Intermolecular Carbophosphination of Alkynes with Phosphole Oxides via Ni-Al Bimetal-Catalyzed C-P Bond Activation.

Intermolecular carbophosphination reaction of alkynes or alkenes with unreactive C-P bonds remains an elusive challenge. Herein, we used a Ni-Al bimetallic catalyst to realize an intermolecular carbophosphination reaction of alkynes with 5-membered phosphole oxides, providing a series of 7-membered phosphepines in up to 94 % yield.

Enantioselective Nickel-Catalyzed C(sp3 )-H Activation of Formamides.

Enantioselective Ni-catalyzed C(sp3 )-H bond activation remains an elusive challenge. Herein, we used phosphine oxide-ligated Ni-Al bimetallic catalyst to realize enantioselective Ni-catalyzed aliphatic C(sp3 )-H activation of formamides, providing a series of chiral N-containing heterocycles in 40-95 % yield and 70-95 % ee.

Carbamoyl Fluoride-Enabled Enantioselective Ni-Catalyzed Carbocarbamoylation of Unactivated Alkenes.

A carbamoyl fluoride-enabled enantioselective Ni-catalyzed carbocarbamoylation of unactivated alkenes was developed, providing a broad range of chiral γ-lactams bearing an all-carbon quaternary center in 45-96% yield and 38-97% ee.

Similar geometric rules govern the distribution of veins and stomata in petals, sepals and leaves.

Investment in leaf veins (supplying xylem water) is balanced by stomatal abundance, such that sufficient water transport is provided for stomata to remain open when soil water is abundant. This coordination is mediated by a common dependence of vein and stomatal densities on cell size. Flowers may not conform to this same developmental pattern if they depend on water supplied by the phloem or have high rates of nonstomatal transpiration. We examined the relationships between veins, stomata and epidermal cells in leaves, sepals and petals of 27 angiosperms to determine whether common spacing rules applied to all tissues. Regression analysis found no evidence for different relationships within organ types. Both vein and stomatal densities were strongly associated with epidermal cell size within organs, but, for a given epidermal cell size, petals had fewer veins and stomata than sepals, which had fewer than leaves. Although our data support the concept of common scaling between veins and stomata in leaves and flowers, the large diversity in petal vein density suggests that, in some species, petal veins may be engaged in additional functions, such as the supply of water for high cuticular transpiration or for phloem delivery of water or carbohydrates.

Leaves, not roots or floral tissue, are the main site of rapid, external pressure-induced ABA biosynthesis in angiosperms.

Rapid biosynthesis of abscisic acid (ABA) in the leaf, triggered by a decrease in cell volume, is essential for a functional stomatal response. However, it is not known whether rapid biosynthesis of ABA is also triggered in other plant tissues. Through the application of external pressure to flower, root, and leaf tissues, we test whether a reduction in cell volume can trigger rapid increases in ABA levels across the plant body in two species, Solanum lycopersicum and Passiflora tarminiana. Our results show that, in contrast to rapid ABA synthesis in the leaf, flower and root tissue did not show a significant, increase in ABA level in response to a drop in cell volume over a short time frame, suggesting that rapid ABA biosynthesis occurs only in leaf, not in flower or root tissues. A gene encoding the key, rate-limiting carotenoid cleavage enzyme (9-cis-epoxycarotenoid dioxygenase, NCED) in the ABA biosynthetic pathway in S. lycopersicum, NCED1, was upregulated to a lesser degree in flowers and roots compared with leaves in response to applied pressure. In both species, floral tissues contained substantially lower levels of the NCED substrate 9'-cis-neoxanthin than leaves, and this ABA precursor could not be detected in roots. Slow and minimal ABA biosynthesis was detected after 2 h in petals, indicating that floral tissue is capable of synthesizing ABA in response to sustained water deficit. Our results indicate that rapid ABA biosynthesis predominantly occurs in the leaves, and not in other tissues.

Are flowers vulnerable to xylem cavitation during drought?

