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Covalent immobilization of chiral dienes in mesoporous solids for asymmetric heterogeneous catalysis is highly attractive. In order to study confinement effects in bimolecular vs monomolecular reactions, a series of pseudo‐C2‐symmetrical tetrahydropentalenes was synthesized and immobilized via click reaction on different mesoporous solids (silica, carbon, covalent organic frameworks) and compared with homogeneous conditions. Two types of Rh‐catalyzed reactions were studied: (a) bimolecular nucleophilic 1,2‐additions of phenylboroxine to N‐tosylimine and (b) monomolecular isomerization of isoxazole to 2H‐azirne. Polar support materials performed better than non‐polar ones. Under confinement, bimolecular reactions showed decreased yields, whereas yields in monomolecular reactions were only little affected. Regarding enantioselectivity the opposite trend was observed, i. e. effective enantiocontrol for bimolecular reactions but only little control for monomolecular reactions was found. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well‐established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large‐pore COF as catalytic support in α,ω‐diene ring‐closing metathesis reactions, leading to increased macrocyclization selectivity. COF pore‐wall modification by immobilization of a Grubbs‐Hoveyda‐type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous olefin metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF‐catalyst (MMC:O=1.35) of up to 51 % compared to the homogeneous catalyst (MMC:O=0.90) was observed along with a substrate‐size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement. [ABSTRACT FROM AUTHOR]

Time-resolved mechanochemical cocrystallisation studies have so-far focused solely on neat and liquid-assisted grinding. Here, we report the investigation of polymer-assisted grinding reactions using in situ X-ray powder diffraction, revealing that reaction rate is almost double compared to neat grinding and independent of the molecular weight and amount of the polymer additive used. [ABSTRACT FROM AUTHOR]

Our recent studies of the diastereo- and enantioselective formation of strained alkylidenecycloalkanes drove us to more-thoroughly investigate the formation of four-membered rings for which only few efficient methods are described. We first developed a strategy to diversify the saturated part of the four-membered ring and applied it to a highly diastereoselective synthesis of more-elaborate alkylidenecyclobutanes, which completed our precedent studies. In parallel, cyclobutene structures were built employing simple organometallic methods and further functionalized to give a diverse range of new substitution patterns, which consequently enriched the pool of cyclobutene-based building blocks. [ABSTRACT FROM AUTHOR]

Interactions between styrene-acrylate latexes and cement are investigated with emphasis of the charge properties of the polymer particles by means of calorimetry, adsorption measurement, and confocal laser scanning microscope. Three latexes with varied surface charges of polymer particles were prepared by respectively using methacrylic acid (MAA), sodium styrene sulfonate (SSS) and methyl poly(ethylene glycol) methacrylate (MPEGMA) as water soluble monomers during synthesis. It is found that the polymer latexes retard cement hydration in two manners, namely the delaying effect represented by a delayed hydration peak and the slowing down effect characterized by a reduced main hydration peak during the acceleration period. The delaying effect is closely related to the concentration of carboxylic groups existing in the latex, while the depression effect of hydration rate is majorly caused by the adsorption of polymer particles on surface of cement grains and proportional to the total charge density of polymer particles. [ABSTRACT FROM AUTHOR]

