Ultrafast observation of a solvent dependent spin state equilibrium in CpCo(CO)

We report the observation of a solvent-dependent spin state equilibrium in the 16-electron photoproduct CpCo(CO). Time-resolved infrared spectroscopy has been used to observe the concurrent formation of two distinct solvated monocarbonyl photoproducts, both of which arise from the same triplet CpCo(CO) precursor. Experiments in different solvent environments, combined with electronic structure theory calculations, allow us to assign the two solvated photoproducts to singlet and triplet CpCo(CO)(solvent) complexes. These results add to our previous picture of triplet reactivity for 16-electron organometallic photoproducts, in which triplets were not believed to interact strongly with solvent molecules. In the case of this photoproduct, it appears that spin crossover does not present a significant barrier to reactivity, and relative thermodynamic stabilities determine the spin state of the CpCo(CO) photoproduct in solution on the picosecond time scale. While the existence of transition metal complexes with two thermally accessible spin states is well-known, this is, to our knowledge, the first observation of a transient photoproduct that exhibits an equilibrium between two stable spin states, and also the first observed case in which a solvent has been able to coordinate as a token ligand to two spin states of the same photoproduct.     

Mechanochemistry: opportunities for new and cleaner synthesis

The aim of this critical review is to provide a broad but digestible overview of mechanochemical synthesis, i.e. reactions conducted by grinding solid reactants together with no or minimal solvent. Although mechanochemistry has historically been a sideline approach to synthesis it may soon move into the mainstream because it is increasingly apparent that it can be practical, and even advantageous, and because of the opportunities it provides for developing more sustainable methods. Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes (including metal-organic frameworks), supramolecular aspects and characterization methods. The historical development, mechanistic aspects, limitations and opportunities are also discussed (314 references).     

Surface-enhanced Raman scattering study of the kinetics of self-assembly of carboxylate-terminated n-alkanethiols on silver

Adsorption of 11-mercaptoundecanoic acid (MUA) on silver from methanol and aqueous solutions was monitored in situ by surface-enhanced Raman scattering (SRES) spectroscopy. While adsorption of MUA from methanol is a one-step formation of a thiol-bound monolayer, SERS spectra reveal that monolayer formation from aqueous solution involves interactions of both carboxylate and thiol groups of MUA with the silver surface. Several Raman scattering bands, including the ν(C-S), ν(s)(COO(-)), and ν(C-C), were used to investigate the evolution of the structure of adsorbed MUA on silver surfaces. The time-dependent profiles of these bands for assembly from aqueous solution indicate a multistep process, which is initiated by the binding of both carboxylate and thiol groups to silver, producing a mixture of gauche and trans conformations. In a subsequent step, the COO-Ag interactions are displaced by stronger S-Ag bonds, leading to ordering of the resulting monolayer with formation of a complete SAM with all-trans conformations. The results also showed that the adsorption process depended strongly on the solution pH and surface potential of the metal. These factors can significantly affect the participation and displacement of -COO(-) during self-assembly of MUA from aqueous solution.     

Unraveling the Mechanism of the Photodeprotection Reaction of 8‐Bromo‐ and 8‐Chloro‐7‐hydroxyquinoline Caged Acetates

Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming “caged compounds” are a powerful means to regulate the action of physiologically active messengers in vivo through 1‐photon excitation (1PE) and 2‐photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8‐chloro‐7‐hydroxyquinolin‐2‐yl)methyl acetate (CHQ‐OAc) and (8‐bromo‐7‐hydroxyquinolin‐2‐yl)methyl acetate (BHQ‐OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time‐resolved spectroscopic studies using transient emission (ns‐EM), transient absorption (ns‐TA), transient resonance Raman (ns‐TR²), and time‐resolved resonance Raman (ns‐TR³) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ‐OAc, but not CHQ‐OAc. A high fluorescence quantum yield and a more efficient excited‐state proton transfer (ESPT) in CHQ‐OAc compared to BHQ‐OAc explain the lower quantum efficiency of CHQ‐OAc relative to BHQ‐OAc.     

