3‐Methyl‐(E)‐stilbene (3MSti) and 4‐(diethylamino)‐(E)‐stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition‐fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo‐first order polymerization kinetics are demonstrated for the synthesis of poly((3‐methyl‐(E)‐stilbene)‐alt‐maleic anhydride) (3MSti‐alt‐MAn) with a thiocarbonylthio CTA (methyl 2‐(dodecylthiocarbonothioylthio)−2‐methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4‐(diethylamino)‐(E)‐stilbene)‐alt‐maleic anhydride) (DEASti‐alt‐MAn) with pseudo‐first order polymerization kinetics. DEASti‐alt‐MAn is chain extended with 4‐acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4‐(diethylamino)‐(E)‐stilbene)‐alt‐maleic acid))‐b‐acryloylmorpholine) (DEASti‐alt‐MA)‐b‐ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid‐containing copolymers are determined using ζ‐potential and acid–base titrations, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 219–227
Double‐hydrophilic block copolymers (DHBCs) of poly((4‐diethylamino)‐(E)‐stilbene)‐alt‐maleic acid)‐block‐acryloyl morpholine (DEASti‐alt‐MA)‐b‐ACMO), semirigid‐b‐flexible coil structures, form polyion complexes (PICs) in aqueous solutions. The pH and salt responsiveness of the PICs are studied using dynamic light scattering (DLS). PIC complex formation is dependent on block segment lengths and pH. The particle size increases as the pH approaches the IEP (isoelectric point) of the DHBC. The salt responsiveness is also measured by using DLS to monitor PIC size for four examples with different segment molar masses. These PICs exhibit an antipolyelectrolyte effect with increasing hydrodynamic diameter as ionic strength (NaCl) increases from 0.01 to 2.0 m. PICs are more stable at higher ionic strengths with higher ACMO molar mass.
No human has returned to the moon since the end of the Apollo program 47 years ago, however, new missions are planned for an orbital outpost. Space radiation and the potential for cancer remain as important issues to the future of human space exploration. While improved shield technologies and protective biologicals are under development, little is known concerning the interaction between cancer cells and host immunity in microgravity. As a hallmark of cancer, tumor cells employ mechanisms of immune evasion to avoid elimination by protective CD4+ and CD8+ T cells. We showed that a murine lymphoma was able to produce a soluble factor that inhibited the function of dendritic cells in activating the CD4+ T cells. Culture of the lymphoma cells in simulated microgravity (SMG), and not Static conditions, restored the CD4+ T cell response and augmented CD8+ T cell-mediated destruction of the cancer cells in vitro and in vivo. Thus, SMG impaired the mechanism of tumor escape and rendered the cancer cells more susceptible to T cell-mediated elimination. The stress of microgravity may expose the most critical components of a tumor’s escape mechanism for astronaut protection and the generation of new cancer therapeutics for patients on Earth.
The reaction of carbon monoxide with ozone was studied in the range of 75-160OC in the presence of varying amounts of COZ and, for a few experiments, of 0 2 . At room temperature the reaction was immeasurably slow, but in a flow system it showed chemiluminescence with undamped oscillations. In a static system above 75°C the emission showed damped oscillations when 0 2 was present. In the absence of added 0 2 the emission showed a slow decay with a half-life of >1 hr. The luminescence consisted of partially resolved hands in the range of 325400 nm, and the source was identified as C02('&) -COz('Z:) + hv. The kinetics were complex, and the observed rate law could be accounted for by a mechanism involving the chain sequence O(3P) + CO(+M) 2 C02(3Bz) (+M), C02(3B2) + 0 3 3, COz(l2,+) + 0 2 + 0. From measurements of -d [Og]/dt and relative emission, rate constant ratios were obtained and estimates of k 3 were made.
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