N-Heterocyclic Carbene-Derived 1,3,5-Trimethylenebenzene: On-Surface Synthesis and Electronic Structure.

1,3,5-Trimethylenebenzene (1,3,5-TMB), a 3-fold-symmetric triradical with a high-spin ground state, is an attractive platform for investigating the unique spin properties of π-conjugated triangular triradicals. Here, we report the on-surface synthesis of N-heterocyclic carbene (NHC)-derived 1,3,5-TMB (N-TMB) via surface-assisted C-C and C-N coupling reactions on Au(111). The chemical and electronic structures of N-TMB on the Au(111) surface are revealed with atomic precision using scanning tunneling microscopy and noncontact atomic force microscopy, combined with density functional theory (DFT) calculations. It is demonstrated that there is substantial charge transfer between N-TMB and the substrate, resulting in a positively charged N-TMB on Au(111). DFT calculations at the UB3LYP/def2-TZVP level of theory and multireference method, e.g., CASSCF/NEVPT2, indicate that N-TMB possesses a doublet ground state with reduced Cs symmetry in the gas phase, contrasting the quartet ground state of 1,3,5-TMB with D3h symmetry, and exhibits a doublet-quartet energy gap of -0.80 eV. The incorporation of NHC structures and the extended π-conjugation promote the spin-orbital overlaps in N-TMB, leading to Jahn-Teller distortion and the formation of a robust doublet state. Our results not only demonstrate the fabrication of polyradicals based on NHC but also shed light on the effect of NHC and π-conjugation on the electronic structure and spin coupling, which opens up new possibilities for precisely regulating the spin-spin exchange coupling of organic polyradicals.

Silver Surface-Assisted Dehydrobrominative Cross-Coupling between Identical Aryl Bromides.

Cross-coupling reactions represent an indispensable tool in chemical synthesis. An intriguing challenge in this field is to achieve selective cross-coupling between two precursors with similar reactivity or, to the limit, the identical molecules. Here we report an unexpected dehydrobrominative cross-coupling between 1,3,5-tris(2-bromophenyl)benzene molecules on silver surfaces. Using scanning tunneling microscopy, we examine the reaction process at the single-molecular level, quantify the selectivity of the dehydrobrominative cross-coupling, and reveal the modulation of selectivity by substrate lattice-related catalytic activity or molecular assembly effect. Theoretical calculations indicate that the dehydrobrominative cross-coupling proceeds via regioselective C-H bond activation of debrominated TBPB and subsequent highly selective C-C coupling of the radical-based intermediates. The reaction kinetics plays an important role in the selectivity for the cross-coupling. This work not only expands the toolbox for chemical synthesis but also provides important mechanistic insights into the selectivity of coupling reactions on the surface.

Evolution of Br⋯Br contacts in enantioselective molecular recognition during chiral 2D crystallization.

Halogen-mediated interactions play an important role in molecular recognition and crystallization in many chemical and biological systems, whereas their effect on homochiral versus heterochiral recognition and crystallization has rarely been explored. Here we demonstrate the evolution of Br⋯Br contacts in chiral recognition during 2D crystallization. On Ag(100), type I contacts prevail at low coverage and lead to homochiral recognition and the formation of 2D conglomerates; whereas type II contacts mediating heterochiral recognition are suppressed at medium coverage and appear in the racemates induced by structural transitions at high coverage. On Ag(111), type I contacts dominate the 2D crystallization and generate 2D conglomerates exclusively. DFT calculations suggest that the energy difference between type I and type II contacts is reversed upon adsorption due to the substrate induced mismatch energy penalty. This result provides fundamental understanding of halogen-mediated interactions in molecular recognition and crystallization on surface.

Aromatic Ring Fusion to Benzoporphyrin via γ-ortho Cyclodehydrogenation on a Ag(111) Surface.

Aromatic ring fusion to porphyrins and their derivatives represents an attractive route to tune the molecular conjugation and thus expand their functionalities. Here, we report the expansion of the aromatic π-system of palladium tetraphenyltetrabenzoporphyrins (Pd-TPTBP) via surface-assisted γ-ortho cyclodehydrogenation on Ag(111). The chemical transformation of Pd-TPTBP into different products at an elevated temperature of 600 K was revealed at the single-molecule level using bond-resolved scanning tunneling microscopy with a CO-functionalized tip. We captured a series of γ-ortho cyclodehydrogenation products, wherein the maximum extent to which the reaction can progress is associated with 7-fold C-C formation to afford nearly planar γ-ortho fused porphyrins with 66 conjugated π-electrons. In addition, a small number of molecules undergo C-C bond dissociation of meso-phenyl at elevated temperature, producing fully planar γ-ortho fused products lacking one or two phenyl moieties. Scanning tunneling spectroscopy measurements and DFT calculations suggest the electronic gap of the γ-ortho fused porphyrin decreases compared to that of the precursor. The HOMO and LUMO of the planar γ-ortho fused products are localized on the partially fused benzo moieties and the meso-position, respectively.

The Texture Change of Chinese Traditional Pig Trotter with Soy Sauce during Stewing Processing: Based on a Thermal Degradation Model of Collagen Fibers.

In order to clarify the influence of the thermal degradation of collagen fibers on the texture profile analysis (TPA) parameters of pig trotter stewed with soy sauce (PTSWSS), TPA (springiness, chewiness, hardness, and gumminess), the secondary structures, the cross-linkage, decorin (DCN) and glycosaminoglycan (GAG) levels, and the histochemical morphology of collagen fibers during the stewing process (0, 30, 60, 120 min) were assessed. The springiness and hardness increased after 30 min of stewing, along with the denaturation of collagen proteins. TPA parameters improved with the prolonged stewing times of 60 and 120 min, along with the ultra-structural dissolution of collagen fibers, and a substantial reduction in cross-linkage, DCN, and GAG levels, and the unfolded triple-helix structure. This study concluded that the TPA parameters of PTSWSS were dependent on the stewing time, and that the improvement in TPA parameters with longer stewing time could primarily be attributed to the thermal degradation of collagen fibers.

