The SAGA (Spt-Ada-Gcn5 acetyltransferase) coactivator complex contains distinct chromatin-modifying activities and is recruited by DNA-bound activators to regulate the expression of a subset of genes. Surprisingly, recent studies revealed little overlap between genome-wide SAGA-binding profiles and changes in gene expression upon depletion of subunits of the complex. As indicators of SAGA recruitment on chromatin, we monitored in yeast and human cells the genome-wide distribution of histone H3K9 acetylation and H2B ubiquitination, which are respectively deposited or removed by SAGA. Changes in these modifications after inactivation of the corresponding enzyme revealed that SAGA acetylates the promoters and deubiquitinates the transcribed region of all expressed genes. In agreement with this broad distribution, we show that SAGA plays a critical role for RNA polymerase II recruitment at all expressed genes. In addition, through quantification of newly synthesized RNA, we demonstrated that SAGA inactivation induced a strong decrease of mRNA synthesis at all tested genes. Analysis of the SAGA deubiquitination activity further revealed that SAGA acts on the whole transcribed genome in a very fast manner, indicating a highly dynamic association of the complex with chromatin. Thus, our study uncovers a new function for SAGA as a bone fide cofactor for all RNA polymerase II transcription.
A new bisphenol monomer, 9,9-bis(3,5-dimethoxy-4-hydroxyphenyl) fluorene, was synthesized and polymerized to form fluorene-based poly(arylene ether sulfone) copolymers containing tetra-methoxy groups (MPAES). After converting the methoxy group to the reactive hydroxyl group, the respective side-chain type sulfonated copolymers (SPAES) were obtained by sulfobutylation. The polymers were characterized by 1H NMR, thermogravimetric analysis (TGA), water uptake, and proton and methanol transport for fuel cell applications. These SPAES copolymers had good overall properties as polymer electrolyte membrane (PEM) materials, having high proton conductivity in the range of 0.061–0.209 and 0.146–0.365 S/cm at 30 and 80 °C (under hydrated conditions), respectively. SPAES-39 (IEC = 1.93 mequiv/g) showed higher or comparable proton conductivity than that of Nafion 117 at 50–95% RH (relative humidity). The methanol permeabilities of these membranes were in the range of 3.22 to 13.1 × 10–7 cm2/s, which is lower than Nafion (15.5 × 10–7 cm2/s). In comparison with some reported sulfonated poly(arylene ether sulfone)s containing pendent sulfophenyl groups, the present fluorene-based SPAES containing clustered flexible pendent aliphatic sulfonic acid groups displayed better properties, such as lower water uptake and higher proton conductivities. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for selected SPAES indicates that they are good candidate proton exchange membrane materials for evaluation in fuel cell applications.
Combed to perfection: Fully aromatic comb‐shaped copolymers based on a poly(arylene ether sulfone) (PAES) backbone with highly sulfonated (SA) poly(phenylene oxide) (PPO) graft chains have a nanochannel morphology (see picture) for efficient proton transport. These molecular structures show a dramatic enhancement in proton conductivity under partially hydrated conditions compared with typical hydrocarbon polymer electrolytes.
Anion exchange membrane (AEM) materials were prepared
from commercial polysulfone (PSf) by functionalization with tertiary
amines via lithiation chemistry. By optimizing the reaction conditions,
a degree of substitution (DS) of 0.81 could be achieved without evident
polymer decomposition or cross-linking. The PSf containing pendent
bis(phenyldimethylamine) substituents were then quaternized with CH3I and ion exchange reaction to provide bis(phenyltrimethylammonium)
(PTMA) polymer with hydroxide-conductive properties. Flexible and
tough membranes with various ion exchange capacities (IEC)s could
be prepared by casting the polymers from DMAc solutions. The ionomeric
membranes showed considerably lower water uptake (less than 20%),
and thus dimensional swelling in water, compared with many reported
AEMs. The hydroxide conductivities of the membranes were above 10
mS/cm at room temperature. The unusually low water uptake and good
hydroxide conductivity may be attributed to the “side-chain-type”
structures of pendent functional groups, which facilitate ion transport.
Although the PTMA substituents on the AEM were found to have insufficient
long-term stability for alkaline fuel cell application, the investigation
gives some insight and directions for polymeric designs by postfunctionalization.
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