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Gossypol is a yellow polyphenol naturally produced by Malvaceae plants such as cotton, which mainly exists in roots, stems, leaves, and seeds of cotton. Gossypol has animal toxicity, and long-term intake of gossypol will accumulate in livestock and cause poisoning, resulting in decreased fecundity, organ lesions, and even death of animals. The cotton output in Xinjiang is huge, accounting for more than 80% of the whole country. After cotton harvest, most of the waste cotton straws are directly crushed and returned to the field, resulting in great waste of resources. Cotton straw is rich in crude protein, cellulose, hemicellulose, and lignin, which is equivalent to common crop straw in nutritional components. However, its gossypol content exceeded the standard, which limited the application of cotton straw feed. How to achieve efficient and low-cost detoxification of gossypol has become the key factor to determining the fodder of cotton straw. The structure, properties, toxicity, detoxification technology, and detoxification mechanism of gossypol were summarized in this paper, which provided a reference for feed utilization of cotton straw. [ABSTRACT FROM AUTHOR]

Pinus L. is the largest genus of conifers and provides a classical model for studying species divergence and phylogenetic evolution by gymnosperms. However, our poor understanding of sequence divergence in the whole plastid genomes of Pinus species severely hinders studies of their evolution and phylogeny. Thus, we analyzed the sequences of 97 Pinus plastid genomes, including four newly sequenced genomes and 93 previously published plastomes, to explore the evolution and phylogenetic relationships in the genus Pinus. The complete chloroplast genomes of Pinus species ranged in size from 109 640 bp (P. cembra L.) to 121 976 bp (P. glabra Walter), and these genomes comprised circular DNA molecules in a similar manner to those of most gymnosperms. We identified 9108 repeats where most of the repeats comprised the dispersed type with 3983 (44%), followed by tandem repeats with 2999 (33%), and then palindromic repeats with 2126 (23%). Sixteen divergence hotspot regions were identified in Pinus plastid genomes, which could be useful molecular markers for future population genetics studies. Phylogenetic analysis showed that Pinus species could be divided into two diverged clades comprising the subgenera Strobus (single needle section) and Pinus (double needles section). Molecular dating suggested that the genus Pinus originated approximately 130.38 Mya during the late Cretaceous. The two subgenera subsequently split 85.86 Mya, which was largely consistent with the other molecular results based on partial DNA markers. These findings provide important insights into the sequence variations and phylogenetic evolution of Pinus plastid genomes. [ABSTRACT FROM AUTHOR]

The most effective way to understand reaction mechanisms and kinetics is to identify the reaction intermediates and determine the possible reaction patterns. The influencing factors that must be considered in the self-assembly of clusters are the type of ligand, metal ion, coordination anion and the pH of the solution. However, changes in ligand substituents resulting in different self-assembly processes to obtain different types of structures are still very rare, especially with –H and –CH3 substituents, which do not exert significant steric hindrance effects. In this study, planar mononuclear Ni(L1)2 (L1 = 2-ethoxy-6-(iminomethyl)phenol) was dissolved in methanol and combined with Dy(NO3)3·6H2O for 48 h at room temperature to obtain a butterfly-like Ni2Dy2 cluster ([Dy2Ni2(L1)4(CH3O)2(NO3)4], 1). The Dy(III) ions in cluster 1 are in an O8N coordination environment, and the Ni(II) ions are in an O5N coordination environment. High-resolution electrospray ionization mass spectrometry (HRESI-MS) was used to track species changes during the formation of cluster 1. Six key intermediate fragments were screened, and the self-assembly mechanism was proposed as Ni(L1)2 → HL1 + NiL1 → DyL1/Ni(L1)2′ → DyNi(L1)2 → Dy2Ni2(L1)4. Through this assembly mechanism, we found that Ni(L1)2 was first cleaved into HL1 + NiL1 and then further assembled to obtain 1. Another butterfly-like tetranuclear heterometallic cluster ([Dy2Ni2(L2)4(CH3O)2(NO3)4], 2) was obtained using planar mononuclear Ni(L2)2 (L2 = (E)-2-ethoxy-6-((methylimino)methyl)phenol) with –CH3 substitution on the nitrogen atom under the same reaction conditions. The structural analysis of cluster 2 showed that the Dy(III) ions are in an O9 coordination environment, and the Ni(II) ions are in an O4N2 coordination environment. HRESI-MS was used to trace species changes during the formation of 2, and the assembly mechanism was proposed as Ni(L2)2 → DyNi(L2)2 → Dy2Ni(L2)2 → Dy2Ni2(L2)4. Analysis of the assembly mechanism of 2 showed that Ni(L2)2 was twisted during the reaction, and its coordination point was exposed to capture the Dy(III) ions. Finally, Dy(NO3)3·6H2O was replaced with NaN3 to obtain a [Ni2Na2(L2)4(N3)4] cluster (3) under the same reaction conditions and verify the above-mentioned torsion step. HRESI-MS was also used to trace the assembly process, and the assembly mechanism was proposed as Ni(L2)2 → NiNa(L2)2 → NiNa2(L2)2 → Ni2Na2(L2)4. Herein, the effect of interference from substitution and the regulation self-assembly process were discovered in the formation of 3d–4f heterometallic clusters, and different types of coordination clusters were obtained. [ABSTRACT FROM AUTHOR]

