Molekül‐Detektive. Biosensoren

Biosensors are analytical devices incorporating biological material (receptor) intimately associated with or integrated within a physicochemical transducer. Advantages are the high selectivity for analyte detection. Examples given comprise the very successful commercial blood glucose biosensors made for the self‐control by the diabetic patients. Other biosensors are part of an analytic system, including the sensor chips of surface plasmon resonance or interferometry based devices, piezoelectric or reflectometric sensors capable of direct measurement of mass changes, and thermometric and other reagentless sensors. The development of nanotubes‐based devices allows for significant enhancment of the signal‐tonoise ratio of the biosensors. A milestone on the way towards miniaturization and parallelization of biosensors is the recently developed and prize‐winning electronic DNA chip.     

Novel thermoplastic elastomers. II. Properties of star‐block copolymers of PSt‐b‐PIB arms emanating from cyclosiloxane cores

Select mechanical, thermal, and rheological properties of star‐blocks consisting of 5–21 polystyrene‐b‐polyisobutylene (PSt‐b‐PIB) arms radiating from cyclosiloxane cores are described. The tensile properties of products containing 23–41 wt % of PSt are substantially higher (9.6–23.8 MPa) than those of linear triblocks of comparable arm molecular weights and compositions over the 25–85°C temperature range. The mechanical properties of star‐blocks seem to be much less sensitive to diblock contamination than linear triblock thermoplastic elastomers of similar hard/soft segment composition. The tensile strength of star‐blocks increases by increasing the number of arms (N_w,arm) and reaches a plateau in the N_w,arm = 5–10 range. Star‐blocks exhibit higher strengths with lower PSt segmental M_n than linear triblocks. Solvent cast triblock copolymers exhibit higher tensile strengths than compression molded products; however, star‐blocks show no significant property differences between cast and molded samples. The dynamic melt viscosities of the star‐blocks are substantially lower than those of linear triblocks with comparable hard/soft segment compositions, which is consistent with the star's unique microarchitecture and should lead to improved overall processibility. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 815–824, 1999     

Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Polymerization of 1,3‐dienes with functional groups. II. Free‐radical polymerization of N‐(2‐methylene‐3‐butenoyl)piperidine

The free‐radical homopolymerization and copolymerization behavior of N‐(2‐methylene‐3‐butenoyl)piperidine was investigated. When the monomer was heated in bulk at 60 °C for 25 h without an initiator, about 30% of the monomer was consumed by the thermal polymerization and the Diels–Alder reaction. No such side reaction was observed when the polymerization was carried out in a benzene solution with 1 mol % 2,2′‐azobisisobutylonitrile (AIBN) as an initiator. The polymerization rate equation was found to be R_p ∝ [AIBN]^0.507[M]^1.04, and the overall activation energy of polymerization was calculated to be 89.5 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure that included both 1,4‐E and 1,4‐Z configurations. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were carried out in benzene solutions at 60 °C with AIBN as an initiator. In the copolymerization with styrene, the monomer reactivity ratios were r₁ = 6.10 and r₂ = 0.03, and the Q and e values were calculated to be 10.8 and 0.45, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1545–1552, 2003     

Strain‐induced crystallization and strength of elastomers. I. cis‐1,4‐polybutadiene

Crosslinked samples of cis‐1,4‐polybutadiene (BR) were crystallized at low temperatures and then slowly melted. From volume changes and differential scanning calorimetry measurements, the degree of crystallization in the unstrained state was estimated to be about 20%, much lower than for natural rubber (NR). Crystallization and melting were followed in stretched samples by corresponding changes in tensile stress. Crystallization was faster at higher strains, and the melting temperature was raised significantly on stretching but less than for NR, and the decrease in stress on crystallizing was smaller. Measurements of tensile strength were made over a wide temperature range and showed a marked drop with heating to temperatures of 40–60 °C, falling to values of only 1–2 MPa. A similar drop in strength occurred in NR vulcanizates at high temperatures and was attributed to failure to crystallize on stretching (A. G. Thomas & J. M. Whittle, Rubber Chem Technol 1970, 43, 222; A. N. Gent, S. Kawahara & J. Zhao, Rubber Chem Technol 1998, 71, 668). At ambient temperatures, where strain‐induced crystallization occurred, the strength of BR samples was only about one‐half of that of similar NR materials. This was attributed to less strain‐induced crystallinity in BR (verified by X‐ray studies), paralleling the lower amount developed at low temperatures. We speculate that the higher density of molecular entanglements in BR than in NR prevents BR from crystallizing to the same degree as NR. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 811–817, 2001