RESUMEN
To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred-handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices. More interestingly, attributed to unique dynamic feature of the [2]catenane pendants, these polymers revealed dynamic response behaviors to solvents, temperature, and sodium ions, resulting in the fully reversible switching on/off of the chirality induction. This work provides not only new design strategy for novel chiroptical switches with topologically chiral molecules but also novel platforms for the development of smart chiral materials.
RESUMEN
Aiming at the further extension of the application scope of traditional molecular muscles, a novel bispyrene-functionalized chiral molecular [c2]daisy chain was designed and synthesized. Taking advantage of the unique dimeric interlocked structure of molecular [c2]daisy chain, the resultant chiral molecular muscle emits strong circularly polarized luminescence (CPL) attributed to the pyrene excimer with a high dissymmetry factor (glum) value of 0.010. More importantly, along with the solvent- or anion- induced motions of the chiral molecular muscle, the precise regulation of the pyrene stacking within its skeleton results in the switching towards either "inversed" state with sign inversion and larger glum values or "down" state with maintained handedness and smaller glum values, making it a novel multistate CPL switch. As the first example of chiral molecular muscle-based CPL switch, this proof-of-concept study not only successfully widens the application scopes of molecular muscles, but also provides a promising platform for the construction of novel smart chiral luminescent materials for practical applications.
RESUMEN
Aiming at the construction of novel stimuli-responsive fluorescent system with precisely tunable emissions, the typical 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration-induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli-responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC-functionalized [2]rotaxanes display interesting VIE behaviors including white-light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion-induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors (glum ) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5-fold increase in glum values up to -0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use.
RESUMEN
In order to clarify the impact of no-tillage on the quality of farmland soil aggregates in China and promote the adaptive application of no-tillage practicesï¼ a Meta-analysis was conducted by collecting data from 116 published studies. The effects of no-tillage on aggregate size distributionï¼ mean weight diameter ï¼MWDï¼ï¼ and aggregate-associated C were studied. The results showed that compared with that under tillageï¼ no-tillage significantly increased the proportion of macroaggregates ï¼10.9%ï¼ and MWD ï¼12.8%ï¼ and decreased the proportion of clay and silt ï¼-15.5%ï¼ but had no significant effect on soil microaggregate and aggregate-associated C. The subgroup and Meta regression analysis showed that no-tillage significantly increased the proportion of macroaggregates in Northwest China ï¼17.6%ï¼ and MWD in North China ï¼15.4%ï¼. In upland and clay loamï¼ no-tillage increased MWD by 12.6% and 18.4%ï¼ respectively. The effect of no-tillage on increasing the proportion of macroaggregates increased with the soil pH. When straw returnedï¼ no-tillage significantly increased the proportion of macroaggregates ï¼9.6%ï¼ and MWD ï¼11.6%ï¼ï¼ but no significant effect of no-tillage on aggregates was found after straw removal. Regarding test durationï¼ short-term ï¼ < 5 aï¼ no-tillage could significantly increase the proportion of macroaggregatesï¼ whereas long-term ï¼ > 10 aï¼ no-tillage could improve the MWD. In different soil layersï¼ no-tillage could only significantly improve the aggregate size distribution and MWD in topsoil ï¼0-20 cmï¼ but had no effect in subsoil ï¼ > 20 cmï¼. In summaryï¼ no-tillage could improve aggregate size distribution and stability but had no effect on aggregate-associated C. Production regionï¼ soil propertiesï¼ field management methodsï¼ and other factors should be fully considered in production practice to effectively improve the quality of soil aggregates.
RESUMEN
In order to investigate the effect of macrocyclization and catenation on the regulation of vibration-induced emission (VIE), the typical VIE luminogen 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) was introduced into the skeleton of a macrocycle and corresponding [2]catenane to evaluate their dynamic relaxation processes. As investigated in detail by femtosecond transient absorption (TA) spectra, the resultant VIE systems revealed precisely tunable emissions upon changing the solvent viscosity, highlighting the key effect of the formation of [2]catenane. Notably, the introduction of an additional pillar[5]arene macrocycle featuring unique planar chirality endows the resultant chiral VIE-active [2]catenane with attractive circularly polarized luminescence in different states. This work not only develops a new strategy for the design of new luminescent systems with tunable vibration induced emission, but also provides a promising platform for the construction of smart chiral luminescent materials for practical applications.
RESUMEN
As a soil amendment, biochar has been widely used to ameliorate agricultural soil. To ensure the effect of biochar on the carbon sequestration of farmlands in China, a Meta-analysis was carried out via collecting published literatures. We quantitatively analyzed the response of biochar application to soil aggregates, aggregate carbon, and soil organic carbon to different experimental conditions. The results showed that the application of biochar significantly increased the proportion of soil macroaggregates(10.8%) and MWD(13.3%) but had no significant effect on soil microaggregates and silty-clay compared with those in the non-biochar-added treatment. Moreover, biochar addition significantly increased soil organic carbon content(56.9%), with the largest increased area in North China(39.4%), and enhanced intra-aggregate carbon contents of each particle size. Biochar could significantly increase soil organic carbon content under different experimental designs. Compared with that under non-fertilization, biochar combined with fertilization could also significantly improve soil structure and soil fertility. We also found that more than two years of biochar application significantly increased the proportion of macroaggregates(15.7%), MWD(21.2%), macroaggregate carbon(31.7%), and soil organic carbon(40.0%). Meanwhile, biochar produced from crop straw had better soil improvement effects than that of wood and sawdust. Biochar applied in high-nitrogen soil was more beneficial to improve soil stability. Thus, we concluded that biochar could meliorate soil structure and promote the accumulation of soil organic carbon, which was of importance for the fertility maintenance and improvement of the farmland.