Platform Synthetic Lectins for Divalent Carbohydrate Recognition in Water

Biomimetic carbohydrate receptors (“synthetic lectins”) have potential as agents for biological research and medicine. However, although effective strategies are available for “all‐equatorial” carbohydrates (glucose, etc.), the recognition of other types of saccharide under natural (aqueous) conditions is less well developed. Herein we report a new approach based on a pyrene platform with polar arches extending from aryl substituents. The receptors are compatible with axially substituted carbohydrates, and also feature two identical binding sites, thus mimicking the multivalency observed for natural lectins. A variant with negative charges forms 1:2 host/guest complexes with aminosugars, with K₁>3000 m ^?1 for axially substituted mannosamine, whereas a positively charged version binds the important α‐sialyl unit with K₁≈1300 m ^?1.     

Rapid analysis of N-methylpyrrolidine in cefepime with thermal desorption ion mobility spectrometry

N-methyl-pyrrolidine (NMP) a potential impurity in the cephalosporin antibiotic cefepime is analysed using a rapid thermal desorption – ion mobility spectrometry (TD-IMS) method. The thermal desorption approach is shown to be capable of rapidly extracting NMP from the cefepime at 80 °C without causing thermal degradation of the cefepime. The ion mobility method has an analysis time of 1 min and demonstrates good linearity over a range from 0.3–3.0 μg ml^?1 of NMP, with limits of detection and quantification of 0.056 and 0.1875 μg ml^?1 respectively. The developed method was applied to the analysis of a cefepime sample and determined that NMP was present in a cefepime sample at a level of 0.0376 % with a percentage relative standard deviation (n = 6) of 3.2 %. This was compared with a LC-UV method which was in close agreement measuring NMP at 0.0384 % in the cefepime sample with a percentage RSD (n = 6) of 5.7 %. These results show that the TD-IMS method gives comparable data to the established LC methods and demonstrates the potential of TD-IMS for rapid measurement of volatile compounds in pharmaceutical matrices.     

Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations

Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular‐scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na?SO₄ exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K?SO₄ show significantly less clustering under equivalent conditions. In mixed systems (Na_xK_2?xSO₄), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure‐breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K⁺ and SO₄^2?, compared with the analogous Na⁺?SO₄^2? interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na?K?SO₄. Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium–sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting‐in in ternary hydrothermal solutions of Na?K?SO₄ reflects the opposing, but complementary, natures of Na?SO₄ versus K?SO₄ interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system.     

Quantum Ergodicity for Quantum Graphs without Back-Scattering

We give an estimate of the quantum variance for d-regular graphs quantised with boundary scattering matrices that prohibit back-scattering. For families of graphs that are expanders, with few short cycles, our estimate leads to quantum ergodicity for these families of graphs. Our proof is based on a uniform control of an associated random walk on the bonds of the graph. We show that recent constructions of Ramanujan graphs, and asymptotically almost surely, random d-regular graphs, satisfy the necessary conditions to conclude that quantum ergodicity holds.     

New figuring model based on surface slope profile for grazing‐incidence reflective optics

Surface slope profile is widely used in the metrology of grazing‐incidence reflective optics instead of surface height profile. Nevertheless, the theoretical and experimental model currently used in deterministic optical figuring processes is based on surface height, not on surface slope. This means that the raw slope profile data from metrology need to be converted to height profile to perform the current height‐based figuring processes. The inevitable measurement noise in the raw slope data will introduce significant cumulative error in the resultant height profiles. As a consequence, this conversion will degrade the determinism of the figuring processes, and will have an impact on the ultimate surface figuring results. To overcome this problem, an innovative figuring model is proposed, which directly uses the raw slope profile data instead of the usual height data as input for the deterministic process. In this paper, first the influence of the measurement noise on the resultant height profile is analyzed, and then a new model is presented; finally a demonstration experiment is carried out using a one‐dimensional ion beam figuring process to demonstrate the validity of our approach.     

Gelatin Nanoparticles with Enhanced Affinity for Calcium Phosphate

Gelatin nanoparticles can be tuned with respect to their drug loading efficiency, degradation rate, and release kinetics, which renders these drug carriers highly suitable for a wide variety of biomedical applications. The ease of functionalization has rendered gelatin an interesting candidate material to introduce specific motifs for selective targeting to specific organs, but gelatin nanoparticles have not yet been modified to increase their affinity to mineralized tissue. By means of conjugating bone‐targeting alendronate to biocompatible gelatin nanoparticles, a simple method is developed for the preparation of gelatin nanoparticles which exhibit strong affinity to mineralized surfaces. It has been shown that the degree of alendronate functionalization can be tuned by controlling the glutaraldehyde crosslinking density, the molar ratio between alendronate and glutaraldehyde, as well as the pH of the conjugation reaction. Moreover, it has been shown that the affinity of gelatin nanoparticles to calcium phosphate increases considerably upon functionalization with alendronate. In summary, gelatin nanoparticles have been developed, which exhibit great potential for use in bone‐specific drug delivery and regenerative medicine.

     

Reverse mathematics,well-quasi-orders,and Noetherian spaces

A quasi-order Q induces two natural quasi-orders on \({\mathcal{P}(Q)}\), but if Q is a well-quasi-order, then these quasi-orders need not necessarily be well-quasi-orders. Nevertheless, Goubault-Larrecq (Proceedings of the 22nd Annual IEEE Symposium 4 on Logic in Computer Science (LICS’07), pp. 453–462, 2007) showed that moving from a well-quasi-order Q to the quasi-orders on \({\mathcal{P}(Q)}\) preserves well-quasi-orderedness in a topological sense. Specifically, Goubault-Larrecq proved that the upper topologies of the induced quasi-orders on \({\mathcal{P}(Q)}\) are Noetherian, which means that they contain no infinite strictly descending sequences of closed sets. We analyze various theorems of the form “if Q is a well-quasi-order then a certain topology on (a subset of) \({\mathcal{P}(Q)}\) is Noetherian” in the style of reverse mathematics, proving that these theorems are equivalent to ACA₀ over RCA₀. To state these theorems in RCA₀ we introduce a new framework for dealing with second-countable topological spaces.     

Versatile Catalytic Hydrogenation Using A Simple Tin(IV) Lewis Acid

Despite the rapid development of frustrated Lewis pair (FLP) chemistry over the last ten years, its application in catalytic hydrogenations remains dependent on a narrow family of structurally similar early main‐group Lewis acids (LAs), inevitably placing limitations on reactivity, sensitivity and substrate scope. Herein we describe the FLP‐mediated H₂ activation and catalytic hydrogenation activity of the alternative LA iPr₃SnOTf, which acts as a surrogate for the trialkylstannylium ion iPr₃Sn⁺, and is rapidly and easily prepared from simple, inexpensive starting materials. This highly thermally robust LA is found to be competent in the hydrogenation of a number of different unsaturated functional groups (which is unique to date for main‐group FLP LAs not based on boron), and also displays a remarkable tolerance to moisture.