Demographic dynamics and molecular evolution of the rare and endangered subsect. Gerardianae of Pinus: insights from chloroplast genomes and mitochondrial DNA markers.

MAIN CONCLUSION: The divergence of subsect. Gerardianae was likely triggered by the uplift of the Qinghai-Tibetan Plateau and adjacent mountains. Pinus bungeana might have probably experienced expansion since Last Interglacial period. Historical geological and climatic oscillations have profoundly affected patterns of nucleotide variability, evolutionary history, and species divergence in numerous plants of the Northern Hemisphere. However, how long-lived conifers responded to geological and climatic fluctuations in East Asia remain poorly understood. Here, based on paternally inherited chloroplast genomes and maternally inherited mitochondrial DNA markers, we investigated the population demographic history and molecular evolution of subsect. Gerardianae (only including three species, Pinus bungeana, P. gerardiana, and P. squamata) of Pinus. A low level of nucleotide diversity was found in P. bungeana (π was 0.00016 in chloroplast DNA sequences, and 0.00304 in mitochondrial DNAs). The haplotype-based phylogenetic topology and unimodal distributions of demographic analysis suggested that P. bungeana probably originated in the southern Qinling Mountains and experienced rapid population expansion since Last Interglacial period. Phylogenetic analysis revealed that P. gerardiana and P. squamata had closer genetic relationship. The species divergence of subsect. Gerardianae occurred about 27.18 million years ago (Mya) during the middle to late Oligocene, which was significantly associated with the uplift of the Qinghai-Tibetan Plateau and adjacent mountains from the Eocene to the mid-Pliocene. The molecular evolutionary analysis showed that two chloroplast genes (psaI and ycf1) were under positive selection, the genetic lineages of P. bungeana exhibited higher transition and nonsynonymous mutations, which were involved with the strongly environmental adaptation. These findings shed light on the population evolutionary history of white pine species and provide striking insights for comprehension of their species divergence and molecular evolution.

Porous {P6Mo18O73}-type Poly(oxometalate) Metal-Organic Frameworks for Improved Pseudocapacitance and Electrochemical Sensing Performance.

{P6Mo18} poly(oxometalate) (POM) clusters have huge steric hindrance and limited active oxygen atoms, which make them difficult to combine with metal-organic units to form three-dimensional (3D) porous structures. Therefore, functionalization of such POMs has always been a bottleneck that is difficult to break through. In this study, {P6Mo18} POM was successfully grafted on a lock-like metal-organic chain to generate a multiporous coordination polymer, [{Na(H2O)(H2btb)}{Cu4I(H2O)(pz)5Cl}{H2Sr⊂P6Mo2VMo16VIO73}]·3H2O (1) (pz = pyrazine; btb = 1,4-bis(1,2,4-triazole) butane). Meanwhile, a zero-dimensional (0-D) control compound with only btb ligands as counterions, (H4btb)[H4Sr⊂P6Mo2VMo16VIO73]·3H2O (2), was also obtained via a hydrothermal reaction. Compound 1 represents the first basket-type 3D poly(oxometalate) metal-organic framework (POMOF) assembly, which possesses interpenetrating pores and complex topology. 1-GO-CPE displays improved supercapacitor (SC) performance (the specific capacitance of 929.4 F g-1 at a current density of 3 A g-1 with 94.1% of cycle efficiency after 5000 cycles) compared with 2-GO-CPE and most reported POMOF electrode materials, which may be due to the outstanding redox capability of basket-POM, introduction of metal-organic chains, intersecting pores, and excellent conductivity of graphene. An asymmetric SC device with 1-GO-CPE as the negative electrode exhibits an energy density of 29.7 Wh kg-1 with a power density of 3148.2 W kg-1 and long-lasting cycling life. In addition, 1-GO-GCE as an electrochemical sensor responds to dopamine (DA) at a voltage of 0.40 V and shows lower detection limits (0.19 µM (signal-to-noise ratio (SNR) = 3)), higher selectivity, and good reproducibility in the linear range of 0.56 µM to 0.24 mM. The ability to accurately detect the content of DA in biological samples further proves the feasibility of the sensor in practical applications.