The formation of high-nuclearity clusters of lanthanide usually involves many complicated self-assembly processes. Thus, tracking the formation process is extremely difficult and research on the assembly mechanism is very rare. In this study, a Dy-exclusive nanocluster containing vertex-sharing [Dy4(μ3-OH)4] cubanes, denoted as [Dy12(L)8(OH)16(CH3O)8(H2O)8]·(CH3O)4 (Dy12, L = quinoline-2-carboxylate), was designed and synthesized from L and DyCl3·6H2O. Eight quinoline-2-carboxylate ligands were encapsulated on the periphery of the Dy12 cluster, which served to stabilize the core. The high stability of the Dy12 cluster core was further confirmed by high-resolution electrospray-ionization mass spectrometry (HRESI-MS). With increased ion-source energy, only CH3O− and OH− bridging ligands were replaced inside the Dy12 cluster. Notably, eight intermediate fragments were successfully observed from the Dy12 cluster formation by time-dependent HRESI-MS. First, ligand L captured Dy3+ to give Dy1, which further formed Dy2 through μ2-O bridging. The Dy12 cluster was constructed in one step with four Dy2 and four Dy3+ as templates: L → Dy1→ Dy2→ Dy12. Moreover, a series of Dy3–Dy6 fragment peaks with relatively weak intensities were observed, and an alternative stepwise-assembly route was proposed: L → Dy1→ Dy2→ Dy3→ Dy4→ Dy5→ Dy6→ Dy12. On comparing the two different assembly methods, the multitemplate guided assembly formed Dy12 was found to be dominant. To the best of our knowledge, this study was the first to propose the involvement of two self-assembly mechanisms in the construction of lanthanide clusters, as further confirmed by HRESI-MS. Magnetic studies further showed that Dy12 clusters exhibited field-induced single-molecule magnet behavior. [ABSTRACT FROM AUTHOR]

Metal nanoclusters have a certain rigidity due to their specific coordination patterns and shapes; thus, they face extreme difficulty in folding into a specific direction to form a double‐helix structure and in further interconnecting to form metal–helix frameworks (MHFs). To date, no MHFs have been produced by the formation of heterometallic clusters. Selecting the appropriate "bonding molecules" to bond metal nanoclusters in a specific multiple direction is one of the most effective strategies for designing synthetic MHFs. In this study, we realized for the first time the control of different orientations of μ3‐NO3− to join heterometallic clusters (Cu10Dy2) and subsequently form a left‐handed double helix chain, which further joins to form MHFs. In the structure of the MHFs, four different directions of bridging μ3‐NO3− exist, three of which are involved in the linkage of the double‐helix chain. Each μ3‐NO3− is connected to three adjacent Cu10Dy2. Herein, we extend a new method for designing synthetic double‐helix structures and MHFs, thereby further laying the foundation for the development of similar DNA double‐helix structures and nucleic acid secondary structures in vitro. [ABSTRACT FROM AUTHOR]