Water stress is known to cause xylem cavitation in the leaves, roots and stems of plants, but little is known about the vulnerability of flowers to xylem damage during drought. This is an important gap in our understanding of how and when plants become damaged by water stress. Here we address fundamental questions about if and when flowers suffer cavitation damage, using a new technique of cavitation imaging to resolve the timing of cavitation in water-stressed flower petals compared with neighbouring leaves. Leaves and flowers from a sample of two herbaceous and two woody eudicots were exposed to a severe water stress while the spatial and temporal propagation of embolism through veins was recorded. Although in most cases water potentials inducing 50% embolism of herbaceous flower veins were more negative than neighbouring leaves, there was no significant difference between the average vulnerability of leaves and petals of herbaceous species. In both woody species, petals were more vulnerable to cavitation than leaves, in one case by more than 3 MPa. Early cavitation and subsequent damage of flowers in the two woody species would thus be expected to precede leaf damage during drought. Similar cavitation thresholds of flowers and leaves in the herb sample suggest that cavitation during water shortage in these species will occur simultaneously among aerial tissues. Species-specific differences in the cavitation thresholds of petals provide a new axis of variation that may explain contrasting flowering ecology among plant species.

[Determination of multi-elements in aquatic feed by microwave plasma-atomic emission spectroscopy].

In the present research, a novel method for quantitative analysis of multi-elements (Cu, Fe, Mn, Zn, K and Na) in aquatic feed was established by using microwave plasma-atomic emission spectroscopy (MP-AES) technology. The sample was pretreated by traditional dry ashing method, and then a series of methodological study experiments, such as the detection limit, the spiked recovery, the precision measurement, the method comparison with AAS and ICP-AES, the standard substance confirmation and so on, were accomplished by MP-AES. The instrument parameters of MP-AES were optimized. In the optimal con- ditions, the linear calibration curve was established for each element, and the linear regression correlation coefficient was more than 0. 999. The limit of detection (LOD) was between 0. 4 and 3. 9 mg . kg-1. The spiked recovery was between 103% and 112%. The relative standard deviation of precision measurement was between 0. 2% and 0. 6%. In the method comparison, the one way ANOVA statistical analysis yielded the p value between 0. 065 and 0. 438, which were greater than 0. 05, there was no statistically significant difference among MP-AES, AAS and ICP-AES. The FAPAS 10102 dairy ration test material and the national standard substances (GBW07602) were prepared for method confirmation in this study, and the measured values were in good agreement with the certified values. Compared with the commercial ICP-AES which typically uses argon as the plasma gas, the MP-AES relies on using nitrogen as the plasma gas, which may provide a more economical alternative to traditional ICP-AES for routine analysis in feed analytical laboratories. The established method was simple, fast, reproducible and accurate, and it was an ideal analysis technique to substitute AAS and ICP-AES for the determination of multi-elements in aquatic feed.

Catalyst-Controlled Nickel-Catalyzed Intramolecular endo-Selective C-H Cyclization of Benzimidazoles with Alkenes.

Compared with the widely explored exo-selective C-H cyclization, transition metal-catalyzed endo-selective C-H cyclization of benzimidazoles with alkenes has been a formidable challenge. Previous efforts mainly rely on substrate-controlled methods, rendering the product complexity restricted. Herein we report a catalyst-controlled method to facilitate endo-cyclization, in which a bulky N-heterocyclic carbene ligand and tBuOK base-enabled Ni-Al bimetallic catalyst prove critical to the endo selectivity.

Convergent relationships between flower economics and hydraulic traits across aquatic and terrestrial herbaceous plants.

Maintaining open flowers is critical for successful pollination and depends on long-term water and carbon balance. Yet the relationship between how flower hydraulic traits are coordinated in different habitats is poorly understood. Here, we hypothesize that the coordination and trade-offs between floral hydraulics and economics traits are independent of environmental conditions. To test this hypothesis, we investigated a total of 27 flower economics and hydraulic traits in six aquatic and six terrestrial herbaceous species grown in a tropical botanical garden. We found that although there were a few significant differences, most flower hydraulics and economics traits did not differ significantly between aquatic and terrestrial herbaceous plants. Both flower mass per area and floral longevity were significantly positively correlated with the time required for drying full-hydrated flowers to 70% relative water content. Flower dry matter content was strongly and positively related to drought tolerance of the flowers as indicated by flower water potential at the turgor loss point. In addition, there was a trade-off between hydraulic efficiency and the construction cost of a flower across species. Our results show that flowers of aquatic and terrestrial plants follow the same economics spectrum pattern. These results suggest a convergent flower economics design across terrestrial and aquatic plants, providing new insights into the mechanisms by which floral organs adapt to aquatic and terrestrial habitats.

