Experimental visualization and verification of a single-molecule rotor operating within a supramolecular bearing is reported. Using a scanning tunneling microscope, single molecules were observed to exist in one of two spatially defined states laterally separated by 0.26 nanometers. One was identified as a rotating state and the other as an immobilized state. Calculations of the energy barrier for rotation of these two states show that it is below the thermal energy at room temperature for the rotating state and above it for the immobilized state.

Hydrothermal liquefaction (HTL) is regarded as a promising technology for the production of biofuels from biomass and wastes. As such, there is a drive towards continuous-flow processing systems to aid process scale-up and eventually commercialization. The current study presents results from a novel pilot-scale HTL reactor with a feed capacity of up to 100 L/h and a process volume of approximately 20 L. The pilot plant employs a heat exchanger for heat recovery and a novel hydraulic oscillation system to increase the turbulence in the tubular reactor. The energy grass Miscanthus and the microalgae Spirulina, both representing advanced dedicated energy crops, as well as sewage sludge as high-potential waste stream were selected to assess the reactor performance. Biomass slurries with up to 16 wt% dry matter content were successfully processed. The heat recovery of the heat exchanger is found to increase with reactor run time, reaching 80% within 5–6 h of operation. The hydraulic oscillation system is shown to improve mixing and enhance heat transfer. Bio-crudes with average yields of 26 wt%, 33 wt% and 25 wt% were produced from Miscanthus, Spirulina and sewage sludge, respectively. The yields also appeared to increase with reactor run time. Bio-crude from HTL of Spirulina was mainly composed of palmitic acid, glycerol, heptadecane and linolelaidic acid, while biocrude from sewage sludge contained mainly palmitic acid, oleic acid and stearic acid. In contrast, biocrude from HTL of Miscanthus consisted of a large number of different phenolics. An energetic comparison between the three feedstocks revealed a thermal efficiency of 47%, 47% and 33% and energy return on investment (EROI) of 2.8, 3.3 and 0.5 for HTL of Miscanthus, Spirulina and sewage sludge, respectively.

The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce a restructuring of a metal surface underneath. This restructuring anchors the molecules on the substrate and is the driving force for a self-assembly process of the molecules into characteristic molecular double rows.

A new bicomponent conetwork, poly(ethyl acrylate)-linked-polyisobutylene (PEtA-l-PIB), was synthesized by radical copolymerization of equal amounts of telechelic α,ω-dimethacrylic PIB (MA−PIB−MA, M n/(kg/mol) = 11.2, M w/M n = 1.12, and MA/chain = 2.0) obtained via quasi-living carbocationic polymerization and ethyl acrylate in 10% solution for each component in a common solvent, tetrahydrofuran, followed by extraction and drying. Low amounts of extractables (2.5% in acetone and 4.6% in hexane) and nearly theoretical composition (51% PEtA and 49% PIB) of the resulting conetwork indicate efficient network formation; i.e., this new conetwork is composed of PIB chains connected at each end to two PEtA chains. DSC experiments gave close to literature value T g's (−68 °C for PIB and −22 °C for PEtA), indicating a segregated morphology in this conetwork. In contrast to reported results for similar conetworks containing PIB and other polymers with polar groups, surface analysis with XPS found no significant difference in surface and bulk compositions in PEtA-l-PIB. For the first time in the field of bicomponent segmented conetworks, the structure of a conetwork was investigated by small-angle neutron scattering (SANS) in both the relaxed and strained states. Two correlation peaks were observed at q*/Å-1 = 0.035 and at 3q*. The measured value of q* is less by more than a factor of 2 than that predicted by de Gennes for random bicomponent (“grafted”) networks. The macroscopically homogeneous conetwork is characterized by nanoscale local layered like segregation with a correlation length of 445 Å and periodicity of 180 Å. This structure does not deform affinely with the macroscopic deformation. The measured modulus is in excellent agreement with an affine network prediction assuming that each MA−PIB−MA chain gives rise to three elastic strands in the network.

A beaded, chemically stable, high capacity amino resin for solid phase synthesis under polar and non-polar conditions is described. By exhaustive reduction of amide carbonyl groups in PEG cross linked poly(ethylene glycol)-poly(-acrylamide) copolymer (PEGA) a significant increase in functional amino groups is obtained. Furthermore, a resin containing 90% PEG which is free of amide carbonyl groups is produced. The polymer was characterized by IR spectroscopy and the macroscopic properties of the beads were analyzed by microscopy. Excellent swelling properties in various solvents ranging from water to DCM were demonstrated. The chemical stability of the polymer in various reagents and solvents was investigated and changes in resin properties monitored by IR spectroscopy.The mechanical stability of the resin was analyzed by measurement of compressive strain. The unique three dimensional structure of the swelled polyethylene glycol network facilitate fast and unhindered diffusion of reagents and the support is excellent for synthesis of peptides or peptide mimetics, which can be produced in high yield/reaction volume. The efficacy of the new resin in solid phase synthesis was demonstrated by synthesizing an a-MSH peptide fragment. A cyclic peptide mimetic was also synthesized on the new resin by the Cu (1) catalyzed intra molecular cyclo addition of alkyne and azide to form a triazole acting as a disulphide mimetic entity in very high yield and purity.