Cotton (Gossypium spp.) is a vital global source of renewable fiber and ranks among the world's most important cash crops. While extensive nuclear genomic data of Gossypium has been explored, the organellar genomic resources of allotetraploid cotton, remain largely untapped at the population level. The plastid genome (plastome) is well suited for studying plant species relationships and diversity due to its nonrecombinant uniparental inheritance. Here, we conducted de novo assembly of 336 Gossypium plastomes, mainly from domesticated cultivars, and generated a pan‐plastome level resource for population structure and genetic diversity analyses. The assembled plastomes exhibited a typical quadripartite structure and varied in length from 160 103 to 160 597 bp. At the species level, seven allotetraploid species were resolved into three clades, where Gossypium tomentosum and Gossypium mustelinum formed an early diverging clade rooted by diploids, followed by splitting two sister clades of Gossypium darwinii–Gossypium barbadense and Gossypium hirsutum–Gossypium ekmanianum–Gossypium stephensii. Within the G. hirsutum clade the resolution of cultivated accessions was less polyphyletic with landrace and wild accessions than in G. barbadense suggesting some selection on plastome in the domestication of this adaptable species of cotton. The nucleotide diversity of G. hirsutum was higher than that of G. barbadense. We specifically compared the plastomes of G. hirsutum and G. barbadense to find mutational hotspots within each species as potential molecular markers. These findings contribute a valuable resource for exploring cotton evolution as well as in the breeding of new cotton cultivars and the preservation of wild and cultivated germplasm. [ABSTRACT FROM AUTHOR]

Copper(II) (Cu 2+ ) is essential for plant growth and development. However, high concentrations are extremely toxic to plants. We investigated the tolerance mechanism of cotton under Cu 2+ stress in a hybrid cotton variety (Zhongmian 63) and two parent lines with different Cu 2+ concentrations (0, 0.2, 50, and 100 μM). The stem height, root length, and leaf area of cotton seedlings had decreased growth rates in response to increasing Cu 2+ concentrations. Increasing Cu 2+ concentration promoted Cu 2+ accumulation in all three cotton genotypes' roots, stems, and leaves. However, compared with the parent lines, the roots of Zhongmian 63 were richer in Cu 2+ and had the least amount of Cu 2+ transported to the shoots. Moreover, excess Cu 2+ also induced changes in cellular redox homeostasis, causing accumulation of hydrogen peroxide (H 2 O 2 ) and malondialdehyde (MDA). Conversely, antioxidant enzyme activity increased, while photosynthetic pigment content decreased. Our findings indicated that the hybrid cotton variety fared well under Cu 2+ stress. This creates a theoretical foundation for the further analysis of the molecular mechanism of cotton resistance to copper and suggests the potential of the large-scale planting of Zhongmian 63 in copper-contaminated soils.