Dark purple nectar as a foraging signal in a bird-pollinated Himalayan plant.

• Some plants secrete coloured nectar to attract pollinators, but little is known about the chemical origins of nectar colouration and its ecological function. Leucosceptrum canum stands out as the only plant with coloured nectar recorded in the Himalayas. Here, we focused on the compound associated with the dark colour of the nectar, as well as its secretion dynamics during the flowering season and its relationship to pollinators. • Fresh nectar was analysed by semi-preparative reversed-phase high-performance liquid chromatography (HPLC), LC-MS and HRESIMS (high resolution electronspray ionization mass spectroscopy) to determine which compound causes the nectar colouration. Behavioural experiments were conducted with birds and honeybees to elucidate the effect of the nectar colour and volume on pollinators. • We identified a purple anthocyanidin, 5-hydroxyflavylium, as a natural nectar product for the first time. Two short-billed birds were found to pollinate this plant, which employs two nectar-based mechanisms to direct bird pollinators to reproductively active flowers, controlling nectar palatability and presenting a foraging signal for birds by altering nectar volume and colour in a developmental stage-specific manner. • 5-Hydroxyflavylium was found to be the cause of the nectar colouration, the function of which is to act as a foraging signal to increase pollination efficiency through nectar visibility and palatability.

[Rapid determination of fatty acids in soybean oils by transmission reflection-near infrared spectroscopy].

In the present research, a novel method was established for determination of five fatty acids in soybean oil by transmission reflection-near infrared spectroscopy. The optimum conditions of mathematics model of five components (C16:0, C18:0, C18:1, C18:2 and C18:3) were studied, including the sample set selection, chemical value analysis, the detection methods and condition. Chemical value was analyzed by gas chromatography. One hundred fifty eight samples were selected, 138 for modeling set, 10 for testing set and 10 for unknown sample set. All samples were placed in sample pools and scanned by transmission reflection-near infrared spectrum after sonicleaning for 10 minute. The 1100-2500 nm spectral region was analyzed. The acquisition interval was 2 nm. Modified partial least square method was chosen for calibration mode creating. Result demonstrated that the 1-VR of five fatty acids between the reference value of the modeling sample set and the near infrared spectrum predictive value were 0.8839, 0.5830, 0.9001, 0.9776 and 0.9596, respectively. And the SECV of five fatty acids between the reference value of the modeling sample set and the near infrared spectrum predictive value were 0.42, 0.29, 0.83, 0.46 and 0.21, respectively. The standard error of the calibration (SECV) of five fatty acids between the reference value of testing sample set and the near infrared spectrum predictive value were 0.891, 0.790, 0.900, 0.976 and 0.942, respectively. It was proved that the near infrared spectrum predictive value was linear with chemical value and the mathematical model established for fatty acids of soybean oil was feasible. For validation, 10 unknown samples were selected for analysis by near infrared spectrum. The result demonstrated that the relative standard deviation between predict value and chemical value was less than 5.50%. That was to say that transmission reflection-near infrared spectroscopy had a good veracity in analysis of fatty acids of soybean oil.

Characterization of the complete chloroplast genome of Dendrobium findlayanum Par. et Rchb. f. 1874 (Orchidaceae).

Dendrobium findlayanum Par. et Rchb. f. 1874 has the high ornamental and medicinal value. Here, we report the first complete chloroplast genome of D. findlayanum. The complete chloroplast genome of D. findlayanum is 153,713 bp in length with 120 genes, including 75 protein-coding genes, 37 tRNA genes, and 8 rRNA genes. The total content of GC of the whole genome is 37.46%. Phylogenetic analysis indicated that D. findlayanum was closely related to other species in Dendrobium, and this study provides new genetic resources for species identification and phylogenetic analyses in Dendrobium.