A morphology transition from spherical mesopores to worm-shaped mesopores within titania block copolymer composite thin films has been observed by varying the sol-gel reaction time from 40 min to 48 h in the four-component templating system of polystyrene- b-poly(ethylene oxide) (PS- b-PEO), 1,4-dioxane, concentrated HCl, and titanium tetraisopropoxide (TTIP) with a PS- b-PEO mass concentration of 0.25 wt.-%. The impact of the sol-gel reaction time on the local structure, long-range lateral structure, and vertical structure of the as-prepared, calcined, and UV-degraded thin films as well as the structural changes in solution have been systematically investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), X-ray reflectivity (XRR), and dynamic light scattering (DLS). With sol-gel reaction times of up to 5 h, hexagonally organized spherical micelles are present within the as-prepared composite films, in which the core of the spherical micelles is composed of the polystyrene (PS) block, and the corona is composed of the poly(ethylene oxide)-titania (PEO-titania) hybrid. Upon calcination or UV exposure, ordered mesoporous structures are formed owing to the removal of the PS block. With the sol-gel reaction time extended to 25 and 48 h, worm-shaped micelles appear, and their quantity increases with increasing sol-gel reaction time. Worm-shaped mesopores are formed by calcination or UV degradation. The GISAXS results prove that the local structural changes are representative over a macroscopic scale. The XRR results suggest that with the sol-gel reaction time extended to 48 h there is an additional thin layer beneath the mesoporous titania layer owing to the presence of a large amount of worm-shaped micelles. The results of the DLS studies imply that the morphology transition from spherical micelles to worm-shaped micelles is caused by a fusion process of the spherical micelles in solution. [ABSTRACT FROM AUTHOR]

A morphology evolution of thin films of titania from spherical mesopores to worm-shaped mesopores was realized by simply varying the sol-gel reaction time from 46 min to 25 h in the quadruple system consisting of polystyrene- block-poly(ethylene oxide) (PS- b-PEO), 1,4-dioxane, concentrated HCl, and titanium tetraisopropoxide (TTIP). Imaging techniques including scanning electron microscopy (SEM) and atomic force microscopy (AFM) were applied to investigate the local structure change of the as-prepared, calcined, and UV-degraded composite films. Grazing incidence small angle X-ray scattering (GISAXS) experiments prove that the structure change in local areas is representative of that over the macroscopic scale. An X-ray reflectivity (XRR) investigation reveals that the vertical structure change happens when the sol-gel reaction is extended from 5 to 25 h. A combination of imaging and scattering techniques provides a powerful tool to elucidate the impact of the sol-gel reaction time on the morphology evolution of the composite films. Dynamic light scattering (DLS) studies imply that the morphology evolution within the films is due to the structure change in solution. A mechanism of the morphology evolution with sol-gel reaction time is proposed on the basis of these results, which provide not only a new way to control the morphology of titania block copolymer composite films but also deep insights into the kinetics of the amphiphilic block copolymer templating process. [ABSTRACT FROM AUTHOR]

The chain dynamics at the glass transition of poly(ethylmethacrylate) in the bulk is compared to that of mixtures of the polymer with nanoparticles by advanced NMR methods. In order to make the two components compatible, the particles were functionalized with the polymer itself. Particular emphasis is placed on the extended local chain conformations of this polymer accessible by 13C NMR spectroscopy. The isotropization dynamics of these extended conformations is only slightly changed in the mixtures, but is significantly slowed down by attachment of the chains to the nanoparticles themselves. The slowing down is studied at various distances from the nanoparticle and is observed for most of the attached chains segments except for the chain ends. The results are put into perspective to the glass transition in polymers attached to surfaces, thin polymer layers, and the chain dynamics of star polymers. [ABSTRACT FROM AUTHOR]

The effects of polymer latexes on cement hydration were investigated by the combination of isothermal calorimetry, in-situ XRD and Cryo-SEM. Two model latexes with varied amounts of anionic charges were used for measurements after cleaned by dialysis to remove the serum components. This study confirms that in-situ XRD technique can be successfully adapted to hydrating cementitious systems in the presences of polymer latexes to quantitatively follow evolution of mineral phases involved in cement hydration. Results show that both polymers retard aluminate reaction and depress silicate reaction, by delaying the dissolution of C 3 A, anhydrite and gypsum and consequently the formation of ettringite, and reducing the dissolution of C 3 S and the formation of C-S-H. The anionic colloidal polymers exhibit more pronounced retardation effect on aluminate reaction than on silicate reaction due to stronger electrostatic interaction between the polymer particles and the positively charged aluminate phases. The more charged latex shows stronger retardation. [ABSTRACT FROM AUTHOR]

