high value of the birefringence (0.29), negative dielectric anisotropy (?4.44) and a broad nematic mesophase with a low melting point and high clearing point. The effects of the terminal alkyl chains, the lateral fluoro substituents, the allyloxy terminal group and alkyne bridge on the mesomorphic and physical properties were also discussed. Meanwhile, Density Functional Theory (DFT) calculations of molecular conformation and polarisability were used to correlate the experimental findings.