Phase-selective solubility of poly(N-alkylacrylamide)s

The extent of the phase-selective solubility of poly(N-alkylacrylamide)s was studied by UV-vis and fluorescence spectroscopy using poly(N-isopropylacrylamide) and poly(N-octadecylacrylamide) as representative polar and nonpolar poly(N-alkylacrylamide)s in a mixture of polar and nonpolar thermomorphic solvents. Phase-selective solubilities of greater than 10000:1 were seen with each labeled polymer in polar and nonpolar solvents such as heptane and DMF or heptane and 90% EtOH-H(2)O. Using a poly(N-acryloxysuccinimide) as a common precursor, a pool-split synthesis was devised to prepare a library of poly(N-alkylacrylamide)s whose members varied only in the size of their N-alkyl substituent. The solubilities of these library members were measured in both the polar and nonpolar phases of a thermomorphic heptane/90% EtOH-H(2)O mixture at 25 degrees C. Such solvent mixtures are miscible hot (70 degrees C) and biphasic cold (25 degrees C). The results show that poly(N-pentylacrylamide) is selectively soluble (>99.5%) in the polar EtOH-rich phase at rest. Poly(N-alkylacrylamide)s with larger N-alkyl groups are predominantly (C(6), 85%; C(7), 95%) or exclusively (>C(8), >99.5%) in the heptane-rich phase at rest.     

X-ray studies of self-assembled organic monolayers grown on hydrogen-terminated Si(111)

The structure of self-assembled monolayers (SAMs) of undecylenic acid methyl ester (SAM-1) and undec-10-enoic acid 2-bromo-ethyl ester (SAM-2) grown on hydrogen-passivated Si(111) were studied by X-ray reflectivity (XRR), X-ray standing waves (XSW), X-ray fluorescence (XRF), atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The two different SAMs were grown by immersion of H-Si(111) substrates into the two different concentrated esters. UV irradiation during immersion was used to create Si dangling bond sites that act as initiators of the surface free-radical addition process that leads to film growth. The XRR structural analysis reveals that the molecules of SAM-1 and SAM-2 respectively have area densities corresponding to 50% and 57% of the density of Si(111) surface dangling bonds and produce films with less than 4 angstroms root-mean-square roughness that have layer thicknesses of 12.2 and 13.2 angstroms. Considering the molecular lengths, these thicknesses correspond to a 38 degrees and 23 degrees tilt angle for the respective molecules. For SAM-2/Si(111) samples, XRF analysis reveals a 0.58 monolayer (ML) Br total coverage. Single-crystal Bragg diffraction XSW analysis reveals (unexpectedly) that 0.48 ML of these Br atoms are at a Si(111) lattice position height that is identical to the T1 site that was previously found by XSW analysis for Br adsorbed onto Si(111) from a methanol solution and from ultrahigh vacuum. From the combined XPS, XRR, XRF, and XSW evidence, it is concluded that Br abstraction by reactive surface dangling bonds competes with olefin addition to the surface.     

In vitro cytotoxicity evaluation of thiourea derivatives bearing Salix sp. constituent against HK-1 cell lines

Abstract

In searching for drugs from natural product scaffolds has gained interest among researchers. In this study, a series of twelve halogenated thiourea (ATX 1-12) via chemical modification of aspirin (a natural product derivative) and evaluated for cytotoxic activity against nasopharyngeal carcinoma (NPC) cell lines, HK-1 via MTS-based colorimetric assay. The cytotoxicity studies demonstrated that halogens at meta position of ATX showed promising activity against HK-1 cells (IC₅₀ value ≤15?µM) in comparison to cisplatin, a positive cytotoxic drug (IC₅₀ value =8.9?±?1.9?µM). ATX 11, bearing iodine at meta position, showed robust cytotoxicity against HK-1 cells with an IC₅₀ value of 4.7?±?0.7?µM. Molecular docking interactions between ATX 11 and cyclooxygenase-2 demonstrated a robust binding affinity value of ?8.1?kcal/mol as compared to aspirin’s binding affinity value of ?6.4?kcal/mol. The findings represent a promising lead molecule from natural product with excellent cytotoxic activity against NPC cell lines.     

Glycosidic linkage,N‐acetyl side‐chain,and other structural properties of methyl 2‐acetamido‐2‐deoxy‐β‐d‐glucopyranosyl‐(1→4)‐β‐d‐mannopyranoside monohydrate and related compounds

The crystal structure of methyl 2‐acetamido‐2‐deoxy‐β‐d ‐glycopyranosyl‐(1→4)‐β‐d ‐mannopyranoside monohydrate, C₁₅H₂₇NO₁₁·H₂O, was determined and its structural properties compared to those in a set of mono‐ and disaccharides bearing N‐acetyl side‐chains in βGlcNAc aldohexopyranosyl rings. Valence bond angles and torsion angles in these side chains are relatively uniform, but C—N (amide) and C—O (carbonyl) bond lengths depend on the state of hydrogen bonding to the carbonyl O atom and N—H hydrogen. Relative to N‐acetyl side chains devoid of hydrogen bonding, those in which the carbonyl O atom serves as a hydrogen‐bond acceptor display elongated C—O and shortened C—N bonds. This behavior is reproduced by density functional theory (DFT) calculations, indicating that the relative contributions of amide resonance forms to experimental C—N and C—O bond lengths depend on the solvation state, leading to expectations that activation barriers to amide cis–trans isomerization will depend on the polarity of the environment. DFT calculations also revealed useful predictive information on the dependencies of inter‐residue hydrogen bonding and some bond angles in or proximal to β‐(1→4) O‐glycosidic linkages on linkage torsion angles ? and ψ. Hypersurfaces correlating ? and ψ with the linkage C—O—C bond angle and total energy are sufficiently similar to render the former a proxy of the latter.