Metal nanoclusters have a certain rigidity due to their specific coordination patterns and shapes; thus, they face extreme difficulty in folding into a specific direction to form a double-helix structure and in further interconnecting to form metal-helix frameworks (MHFs). To date, no MHFs have been produced by the formation of heterometallic clusters. Selecting the appropriate "bonding molecules" to bond metal nanoclusters in a specific multiple direction is one of the most effective strategies for designing synthetic MHFs. In this study, we realized for the first time the control of different orientations of μ 3 -NO 3 - to join heterometallic clusters (Cu 10 Dy 2 ) and subsequently form a left-handed double helix chain, which further joins to form MHFs. In the structure of the MHFs, four different directions of bridging μ 3 -NO 3 - exist, three of which are involved in the linkage of the double-helix chain. Each μ 3 -NO 3 - is connected to three adjacent Cu 10 Dy 2 . Herein, we extend a new method for designing synthetic double-helix structures and MHFs, thereby further laying the foundation for the development of similar DNA double-helix structures and nucleic acid secondary structures in vitro., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The formation of high-nuclearity clusters of lanthanide usually involves many complicated self-assembly processes. Thus, tracking the formation process is extremely difficult and research on the assembly mechanism is very rare. In this study, a Dy-exclusive nanocluster containing vertex-sharing [Dy 4 (μ 3 -OH) 4 ] cubanes, denoted as [Dy 12 (L) 8 (OH) 16 (CH 3 O) 8 (H 2 O) 8 ]·(CH 3 O) 4 (Dy 12 , L = quinoline-2-carboxylate), was designed and synthesized from L and DyCl 3 ·6H 2 O. Eight quinoline-2-carboxylate ligands were encapsulated on the periphery of the Dy 12 cluster, which served to stabilize the core. The high stability of the Dy 12 cluster core was further confirmed by high-resolution electrospray-ionization mass spectrometry (HRESI-MS). With increased ion-source energy, only CH 3 O - and OH - bridging ligands were replaced inside the Dy 12 cluster. Notably, eight intermediate fragments were successfully observed from the Dy 12 cluster formation by time-dependent HRESI-MS. First, ligand L captured Dy 3+ to give Dy 1 , which further formed Dy 2 through μ 2 -O bridging. The Dy 12 cluster was constructed in one step with four Dy 2 and four Dy 3+ as templates: L → Dy 1 → Dy 2 → Dy 12 . Moreover, a series of Dy 3 -Dy 6 fragment peaks with relatively weak intensities were observed, and an alternative stepwise-assembly route was proposed: L → Dy 1 → Dy 2 → Dy 3 → Dy 4 → Dy 5 → Dy 6 → Dy 12 . On comparing the two different assembly methods, the multitemplate guided assembly formed Dy 12 was found to be dominant. To the best of our knowledge, this study was the first to propose the involvement of two self-assembly mechanisms in the construction of lanthanide clusters, as further confirmed by HRESI-MS. Magnetic studies further showed that Dy 12 clusters exhibited field-induced single-molecule magnet behavior.

Two polymorphs of supramolecular isomers, a discrete dimer and a zig-zag chain, having the same chemical composition, [Mn(Hbit)Cl 2 ] (Hbit=1-methyl-2-(1H-1,2,3-triazol-4-yl)-1H-benzo[d]imidazole), were obtained solvothermally in a one-pot synthesis. The isomers differ in a number of ways: orange blocks versus pale-yellow needles, triclinic P1‾ versus orthorhombic Pbcn, double μ 2 -Cl versus alternate single and triple μ 2 -Cl, coordination number 5 versus 6, and antiparallel versus parallel near-neighbor orientation of Hbit. The packing in each case is driven by the supramolecular interactions, H-bonds (N-H⋅⋅⋅Cl, C-H⋅⋅⋅Cl) and π⋅⋅⋅π overlaps, calculated to be in the range 20-36 kcal mol -1 . Calculations gave a difference of only 2 kcal mol -1 in favor of the dimer, which confirms with the observation of principally the dimer at short reaction time. ESI-MS spectra of the dissolved crystals reveal the same fragments with similar distributions. The presence of two fragments at m/z 286.96 [Mn IV (Hbit)Cl-2H] + and 323.94 [Mn III (Hbit)Cl 2 ] + indicates that [Mn(Hbit)Cl 2 ] is the building unit in both cases; thus, the different orientations of the ligands lead to the two polymorphs stabilized by the respective supramolecular interactions. Importantly, the chain form represents the first example with alternate single and triple μ 2 -Cl bridges. The magnetic interactions are weakly antiferromagnetic in both cases, with J in the range 0.07-0.34 cm -1 ; however, high-field EPR analysis reveals moderate magneto-anisotropy with D=0.26(1) cm -1 , E=0.06(1) cm -1 and D=0.17(1) cm -1 , E=0.03(1) cm -1 , respectively., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)