Stimuli-responsive poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock copolymers and complexation with poly(acrylic acid) at low pH

The self-organization of the double hydrophilic triblock copolymer poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide), PEO-b-P2VP-b-PEO, was investigated in dilute aqueous solution under several experimental conditions using turbidimetry, as well as static and dynamic light scattering. As a result of the temperature-sensitive properties of the end PEO blocks and the p H-responsive properties of the middle P2VP block, the formation of large star-like micellar nanostructures is observed at high p H, while at low p H, but in the presence of salt and at high temperature, flower-like micelles are formed. Moreover, the viscosimetric and dynamic light scattering studies at low p H revealed that micelle-like nanostructures are formed upon mixing the triblock copolymer with poly(acrylic acid), PAA, due to hydrogen bonding interpolymer complexation.     

Performance of interventions with manipulator-driven real-time MR guidance: implementation and initial in vitro tests

The purpose of this work was to implement and assess the performance of interventions inside a cylindrical magnetic resonance imaging (MRI) scanner with an MR-compatible manipulator system and manipulator-driven real-time MR guidance. The interventional system is based on a seven degree-of-freedom MR-compatible manipulator, which offers man-in-the-loop control either with a graphical user interface or with a master/slave device. The position and the orientation of the interventional tool are sent to an MR scanner for a manipulator-driven dynamic update of the imaging plane to track, visualize and guide the motion of an end-effector. Studies on phantoms were performed with a cylindrical 1.5-T scanner using an operator-managed triggered gradient-recalled echo (GRE) or a computer-managed dynamic True Fast Imaging with Steady Precession (TrueFISP). Targets were acquired with an accuracy of 3.2 mm and with an in-plane path orientation of 2.5 degrees relative to the prescribed one. Path planning, including negotiation of obstacles and needle bending, was successfully performed. The signal-to-noise ratio (SNR) of TrueFISP was 25.3+/-2.1 when the manipulator was idle and was 18.6+/-2.4 during its operation. The SNR of triggered GRE (acquired only when the manipulator was idle) was 61.3+/-1.8. In conclusion, this study shows the feasibility of performing manually directed interventions inside cylindrical MR scanners with real-time MRI.     

Divergent synthesis and chemical reactivity of bicyclic lactone fragments of complex rearranged spongian diterpenes

The synthesis and direct comparison of the chemical reactivity of the two highly oxidized bicyclic lactone fragments found in rearranged spongian diterpenes (8-substituted 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one and 6-substituted 7-acetoxy-2,8-dioxabicyclo[3.3.0]octan-3-one) are reported. Details of the first synthesis of the 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one ring system, including an examination of several possibilities for the key bridging cyclization reaction, are described. In addition, the first synthesis of 7-acetoxy-2,8-dioxabicyclo[3.3.0]octanones containing quaternary carbon substituents at C6 is disclosed. Aspects of the chemical reactivity and Golgi-modifying properties of these bicyclic lactone analogs of rearranged spongian diterpenes are also reported. Under both acidic and basic conditions, 8-substituted 2,7-dioxabicyclo[3.2.1]octanones are converted to 6-substituted-2,8-dioxabicyclo[3.3.0]octanones. Moreover, these dioxabicyclic lactones react with primary amines and lysine side chains of lysozyme to form substituted pyrroles, a conjugation that could be responsible for the unique biological properties of these compounds. These studies demonstrate that acetoxylation adjacent to the lactone carbonyl group, in either the bridged or fused series, is required to produce fragmented Golgi membranes in the pericentriolar region that is characteristic of macfarlandin E.