Transition-metal-free radical difluorobenzylation/cyclization of unactivated alkenes: access to ArCF2-substituted ring-fused quinazolinones.

A mild and efficient transition-metal-free radical difluorobenzylation/cyclization of unactivated alkenes toward the synthesis of difluorobenzylated polycyclic quinazolinone derivatives with easily accessible α,α-difluoroarylacetic acids has been developed. This transformation has the advantages of wide functional group compatibility, a broad substrate scope, and operational simplicity. This methodology provided a highly attractive access to pharmaceutically valuable ArCF2-containing polycyclic quinazolinones.

Nitrogen deposition increases xylem hydraulic sensitivity but decreases stomatal sensitivity to water potential in two temperate deciduous tree species.

Although the effects of nitrogen deposition on tree water relations are studied extensively, its impact on the relative sensitivities of stomatal and xylem hydraulic conductance to vapor pressure deficit and water potential is still poorly understood. This study investigated the effects of a 7-year N deposition treatment on the responses of leaf water relations and sensitivity of canopy stomatal conductance to vapor pressure deficit (VPD) and water potential, as well as the sensitivity of branch hydraulic conductance to water potential in a dominant tree species (Quercus wutaishanica) and an associated tree species (Acer mono) in a temperate forest. It was found that the N deposition increased stomatal sensitivity to VPD, decreased stomatal sensitivity to water potential, and increased the vulnerability of the hydraulic system to cavitation in both species. The standardized stomatal sensitivity to VPD, however, was not affected by the N deposition, indicating that the stomata maintained the ability to regulate the water balance under nitrogen deposition condition. Although the increased stomatal sensitivity to VPD could compensate the decreased stomatal sensitivity to water potential to some extent, the combined response would increase the percentage loss of hydraulic conductivity (PLC) when 50 % loss in stomatal conductance occurred, particularly in the dominant species Q. wutaishanica. The result indicates that N deposition would increase the risk of hydraulic failure in those species if the soil and/or air becomes drier under future climate change scenarios. The results of the study can have significant implications on the modelling of ecosystem vulnerability to drought under the scenario of atmospheric nitrogen deposition.

Transition-metal catalyzed oxidative spirocyclization of N-aryl alkynamides with methylarenes under microwave irradiation.

A practical synthetic route to construct a variety of 3-benzyl spiro[4,5]trienones was developed via transition-metal Cu/Ag-catalyzed oxidative ipso-annulation of activated alkynes with unactivated toluenes using TBPB as an oxidant under microwave irradiation. This method allows the formation of two carbon-carbon bonds and one carbon-oxygen bond in a single reaction through a sequence of C-H oxidative coupling, ipso-carbocyclization and dearomatization. The advantages of this protocol are its operational simplicity and broad substrate scope, and the ability to afford the desired products in moderate to good yields.

Stomatal Sensitivity to Vapor Pressure Deficit and the Loss of Hydraulic Conductivity Are Coordinated in Populus euphratica, a Desert Phreatophyte Species.

There are considerable variations in the percentage loss of hydraulic conductivity (PLC) at mid-day minimum water potential among and within species, but the underpinning mechanism(s) are poorly understood. This study tested the hypothesis that plants can regulate leaf specific hydraulic conductance (K l) via precise control over PLC under variable ΔΨ (water potential differential between soil and leaf) conditions to maintain the -m/b constant (-m: the sensitivity of stomatal conductance to VPD; b: reference stomatal conductance at 1.0 kPa VPD), where VPD is vapor pressure deficit. We used Populus euphratica, a phreatophyte species distributed in the desert of Northwestern China, to test the hypothesis. Field measurements of VPD, stomatal conductance (g s), g s responses to VPD, mid-day minimum leaf water potential (Ψ lmin), and branch hydraulic architecture were taken in late June at four sites along the downstream of Tarim River at the north edge of the Taklamakan desert. We have found that: 1) the -m/b ratio was almost constant (=0.6) across all the sites; 2) the average Ψ 50 (the xylem water potential with 50% loss of hydraulic conductivity) was -1.63 MPa, and mid-day PLC ranged from 62 to 83%; 3) there were tight correlations between Ψ 50 and wood density/leaf specific hydraulic conductivity (k l) and between specific hydraulic conductance sensitivity to water potential [d(k s)/dln(-Ψ)] and specific hydraulic conductivity (k s). A modified hydraulic model was applied to investigate the relationship between g s and VPD under variable ΔΨ and K l conditions. It was concluded that P. euphratica was able to control PLC in order to maintain a relatively constant -m/b under different site conditions. This study demonstrated that branchlet hydraulic architecture and stomatal response to VPD were well coordinated in order to maintain relatively water homeostasis of P. euphratica in the desert. Model simulations could explain the wide variations of PLC across and within woody species that are often observed in the field.