Galois representations,automorphic forms,and the Sato-Tate Conjecture

The present text consists of notes of several lectures on the proof of the Sato-Tate Conjecture given up through 2008. The goal of the lectures was to explain the statement and the main ideas of the proof. The notes are somewhat dated; shortly after they were written, the author, together with Bernet-Lamb, Geraghty, and Taylor, were able to prove the analogue of the Sato-Tate conjecture for all elliptic modular forms. In particular, Theorems 2.4 and 2.5 are not conditional, and the condition on the j-invariant in Theorem 1.1 is superfluous. Moreover, the methods of proof outlined in sections 3 and 4 have been generalized and extended in a number of ways, notably in a series of articles by Barnet-Lamb, Gee, Geraghty, and Taylor, by Thorne, and by Calegari and Geraghty.     

Branching Brownian Motion with Catalytic Branching at the Origin

We consider a branching Brownian motion in which binary fission takes place only when particles are at the origin at a rate β>0 on the local time scale. We obtain results regarding the asymptotic behaviour of the number of particles above λt at time t, for λ>0. As a corollary, we establish the almost sure asymptotic speed of the rightmost particle. We also prove a Strong Law of Large Numbers for this catalytic branching Brownian motion.     

Synthesis of methyl N-Boc-(2S,4R)-4-methylpipecolate

An efficient stereoselective synthesis of fully protected (2S,4R)-4-methylpipecolic acid has been developed. The synthesis was achieved by initial asymmetric α-alkylation of glycine with a chiral iodide, affording the linear precursor as a single stereoisomer. Subsequent aldehyde formation using OsO(4)/NaIO(4) followed by immediate intramolecular cyclization afforded an enamine that was then subjected to hydrogenation to give the final compound in 23% yield over 10 steps.     

Pressure dependence of space charge deposition in piezoelectric polymer foams: simulations and experimental verification

The piezoelectric activity of PQ-50 cellular polypropylene (PP) foam (an example of a so-called ferroelectret) is measured after repeated charging in a nitrogen atmosphere at a range of pressures between 61 and 381?kPa. The results are compared against simulations using a multilayer electromechanical model based on Townsend??s model of Paschen breakdown and a realistic distribution of void heights determined from scanning electron micrographs. The modeled piezoelectric coefficients versus pressure are in good agreement with experimental data when adjusted Paschen coefficients are used, indicating that the Paschen curve for electric breakdown in gases needs to be modified for dielectric barrier discharges in microcavities. The highest d ₃₃ coefficients were achieved for pressures above 251?kPa. For previously uncharged PP foam, the model predicts an optimal charging pressure of 186 kPa.     

Alhydrogel® adjuvant, ultrasonic dispersion and protein binding: a TEM and analytical study

Aluminium-based vaccine adjuvants have been in use since the 1920s. Aluminium hydroxide (alum) that is the chemical basis of Alhydrogel, a widely used adjuvant, is a colloid that binds proteins to the particular surface for efficient presentation to the immune system during the vaccination process. Using conventional TEM and cryo-TEM we have shown that Alhydrogel can be finely dispersed by ultrasonication of the aqueous suspension. Clusters of ultrasonicated aluminium hydroxide micro-fibre crystals have been produced (～ 10-100 nm), that are significantly smaller than those present the untreated Alhydrogel (～ 2-12 μm). However, even prolonged ultrasonication did not produce a homogenous suspension of single aluminium hydroxide micro-fibres. The TEM images of unstained and negatively stained air-dried Alhydrogel are very similar to those obtained by cryo-electron microscopy. Visualization of protein on the surface of the finely dispersed Alhydrogel by TEM is facilitated by prior ultrasonication. Several examples are given, including some of medical relevance, using proteins of widely ranging molecular mass and oligomerization state. Even with the smaller mass proteins, their presence on the Alhydrogel surface can be readily defined by TEM. It has been found that low quantities of protein tend to cross-link and aggregate the small Alhydogel clusters, in a more pronounced manner than high protein concentrations. This indicates that complete saturation of the available Alhydrogel surface with protein may be achieved, with minimal cross-linkage, and future exploitation of this treatment of Alhydrogel is likely to be of immediate value for more efficient vaccine production.