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Covalent organic frameworks (COFs) with a pore size beyond 5 nm are still rarely seen in this emerging field. Besides obvious complications such as the elaborated synthesis of large linkers with sufficient solubility, more subtle challenges regarding large-pore COF synthesis, including pore occlusion and collapse, prevail. Here we present two isoreticular series of large-pore imine COFs with pore sizes up to 5.8 nm and correlate the interlayer interactions with the structure and thermal behavior of the COFs. By adjusting interlayer interactions through the incorporation of methoxy groups acting as pore-directing "anchors", different stacking modes can be accessed, resulting in modified stacking polytypes and, hence, effective pore sizes. A strong correlation between stacking energy toward highly ordered, nearly eclipsed structures, higher structural integrity during thermal stress, and a novel, thermally induced phase transition of stacking modes in COFs was found, which sheds light on viable design strategies for increased structural control and stability in large-pore COFs.

Our recent studies of the diastereo- and enantioselective formation of strained alkylidenecycloalkanes drove us to more-thoroughly investigate the formation of four-membered rings for which only few efficient methods are described. We first developed a strategy to diversify the saturated part of the four-membered ring and applied it to a highly diastereoselective synthesis of more-elaborate alkylidenecyclobutanes, which completed our precedent studies. In parallel, cyclobutene structures were built employing simple organometallic methods and further functionalized to give a diverse range of new substitution patterns, which consequently enriched the pool of cyclobutene-based building blocks., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report measurements of structure, mechanical properties, glass transition temperature, and contact angle of a novel nanocomposite material consisting of swellable silsesquioxane nanoparticles with grafted poly(ethyl methacrylate) (PEMA) brushes and PEMA matrices with varying molecular weight. We measured the interparticle distance at the surface of the composites using scanning probe microscopy (SPM) and in the bulk of ∼0.5 μm thick films by grazing incidence small angle X-ray scattering (GISAXS). For a given molecular weight of the brush unstable dispersions at high molecular weight of the matrix indicate an intrinsic incompatibility between polymer-grafted-nanoparticles and homopolymer matrices. This incompatibility is affirmed by a high contact angle between the polymer-grafted-nanoparticles and the high molecular weight matrix as measured by SPM. For unstable dispersions, we measured a decreased glass transition temperature along with a decreased plateau modulus by dynamic mechanical thermal analysis (DMTA) which indicates the formation of a liquid-like layer at the brush-matrix interface. This proves the ability to decouple the structural and mechanical properties from the potential to be swollen with small molecules. It opens a new area of use of these soft nanocomposites as slow release materials with tailored mechanical properties.

We explore the effect of an ultrathin elastic coating to optimize the mechanical stability of an underlying polymer film for nanoscale applications. The coating consists of a several nanometer thin plasma-polymerized norbornene layer. Scanning probes are used to characterize the system in terms of shear-force-induced wear and thermally assisted indentation. The layer transforms a weakly performing polystyrene film into a highly wear-resistive system, ideal for high-density and low-power data storage applications. The result can be understood from the indentation characteristics with a hot and sharp indenter tip. The latter gives rise to a deformation mode in the fully plastic regime, enabling a simple interpretation of the results. The softening transition and the yield stress of the system on a microsecond time scale and a nanometer size scale were obtained. We show that the plastic deformation is governed by yielding in the polystyrene sublayer, which renders the overall system soft for plastic deformation. The ultrathin protection layer contributes as an elastic skin, which shields part of the temperature and pressure and enables the high wear resistance against lateral forces. Moreover, the method of probing polymers at microsecond and nanometer size scales opens up new opportunities for studying polymer physics in a largely unexplored regime. Thus, we find softening temperatures of more than 100 °C above the polystyrene glass transition, which implies that for the short interaction time scales the glassy state of the polymer is preserved up to this temperature.