Reduced number of IFN-γ producing cells in peripheral blood is a biomarker for patients with renal cell carcinoma.

Renal cell cancer (RCC) is the most lethal of all the common urologic cancers and constitutes 2.2% of all malignancy diagnoses. The incidence of RCC has been steadily increasing in recent decades. The classic risk factors of RCC include smoking, hypertension, obesity, genetics, and genetic mutations. Recent studies also revealed that RCC was an immunogenic tumor and affected by host immune status. Among the pan-cance, RCC presented with the highest degree of immune infiltration, indicating RCC patients might benefit from immunotherapy. A new immune classification of RCC has been developed by Su et al. based on tumor-infiltrating lymphocytes to guide clinical practice. However, these studies mainly focus on biomarkers derived from tumor microenvironment (TME), the biomarkers based on peripheral blood samples to RCC have rarely been described. We collected peripheral blood samples from RCC patients and their matched healthy controls and detected the number of IL-2 and IFN-γ producing cells by implementing an enzyme-linked immunospot (ELISPOT) assay. This is the first study to report blood-based immune biomarkers for RCC using an ELISPOT assay. Our results suggested the frequency of IFN-γ producing cells but not IL-2 producing cells was associated with RCC risk. These findings warrant further validation in larger prospective studies.

Genome Size and Labellum Epidermal Cell Size Are Evolutionarily Correlated With Floral Longevity in Paphiopedilum Species.

Genome size is known to influence phenotypic traits in leaves and seeds. Although genome size is closely related to cellular and developmental traits across biological kingdoms, floral longevity is a floral trait with important fitness consequence, but less is known about the link between floral longevity and sizes of genomes and cells. In this study, we examined evolutionary coordination between genome size, floral longevity, and epidermal cell size in flowers and leaves in 13 Paphiopedilum species. We found that, across all the study species, the genome size was positively correlated with floral longevity but negatively associated with labellum epidermal cell size, and a negative relationship was found between floral longevity and labellum epidermal cell size. This suggested that genome size is potentially correlated with floral longevity, and genome size has an important impact on life-history trait. In addition, genome size was positively correlated with leaf epidermal cell size, which was different from the relationship in flower due to different selective pressures they experienced or different functions they performed. Therefore, genome size constraints floral longevity, and it is a strong predictor of cell size. The impact of genome size on reproduction might have more implications for the evolution of flowering plants and pollination ecology.

Cavitation resistance of peduncle, petiole and stem is correlated with bordered pit dimensions in Magnolia grandiflora.

Variation in resistance of xylem to embolism among flowers, leaves, and stems strongly influences the survival and reproduction of plants. However, little is known about the vulnerability to xylem embolism under drought stress and their relationships to the anatomical traits of pits among reproductive and vegetative organs. In this study, we investigated the variation in xylem vulnerability to embolism in peduncles, petioles, and stems in a woody plant, Magnolia grandiflora. We analyzed the relationships between water potentials that induced 50% embolism (P50) in peduncles, petioles, and stems and the conduit pit traits hypothesized to influence cavitation resistance. We found that peduncles were more vulnerable to cavitation than petioles and stems, supporting the hypothesis of hydraulic vulnerability segmentation that leaves and stems are prioritized over flowers during drought stress. Moreover, P50 was significantly correlated with variation in the dimensions of inter-vessel pit apertures among peduncles, petioles and stems. These findings highlight that measuring xylem vulnerability to embolism in reproductive organs is essential for understanding the effect of drought on plant reproductive success and mortality under drought stress.

Characterization of the complete chloroplast genome of Dendrobium christyanum and its phylogenetic analysis.

Dendrobium christyanum H.G. Reichenbach (Orchidaceae) is used as a source of the Chinese traditional medicine. Here, we report that the complete chloroplast (cp) genome sequence of D. christyanum is 157972 bp in length with134 genes, of which 114 are unique genes (80 protein-coding genes, 30 tRNAs, and 4 rRNAs). Phylogenetic analysis indicated that D. christyanum was closely related to D. strongylanthum, and D. longicornu. The newly sequenced cp genome will be useful for the phylogenetic and genetic conservation studies of Dendrobium.

