Use of ambient ionization high-resolution mass spectrometry for the kinetic analysis of organic surface reactions

In contrast to homogeneous systems, studying the kinetics of organic reactions on solid surfaces remains a difficult task due to the limited availability of appropriate analysis techniques that are general, highthroughput, and capable of offering quantitative, structural surface information. Here, we demonstrate how direct analysis in real time mass spectrometry (DART-MS) complies with above considerations and can be used for determining interfacial kinetic parameters. The presented approach is based on the use of a MS tag that in principle allows application to other reactions. To show the potential of DART-MS, we selected the widely applied strain-promoted alkyne−azide cycloaddition (SPAAC) as a model reaction to elucidate the effects of the nanoenvironment on the interfacial reaction rate

Homocysteine and Familial Longevity: The Leiden Longevity Study

Homocysteine concentrations are a read-out of methionine metabolism and have been related to changes in lifespan in animal models. In humans, high homocysteine concentrations are an important predictor of age related disease. We aimed to explore the association of homocysteine with familial longevity by testing whether homocysteine is lower in individuals that are genetically enriched for longevity. We measured concentrations of total homocysteine in 1907 subjects from the Leiden Longevity Study consisting of 1309 offspring of nonagenarian siblings, who are enriched with familial factors promoting longevity, and 598 partners thereof as population controls. We found that homocysteine was related to age, creatinine, folate, vitamin B levels and medical history of hypertension and stroke in both groups (all p<0.001). However, levels of homocysteine did not differ between offspring enriched for longevity and their partners, and no differences in the age-related rise in homocysteine levels were found between groups (p for interaction 0.63). The results suggest that homocysteine metabolism is not likely to predict familial longevity

19 nm‐Thick Grafted‐To Polymer Brushes onto Optimized Poly(Dopamine)‐Coated Surfaces

Abstract Grafting‐to polymer coatings are typically easy to apply, but the thickness of such coatings is typically limited to a few nanometers, which may hamper applications. This paper presents a grafting‐to coating approach that yields polymer brushes up to an unprecedented thickness of 19 nm. To this aim, an easy‐to‐apply poly(dopamine) (PDA) primer layer is optimized. PDA is an easy‐to‐apply, but highly complex and chemically not well understood primer layer. In this study, PDA is deposited on silicon substrates using several deposition protocols (pH 4–7 in presence of NaIO4, and from Tris solution at pH 8.5). The modified surfaces are characterized using X‐ray photoelectron spectroscopy, spectroscopic ellipsometry, static water contact angle measurements, and atomic force microscopy. Subsequently, block copolymers of poly(glycidyl methacrylate)20‐b‐poly(N‐isopropylacrylamide)n are attached onto the PDA films using a grafting‐to approach. The results indicate that the conditions of PDA deposition and the PDA film thickness strongly influence the stability and grafting efficiency of the block copolymers. PDA films deposited at pH 7 with NaIO4 are stable, and yield the most efficient grafting, with grafted polymer layers as thick as 19 nm. Polymer layers of such thickness are rarely achieved using grafting‐to procedures from solution

Structure and Long-Term Stability of Alkylphosphonic Acid Monolayers on SS316L Stainless Steel

Surface modification of stainless steel (SS316L) to improve surface properties or durability is an important avenue of research, as SS316L is widely used in industry and science. We studied, therefore, the formation and stability of a series of organic monolayers on SS316L under industrially relevant conditions. These included acidic (pH 3), basic (pH 11), neutral (Milli-Q water), and physiological conditions [10 mM phosphate-buffered saline (PBS)], as well as dry heating (120 °C). SS316L was modified with alkylphosphonic acids of chain length (CH₂)_<i>n</i> with <i>n</i> varying between 3 and 18. While alkylphosphonic acids of all chain lengths formed self-assembled monolayers with hydrophobic properties, only monolayers of chain lengths 12–18 formed ordered monolayers, as evidenced by static water contact angle (SCA), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and infrared reflection absorption spectroscopy (IRRAS). A long-term stability study revealed the excellent stability of monolayers with chain lengths 12–18 for up to 30 days in acid, neutral, and physiological solutions, and for up to 7 days under dry heating. Under strong basic conditions a partial breakdown of the monolayer was observed, especially for the shorter chain lengths. Finally, the effect of multivalent surface attachment on monolayer stability was explored by means of a series of divalent bisphosphonic acids

Quantitative Understanding of Guest Binding Enables the Design of Complex Host–Guest Behavior

We report a detailed binding study addressing both the thermodynamics and kinetics of binding of a large set of guest molecules with widely varying properties to a water-soluble M₄L₆ metal–organic host. The effects of different guest properties upon the binding strength and kinetics were elucidated by a systematic analysis of the binding data through principal component analysis, thus allowing structure–property relationships to be determined. These insights enabled us to design more complex encapsulation sequences in which multiple guests that were added simultaneously were bound and released by the host in a time-dependent manner, thus allowing multiple states of the system to be accessed sequentially. Moreover, by inclusion of the pH-sensitive guest pyridine, we were able to further extend our control over the binding by creating a reversible pH-controlled three-guest sequential binding cycle