Stimuli‐Responsive Theragrippers for Chemomechanical Controlled Release

We report on a therapeutic approach using thermo‐responsive multi‐fingered drug eluting devices. These therapeutic grippers referred to as theragrippers are shaped using photolithographic patterning and are composed of rigid poly(propylene fumarate) segments and stimuli‐responsive poly(N‐isopropylacrylamide‐co‐acrylic acid) hinges. They close above 32 °C allowing them to spontaneously grip onto tissue when introduced from a cold state into the body. Due to porosity in the grippers, theragrippers could also be loaded with fluorescent dyes and commercial drugs such as mesalamine and doxorubicin, which eluted from the grippers for up to seven days with first order release kinetics. In an in vitro model, theragrippers enhanced delivery of doxorubicin as compared to a control patch. We also released theragrippers into a live pig and visualized release of dye in the stomach. The design of such tissue gripping drug delivery devices offers an effective strategy for sustained release of drugs with immediate applicability in the gastrointestinal tract.     

First-order transitions in spherical models: Finite-size scaling

Finite-size behavior near the first-order phase boundary of ferromagnetic spherical models is investigated for block- and cylinder-shaped systems ind dimensions. The bulk thermodynamic singularities are rounded and, asymptotically for large size, obey appropriate scaling laws. Both short-range interactions and long-range couplings, decaying like 1/r^d+ with >0, are analyzed: the short-range results agree precisely with a recently developed scaling theory forO(n) symmetric systems in the limitn. More generally, the scaling functions are universal, depending only on . Explicit aspects of the shape and interactions enter only in the spin wave or Goldstone mode contributions which appear, technically, as corrections to scaling. An appendix analyzes the truncation error in the approximation, by many-fold sums, of multivariate integrals with integrands diverging like [_ja_{j j} ² ]^- as 0.     

Phase diagram of the A and B phases of superfluid 3He in aerogel

We report the first measurements of the A-B phase transition of superfluid 3He confined within 98% silica aerogel in high magnetic fields and low temperatures. A disk of aerogel is attached to a vibrating wire resonator. The resonant frequency yields a measure of the superfluid fraction rho(s)/rho of the 3He within the aerogel. The inferred rho(s)/rho value increases substantially at the A-to- B transition of the confined superfluid, allowing us to map the A-B phase diagram as a function of field and temperature. At 4.8 bars, the B-T transition curve looks very similar to that in bulk with a simple reduction factor of order 0.45 for both transition field and temperature.     

Simulated cosmic strings in a “big bang” in superfluid3He at 100 μK

During studies of the impact of single neutrons on superfluid³He at around 100μK we have measured the thermal energy released in the superfluid following the nuclear reaction, n+³He→p+³H+764keV. However, we find that the measured energy deposited in the quasiparticle system shortly after this reaction is substantially less than what we expect. We believe that this energy deficit represents that energy which has gone into the creation of vortices, in analogy to the creation of cosmic strings in the early universe via the Kibble mechanism. Furthermore, from the magnitude of the deficit, we can infer the vortex density which compares favorably with that predicted in Zurek’s scenairo.     

The free energy of a macroscopic system

The statistical mechanics of classical and quantum mechanical systems interacting with many-body forces are investigated in the canonical and grand canonical ensembles. Under various general conditions on the attractive and repulsive parts of the potential energy and on the shapes of the domains _k confining the system, it is shown that the canonical free energy per particle and the grand canonical pressure have unique limits for infinite systems which are convex monotonie functions of the specific volume and chemical potential respectively, and satisfy the expected thermodynamic relations.For pure pair forces with potential (r) sufficient conditions are: (r)D ₁/r³⁺ as r0, |(r)|D ₂/r³⁺ as r (>0), and (r)-w₀ all r; the domains _k may be constructed from a finite set of bounded domains of arbitrary shape by any sequence of isotropic expansions such that the volume V(_k) approaches infinity with k.The work reported here was done while the author was on leave of absence from The Wheatstone Physics Laboratory, King's College, London W. C. 2, England.     

Modification of porous poly(ether sulfone) membranes by low‐temperature CO2‐plasma treatment

A general method of modifying the entire cross section of porous poly(ether sulfone) membranes with a low‐temperature CO₂‐plasma treatment is reported. Both surfaces of the membranes are highly hydrophilic, with a water drop on the surface disappearing in less than 1 s, even 6 months after plasma treatment. This high hydrophilicity of both membrane surfaces results from the incorporation of hydrophilic functionalities, as evidenced by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The incorporation of these hydrophilic functionalities takes place primarily during plasma treatment, with some incorporation of atmospheric oxygen and nitrogen immediately upon exposure to air. Scanning electron microscopy shows that the membrane surface is covered by a thin, white layer that is likely the result of etching and redeposition of sputtered surface fragments. An increase in the water bubble point and glass‐transition temperature is also observed for CO₂‐plasma‐treated membranes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2473–2488, 2002     

Enantioselective synthesis of the carbacephem antibiotic loracarbef via Mitsunobu and Dieckmann cyclization from an unnatural amino acid

The nucleus of the carbacephem antibiotic loracarbef was synthesized in a highly efficient and enantioselective fashion from 2S,3S-2-amino-3-hydroxy-6-heptenoic acid (AHHA), which was derived from enzyme-catalyzed condensation of glycine and 4-pentenaldehyde. The bicyclic framework of this compound was established through sequential Mitsunobu reaction and aldol condensations.