Nucleation has been generally acknowledged as a rapid but uncontrollable process that is difficult to decouple from the subsequent growth phase. Here, we report our finding that nucleation of semiconductor magic-size clusters (MSCs) can be well-regulated, without a subsequent evolution in size. Colloidal semiconductor CdS MSCs were synthesized by a two-step approach intentionally designed, without the simultaneous formation of nanocrystals of other sizes. The nuclei MSCs exhibit a sharp optical absorption peaking at 311 nm and are thus denoted by MSC−311. We prepared the immediate precursor for MSC−311 denoted by IP311 which is liquid-like, through a reaction which was normally performed to grow CdS conventional quantum dots (QDs), but at a different temperature (180°C) prior to the nucleation and growth of CdS QDs. We demonstrate that the nucleation of MSC−311 from IP311 followed first order kinetics remarkably well, and the presence of a small amount of methanol accelerated this process effectively. Moreover, the liquid-like prenucleation cluster IP311 and the nuclei MSC−311 have similar masses. Accordingly, we propose that the intramolecular reorganization of IP311 results in the nuclei MSC−311, the formation of which features a two-step nucleation pathway. The present study introduces methodology via absorption spectroscopy to monitor the nucleation kinetics of semiconductor MSCs from their immediate precursors. The repeatable, predictable, and controllable nucleation process investigated here brings a deeper insight into nucleation of other semiconductor nanocrystals and contributes to the foundation for the future development of advanced theoretical models for crystal nucleation.
Little is known about the formation pathway of colloidal semiconductor magic‐size clusters (MSCs). Here, the synthesis of the first single‐ensemble ZnSe MSCs, which exhibit a sharp optical absorption singlet peaking at 299 nm, is reported; their formation is independent of Zn and Se precursors used. It is proposed that the formation of MSCs starts with precursor self‐assembly followed by Zn and Se covalent bond formation to result in immediate precursors (IPs) which can transform into the MSCs. It is demonstrated that the IPs in cyclohexane appear transparent in optical absorption, and become visible as MSCs exhibiting one sharp optical absorption peak when a primary amine is added at room temperature. It is shown that when the preparation of the IP is controlled to be within the induction period, which occurs prior to nucleation and growth of conventional quantum dots (QDs), the resulting MSCs can be produced without the complication of the simultaneous coproduction of conventional QDs. The present study reveals the existence of precursor self‐assembly which leads to the formation of colloidal semiconductor MSCs and provides insights into a multistep nucleation process in cluster science.
The giant panda (Ailuropoda melanoleuca) is currently threatened by habitat loss, fragmentation, and human persecution. Its dietary specialization, habitat isolation, and reproductive constraints have led to a perception that this is a species at an "evolutionary dead end," destined for deterministic extinction in the modern world. Here we examine this perception by a comprehensive investigation of its genetic diversity, population structure, and demographic history across its geographic range. We present analysis of 655 base pairs of mitochondrial (mt) control region (CR) DNA and 10 microsatellite loci for samples from its 5 extant mountain populations (Qinling, Minshan, Qionglai, Liangshan, and Lesser Xiangling). Surprisingly, extant populations display average to high levels of CR and microsatellite diversity compared with other bear species. Genetic differentiation among populations was significant in most cases but was markedly higher between Qinling and the other mountain ranges, suggesting, minimally, that the Qinling population should comprise a separate management unit for conservation purposes. Recent demographic inference using microsatellite markers demonstrated a clear genetic signature for population decline starting several thousands years ago or even further back in the past, and being accelerated and enhanced by the expansion of human populations. Importantly, these data suggest that the panda is not a species at an evolutionary "dead end," but in common with other large carnivores, has suffered demographically at the hands of human pressure. Conservation strategies should therefore focus on the restoration and protection of wild habitat and the maintenance of the currently substantial regional genetic diversity, through active management of disconnected populations.
Ciprofibrate, a hypolipidemic drug that acts as a peroxisome proliferator, induces the transcription of genes encoding peroxisomal (oxidation enzymes. To identify cisacting promoter elements involved in this induction, 5.8 kilobase pairs of promoter sequence from the gene encoding rat peroxisomal enoyl-CoA hydratase/3-hydroxyacyl-CoA dehydrogenase (EC 4.2
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