Adhesion and friction properties of fluoropolymer brushes: on the tribological inertness of fluorine.

The effects of fluorination on the adhesion and friction properties of covalently bound poly(fluoroalkyl methacrylate) polymer brushes (thickness ∼80 nm) were systematically investigated. Si(111) surfaces were functionalized with a covalently bound initiator via a thiol-yne click reaction to have a high surface coverage for initiator immobilization. Surface-initiated atom-transfer radical polymerization (SI-ATRP) was employed for the synthesis of four different fluoropolymer brushes (SPFx, where x = 0, 3, 7, or 17 F atoms per monomer), based on fluoroalkyl methacrylates.

Hydrolytic and thermal stability of organic monolayers on various inorganic substrates.

A comparative study is presented of the hydrolytic and thermal stability of 24 different kinds of monolayers on Si(111), Si(100), SiC, SiN, SiO2, CrN, ITO, PAO, Au, and stainless steel surfaces. These surfaces were modified utilizing appropriate organic compounds having a constant alkyl chain length (C18), but with different surface-reactive groups, such as 1-octadecene, 1-octadecyne, 1-octadecyltrichlorosilane, 1-octadecanethiol, 1-octadecylamine and 1-octadecylphosphonic acid. The hydrolytic stability of obtained monolayers was systematically investigated in triplicate in constantly flowing aqueous media at room temperature in acidic (pH 3), basic (pH 11), phosphate buffer saline (PBS) and deionized water (neutral conditions), for a period of 1 day, 7 days, and 30 days, yielding 1152 data points for the hydrolytic stability.

Adhesion and friction properties of polymer brushes: fluoro versus nonfluoro polymer brushes at varying thickness.

A series of different thicknesses of fluoro poly(2,2,2-trifluoroethyl methacrylate) and its analogous nonfluoro poly(ethyl methacrylate) polymer brushes were prepared via surface-initiated ATRP (SI-ATRP) on Si(111) surfaces. The thiol-yne click reaction was used to immobilize the SI-ATRP initiator with a high surface coverage, in order to achieve denser polymer brushes (grafting density from ~0.1 to 0.

Ambient surface analysis of organic monolayers using direct analysis in real time Orbitrap mass spectrometry.

A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au).

Efficient functionalization of oxide-free silicon(111) surfaces: thiol-yne versus thiol-ene click chemistry.

Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol-ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbonyl cysteine, thio-β-d-glucose tetraacetate, thioacetic acid, thioglycerol, thioglycolic acid, and 1H,1H,2H,2H-perfluorodecanethiol was immobilized using TYC under photochemical conditions, and all modified surfaces were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy (including a simulation thereof by density functional calculations), and infrared absorption reflection spectroscopy. Surface-bound TYC proceeds with an efficiency of up to 1.