Allometry Between Vegetative and Reproductive Traits in Orchids.

In flowering plants, inflorescence characteristics influence both seed set and pollen contribution, while inflorescence and peduncle size can be correlated with biomass allocation to reproductive organs. Peduncles also play a role in water and nutrient supply of flowers, and mechanical support. However, it is currently unclear whether inflorescence size is correlated with peduncle size. Here, we tested whether orchids with large diameter peduncles bear more and larger flowers than those with smaller peduncles by analyzing 10 traits of inflorescence, flower, and leaf in 26 species. Peduncle diameters were positively correlated with inflorescence length and total floral area, indicating that species with larger peduncles tended to have larger inflorescences and larger flowers. We also found strongly positive correlation between inflorescence length and leaf area, and between total floral area and total leaf area, which suggested that reproductive organs may be allometrically coordinated with vegetative organs. However, neither flower number nor floral dry mass per unit area were correlated with leaf number or leaf dry mass per unit area, implying that the function between leaf and flower was uncoupled. Our findings provided a new insight for understanding the evolution of orchids, and for horticulturalists interested in improving floral and inflorescence traits in orchids.

Is seasonal flowering time of Paphiopedilum species caused by differences in initial time of floral bud differentiation?

Members of the genus Paphiopedilum are world-famous for their large, colourful flowers, unique floral morphology and long floral lifespan. Most Paphiopedilum species bloom in spring or autumn. The control of flowering time is of great significance to the commercial production of floral crops, because it affects the sales and prices of flowers. However, the mechanism that regulates when Paphiopedilum species bloom is unclear. In the present study, floral bud initiation and development of P. micranthum (spring-flowering species with one flower per stalk), P. dianthum (autumn-flowering species with multiple flowers per stalk) and P. henryanum (autumn-flowering species with one flower per stalk) were investigated by morphological and anatomical methods. We divided Paphiopedilum floral bud differentiation into six phases: the initiation of differentiation, inflorescence primordium differentiation, flower primordium differentiation, sepal primordium differentiation, petal primordium differentiation and column primordium differentiation. We found that the timing of floral bud differentiation for the three species was synchronized when experiencing the same environment, while the period from initiation to flowering largely differed. In addition, initiation of floral bud differentiation in P. dianthum was earlier at a warmer environment. The difference in flowering time of three species was mainly caused by the duration of floral bud development, rather than the initiation time. The findings were of great significance for the cultivation and flowering regulation of Paphiopedilum species.

Floral Longevity of Paphiopedilum and Cypripedium Is Associated With Floral Morphology.

Floral longevity (FL) is an important trait influencing plant reproductive success by affecting the chance of insect pollination. However, it is still unclear which factors affect FL, and whether FL is evolutionarily associated with structural traits. Since construction costs and water loss by transpiration play a role in leaf longevity, we speculated that floral structures may affect the maintenance and loss of water in flowers and, therefore, FL. Here, we investigated the slipper orchid Paphiopedilum and Cypripedium, which are closely related, but strongly differ in their FL. To understand the evolutionary association of floral anatomical traits with FL, we used a phylogenetic independent comparative method to examine the relationships between 30 floral anatomical traits and FL in 18 species of Paphiopedilum and Cypripedium. Compared with Paphiopedilum species, Cypripedium species have lower values for floral traits related to drought tolerance and water retention capacity. Long FL was basically accompanied by the thicker epidermal and endodermal tissues of the floral stem, the thicker adaxial and abaxial epidermis of the flower, and low floral vein and stomatal densities. Vein density of the dorsal sepals and synsepals was negatively correlated with stomatal density. Our results supported the hypothesis that there was a correlation between FL and floral anatomical traits in slipper orchids. The ability to retain water in the flowers was associated with FL. These findings provide a new insight into the evolutionary association of floral traits with transpirational water loss for orchids under natural selection.