Silver-catalyzed direct C-H oxidative carbamoylation of quinolines with oxamic acids.

A silver-catalyzed efficient and direct C-H carbamoylation of quinolines with oxamic acids to access carbamoylated quinolines has been developed through oxidative decarboxylation reaction. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance and excellent yields under mild conditions.

Transition-metal free C3-amidation of quinoxalin-2(1H)-ones using Selectfluor as a mild oxidant.

A practical and efficient synthetic route to construct a variety of 3-amidated quinoxalin-2(1H)-ones was developed via transition-metal free direct oxidative amidation of quinoxalin-2(1H)-ones with amidates using Selectfluor reagent as a mild oxidant. This protocol features mild reaction conditions, operational simplicity, broad substrate scope, and good to excellent yields.

The trade-off between safety and efficiency in hydraulic architecture in 31 woody species in a karst area.

Karst topography is a special landscape shaped by the dissolution of one or more layers of soluble bedrock, usually carbonate rock such as limestone or dolomite. Due to subterranean drainage, overland flow, extraction of water by plants and evapotranspiration, there may be very limited surface water. The hydraulic architecture that plants use to adapt to karst topography is very interesting, but few systematic reports exist. The karst area in southwestern China is unique when compared with other karst areas at similar latitudes, because of its abundant precipitation, with rainfall concentrated in the growing season. In theory, resistance to water-stress-induced cavitation via air seeding should be accompanied by decreased pore hydraulic conductivity and stem hydraulic conductivity. However, evidence for such trade-offs across species is ambiguous. We measured the hydraulic structure and foliar stable carbon isotope ratios of 31 karst woody plants at three locations in Guizhou Province, China, to evaluate the functional coordination between resistance to cavitation and specific conductivity. We also applied phylogenetically independent contrast (PIC) analysis in situations where the inter-species correlations of functional traits may be biased on the potential similarity of closely related species. The average xylem tension measurement, at which 50% of hydraulic conductivity of the plants was lost (Ψ(50)), was only -1.27 MPa. Stem Ψ(50) was positively associated with specific conductance (K(s)) (P < 0.05) and leaf specific conductance (K(l)) (P < 0.05). However, the PIC correlation for both relationships was not statistically significant. δ(13)C was positively related to K(l) in both the traditional cross-species correlation analysis and the corresponding PIC correlations (P < 0.05). The Huber value (sapwood area:leaf area ratio) was negatively correlated with K(s) in both the traditional cross-species correlation and the corresponding PIC correlations (P < 0.01). The characteristics of hydraulic architecture measured in this study showed that karst plants in China are not highly cavitation-resistant species. This study also supports the idea that there may not be an evolutionary trade-off between resistance to cavitation and specific conductivity in woody plants. Whole-plant hydraulic adjustment may decouple the trade-off relationship between safety and efficiency at the branch level.

[Studies on chemical constituents of Halenia elliptica guided by in vivo absorption and distribution of the constituents].

AIM: To investigate the chemical constituents of the Tibetan herbal medicine Halenia elliptica by guidance of in vivo absorption and distribution of the constituents. METHODS: HPLC with a diode array detector (DAD) and HPLC-MS were used for detecting the constituents of extracts of Halenia elliptica and animal samples. Several kinds of column chromatography were used for the isolation and purification of the main in vivo absorbed and distributed compounds from the extract of Halenia elliptica. RESULTS: Six main components detected in the extracts of the animal samples were isolated from the ethanolic extract of Halenia elliptica. CONCLUSION: After rats were treated with different extracts of Halenia elliplica, low polar components xanthone aglycon of Halenia elliptica were clearly observed in the extracts of liver, lipid, blood, hidney, heart and brain tissue of rats, while the polar components xanthone glycosides were detected in very small amounts in the animal samples. The xanthone glycosides can be decomposed into xanthone aglycons during the digestion, absorption and metabolism procedure. Therefore, the in vivo activity of the xanthone glycosides might be exhibited by their decomposed products. It is an accessibly valuable method to investigate chemical components of herbal medicines under the guidance by detecting in vivo absorption and distribution of chemical components of the herbal medicine extract.