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We have developed two new star-shaped donor–acceptor oligomers, named TxBT and TxNT, with a truxene donor core and either 2,1,3-benzothiadiazole (BT) or a naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) unit, respectively. Femtosecond transient absorption spectroscopy suggested that both oligomer nanoparticles (NPs) generate long-lived triplet charge-transfer (CT) states following photoexcitation, which undergo reductive quenching by ascorbate. TxNT NPs generate a larger population of reduced species that accumulate and escape recombination compared to TxBT NPs, indicating more efficient charge separation. TxNT NPs show significantly higher hydrogen evolution rate (54 mmol h⁻¹ g⁻¹) compared to TxBT NPs, which is comparable to the performance of the most efficient heterojunction polymer NP systems. Additionally, morphological analysis revealed that Pt deposition was significantly lower on TxBT than on TxNT NPs. These findings highlight the critical role of triplet CT states, tuning molecular energy levels, optimizing excited-state dynamics, and engineering NP architecture to increase photocatalytic hydrogen evolution of organic photocatalysts. To our knowledge, this is the first report where triplet CT states can mediate photocatalytic hydrogen evolution in donor–acceptor oligomer NPs.

The development of photocatalysts to drive organic reactions is a frontier research topic. Organic polymers can be well tuned in terms of structural and photophysical properties and, therefore, constitute a promising class of photocatalysts in photoredox catalysis for organic synthesis. In this review article, we provide an overview of the concept of photoredox catalysis and recent developments in organic polymers as photocatalysts including porous organic polymers, graphitic carbon nitride, carbon dots, and polymer dots with adjustable reactivity that have undergone state-of-the-art advancement in different photoredox catalytic organic reactions.

Three conjugated polymers consisting of truxene donor units and different acceptor units are synthesized and prepared into polymer dots for photocatalytic H2O2 production, exhibiting performance of over 100 mmol h(-1) g(Pdots)(-1). The best external quantum efficiency is determined to be 8.4% at 450 nm in 60 min which is higher than the majority of conjugated polymeric photocatalysts. Optical properties and surface reaction capabilities of Pdots are studied to understand the origin of the photocatalytic performance. The degradation pathway of Pdots is investigated and explained with the help of various spectroscopic characterizations.

BACKGROUND:

Empirical evaluations of sexually dimorphic expression of genes on the mammalian X-chromosome are needed to understand the evolutionary forces and the gene-regulatory mechanisms controlling this chromosome. We performed a large-scale sex-bias expression analysis of genes on the X-chromosome in six different somatic tissues from mouse.

RESULTS:

Our results show that the mouse X-chromosome is enriched with female-biased genes and depleted of male-biased genes. This suggests that feminisation as well as de-masculinisation of the X-chromosome has occurred in terms of gene expression in non-reproductive tissues. Several mechanisms may be responsible for the control of female-biased expression on chromosome X, and escape from X-inactivation is a main candidate. We confirmed escape in case of Tmem29 using RNA-FISH analysis. In addition, we identified novel female-biased non-coding transcripts located in the same female-biased cluster as the well-known coding X-inactivation escapee Kdm5c, likely transcribed from the transition-region between active and silenced domains. We also found that previously known escapees only partially explained the overrepresentation of female-biased X-genes, particularly for tissue-specific female-biased genes. Therefore, the gene set we have identified contains tissue-specific escapees and/or genes controlled by other sexually skewed regulatory mechanisms. Analysis of gene age showed that evolutionarily old X-genes (>100 myr, preceding the radiation of placental mammals) are more frequently female-biased than younger genes.

CONCLUSION:

Altogether, our results have implications for understanding both gene regulation and gene evolution of mammalian X-chromosomes, and suggest that the final result in terms of the X-gene composition (masculinisation versus feminisation) is a compromise between different evolutionary forces acting on reproductive and somatic tissues.

Establishment of silencing by noncoding RNAs (ncRNAs) via targeting of chromatin remodelers is relatively well investigated; however, their role in the maintenance of silencing is poorly understood. Here, we explored the functional role of the long ncRNA Kcnq1ot1 in the maintenance of transcriptional gene silencing in the one mega-base Kcnq1 imprinted domain in a transgenic mouse model. By conditionally deleting the Kcnq1ot1 ncRNA at different stages of mouse development, we suggest that Kcnq1ot1 ncRNA is required for the maintenance of the silencing of ubiquitously imprinted genes (UIGs) at all developmental stages. In addition, Kcnq1ot1 ncRNA is also involved in guiding and maintaining the CpG methylation at somatic differentially methylated regions flanking the UIGs, which is a hitherto unknown role for a long ncRNA. On the other hand, silencing of some of the placental-specific imprinted genes (PIGs) is maintained independently of Kcnq1ot1 ncRNA. Interestingly, the non-imprinted genes (NIGs) that escape RNA-mediated silencing are enriched with enhancer-specific modifications. Taken together, this study illustrates the gene-specific maintenance mechanisms operational at the Kcnq1 locus for tissue-specific transcriptional gene silencing and activation.

Genomic analyses have demonstrated that although less than 2% of the mammalian genome encodes proteins, at least two thirds is transcribed. Many nontranslated RNAs have now been characterized, and several long transcripts, ranging from 0.5 to over 100 kb, have been shown to regulate gene expression by modifying chromatin structure. Functions uncovered at a few well characterized loci demonstrate a wide diversity of mechanisms by which long noncoding RNAs can regulate chromatin over a single promoter, a gene cluster, or an entire chromosome, in order to activate or silence genes in cis or in trans. In reviewing the activities of these ncRNAs, we will look for common features in their interactions with the chromatin modifying machinery, and highlight new experimental approaches by which to address outstanding issues in ncRNA-dependent regulation of gene expression in development, disease and evolution.