Highly efficient, one-step macrocyclizations leading to the formation of macrocyclic hexa(aramides) in high yields (69-82%) are described. The one-step macrocyclizations were facilitated by the preorganization or folding of the backbones of uncyclized precursors in the course of macrocyclization. The preorganization of backbones was achieved by the presence of localized three-centered hydrogen bonds that were adopted in the design of a class of closely related, backbone-rigidified foldamers. The macrocyclization involved reactions between diacid chloride 1 and diamine 2. The crude reaction mixtures and products were conveniently examined by mass spectrometric method (MALDI-TOF). Compared to most traditional one-step macrocyclizations that usually require high dilution conditions and often lead to very low overall yields of the desired products, cyclic hexamers 3 were obtained as the overwhelmingly major product under a variety of reaction conditions, suggesting the generality of this approach. 相似文献
Surface modification of fabrics is a powerful strategy that can endow fabrics with desired effects while keeping the intrinsic properties. Herein, an ordinary strategy, dipping-drying based layer-by-layer self-assembly (LbL) coating, is reported to functionalize fabrics’ surfaces. Firstly, the novel cation waterborne polyurethanes (QAHDPU) and anion waterborne polyurethanes (HDPU) are successfully designed and synthesized. By incorporating targeted molecule, hydantoin diol (HD) and quaternary ammonium salt with long alkyl chain (DOQA), the QAHDPU are antibacterial and hydrophobically functionalized. Taking advantage of strong adhesion, waterborne polyurethanes (WPUs) are physically bonded to surfaces of fabrics to generate durable antibacterial and hydrophobic fabrics. The QAHDPU with long alkyl chain combined with rough and porous fabric surface fabricates hydrophobic fabric surface, which can prevent bacteria from adhering to the fabrics. Furthermore, the coated fabrics present excellent antibacterial properties after chlorination, forming a second barrier against bacteria. The chlorinated coated fabrics, can inactivate 85.0–99.9% of Staphylococcus aureus and 85.0–97.7% of Escherichia coli with contact time of 60 min. The hydrophobic properties of coated fabrics are greatly improved with water contact angles of 122.0°–141.1°. In addition, the proposed method is applicable for a variety of fibers and expected to be used for industrial production.
Cellulose gel with < 10% of crystallinity was prepared by treatment of microcrystalline cellulose, Avicel, with zinc chloride
solution at a ratio of zinc chloride to cellulose from 1.5 to 18 (w/w). The presence of zinc ions in the cellulose gels enhanced
the rate of hydrolysis and glucose yield. The evidence obtained from X-ray diffraction, iodine absorption experiments; and
Nuclear Magnetic Resonance spectra analysis suggested the presence of zinc-cellulose complex after Avicel was treated with
zinc chloride. Zinc-cellulose complex was more susceptible to hydrolysis than amorphous cellulose. Under the experimental
condition, cellulose gels with zinc ions were hyrolyzed to glucose with 95% theoretical yield and a concentration of 14% (w/v)
by cellulases within 20 h. The same gel was hydrolyzed by acid to glucose with 91.5% yield and a concentration of 13.4% (w/v). 相似文献
A new flow injection-kinetic method has been developed for the determination of trace amount of osmium(WI), based on its catalytic effect on the bromopyrogallol red and hydrogen peroxide reaction. The reaction is followed spectrophotometrically by measuring the decrease in absorbance at 559 nm. The calibration graph for osmium(VIII) is linear over the range from 0.0040 to 0.10 μg/ml and the detection limit and sampling frequency are 0.0030 μg/ml and 47 per hour, respectively. The proposed method was applied to the determination of trace amounts of osmium in refined ores and chlorination residues with satisfactory results. 相似文献
By use of the three-layer diffusion method, reactions of flexible bipyridyl ligands (4,4′-bpp or 3,3′-bpp) with M(II) salts (M = Zn, Cd) and multi-carboxylate ligands resulted in the formation of four interesting d10 metal–organic coordination polymers: [Zn(μ-4,4′-bpp)Br2]n (1), [Zn(μ-4,4′-bpp)(1,2-bdc)]n · nH2O (2), [Zn(μ-3,3′-bpp)(1,3-bdc)]n · nCH3OH · 2nH2O (3) and [Cd(μ-3,3′-bpp)(C4H2O4)]n · 3nH2O (4) (4,4′-bpp = 2,2′-bis(4-pyridylmethyleneoxy)-1,1′-biphenylene; 3,3′-bpp = 2,2 ′-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene; bdc=benzenedicarboxylate, C4H4O4 = fumaric acid). Complex 1 has a 2D sheet structure consisting of two unusual zigzag Zn(II) chains which are nearly perpendicular to each other. Complex 2 is comprised of two-leg ladders, in which [Zn(4,4′-bpp)] chains serve as the side rails and 1,2-bdc ligands serve as the cross rungs. In complex 3, every two 1,3-bdc ligands connect the neighbouring Zn(II)-3,3′-bpp dimetallic rings in η1 coordination modes into an interesting chain structure. Complex 4 consists of an anionic macrocycle-containing cadmium dicarboxylate sheets that are separated by 3,3′-bpp. These d10 metal complexes exhibit high thermal stabilities and strong luminescence efficiencies. 相似文献
Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues. 相似文献
A new abietane diterpene 12-hydroxy-7-oxo-5, 8, 11, 13-tetraene-18, 6-abietanolide, together with a new natural sterol stigmasta-7, 22-diene-3β, 5α, 6α-triol have been isolated from the fruiting body of the fungus Phellinus igniarius. Their structures were elucidated by spectroscopic methods including 2D NMR techniques. 相似文献
This work emphasizes easy access to α-vinyl and aryl amino acids via Ni-catalyzed cross-electrophile coupling of bench-stable N-carbonyl-protected α-pivaloyloxy glycine with vinyl/aryl halides and triflates. The protocol permits the synthesis of α-amino acids bearing hindered branched vinyl groups, which remains a challenge using the current methods. On the basis of experimental and DFT studies, simultaneous addition of glycine α-carbon (Gly) radicals to Ni(0) and Ar–Ni(ii) may occur, with the former being more favored where oxidative addition of a C(sp2) electrophile to the resultant Gly–Ni(i) intermediate gives a key Gly–Ni(iii)–Ar intermediate. The auxiliary chelation of the N-carbonyl oxygen to the Ni center appears to be crucial to stabilize the Gly–Ni(i) intermediate.We have developed Ni-catalyzed reductive coupling of N-carbonyl protected α-pivaloyloxy glycine with Csp2-electrophiles that enabled facile preparation of α-amino acids, including those bearing hindered branched vinyl groups.相似文献