Shoot-Root Interplay Mediates Defoliation-Induced Plant Legacy Effect.

Shoot defoliation by grazers or mowing can affect root traits of grassland species, which may subsequently affect its aboveground traits and ecosystem functioning (e.g., aboveground primary production). However, experimental evidence for such reciprocal feedback between shoots and roots is limited. We grew the perennial grass Leymus chinensis-common across the eastern Eurasian steppe-as model species in a controlled-hydroponics experiment, and then removed half of its shoots, half of its roots, or a combination of both. We measured a range of plant aboveground and belowground traits (e.g., phenotypic characteristics, photosynthetic traits, root architecture) in response to the shoot and/or root removal treatments. We found the regenerated biomass was less than the lost biomass under both shoot defoliation and root severance, generating a under-compensatory growth. Root biomass was reduced by 60.11% in the defoliation treatment, while root severance indirectly reduced shoot biomass by 40.49%, indicating a feedback loop between shoot and root growth. This defoliation-induced shoot-root feedback was mediated by the disproportionate response and allometry of plant traits. Further, the effect of shoot defoliation and root severance on trait plasticity of L. chinensis was sub-additive. That is, the combined effects of the two treatments were less than the sum of their independent effects, resulting in a buffering effect on the existing negative influences on plant persistence by increased photosynthesis. Our results highlight the key role of trait plasticity in driving shoot-root reciprocal feedbacks and growth persistence in grassland plants, especially perennial species. This knowledge adds to earlier findings of legacy effects and can be used to determine the resilience of grasslands.

Mechanistic Insight into Etching Chemistry and HF-Assisted Etching of MgO-Al2O3-SiO2 Glass-Ceramic.

The present study focuses on the etching conditions and mechanism of MgO-Al2O3-SiO2 glass-ceramic (MAS) in hydrofluoric acid (HF). The results show that the amorphous phase has 218 times higher etching rate than pure cordierite crystal at room temperature. In addition, the activation energies of cordierite and amorphous phases in the HF solution are 52.5 and 30.6 kJ/mol, respectively. The time (tad) taken for complete dissolution of the amorphous phase depends on the HF concentration (CHF). Based on the etching experiments, a new model is established and refined to assess the tad evolution. In addition, a highly crystalline cordierite phase, with the high specific surface area (59.4 m²·g-1) and mesoporous structure, has been obtained by HF etching. This paper presents novel insights into the etching chemistry and opens up avenues for further research in the area of cordierite-based catalytic ceramics.

Nutrient Characteristics in Relation to Plant Size of a Perennial Grass Under Grazing Exclusion in Degraded Grassland.

Identifying the linkages between nutrient properties and plant size is important for reducing uncertainty in understanding the mechanisms of plant phenotypic plasticity. Although the positive effects of grazing exclusion on plant morphological plasticity has been well documented, surprisingly little is known about the relationship of nutrient strategies with plant shoot size after long-term grazing exclusion. We experimentally investigated the impacts of grazing exclusion over time (0, 9, 15, and 35 years) on the relationships of nutrient traits (nutrient concentration, allocation, and stoichiometry) of with morphological plasticity in Leymus chinensis, which is a dominant species in grasslands of Inner Mongolia, China. Our results showed that there was a significantly negative correlation between the degrees of plasticity and stability of various morphological traits. Increases in plant size by 126.41, 164.17, and 247.47% were observed with the increase of grazing exclusion time of 9, 15, and 35 years, respectively. Plant size was negatively correlated with nitrogen (N) and phosphorus (P) concentrations, but was positively correlated with carbon (C) concentration. Biomass partitioning and leaf to stem ratios of nutrient concentrations contributed more than 95% of the changes in N, P, and C allocation in L. chinensis leaves and stems induced by grazing exclusions. Nine years' grazing exclusion rapidly changed the nutrient concentrations (averaged by -34.84%), leaf to stem nutrient allocations (averaged by -86.75%), and ecological stoichiometry (averaged by +46.54%) compared to free-grazing, whereas there was no significant trend of these nutrient traits across the 9, 15, and 35 years' grazing exclusion in L. chinensis individuals. Our findings suggest that with the increase of the duration of the grazing exclusion, time effects on plant performances gradually weakened both in plant morphological plasticity and nutrient properties. There is a significant negative effect between plant sizes and nutrient traits under long-term grazing exclusion.

Contrasting Effects of Long-Term Grazing and Clipping on Plant Morphological Plasticity: Evidence from a Rhizomatous Grass.

Understanding the mechanism of plant morphological plasticity in response to grazing and clipping of semiarid grassland can provide insight into the process of disturbance-induced decline in grassland productivity. In recent studies there has been controversy regarding two hypotheses: 1) grazing avoidance; and 2) growth limiting mechanisms of morphological plasticity in response to defoliation. However, the experimental evidence presented for the memory response to grazing and clipping of plants has been poorly reported. This paper reports on two experiments that tested these hypotheses in field and in a controlled environment, respectively. We examined the effects of long-term clipping and grazing on the functional traits and their plasticity for Leymus chinensis (Trin.) Tzvelev (the dominate species) in the typical-steppe grassland of Inner Mongolia, China. There were four main findings from these experiments. (i) The majority of phenotypic traits of L. chinensis tended to significantly miniaturize in response to long-term field clipping and grazing. (ii) The significant response of morphological plasticity with and without grazing was maintained in a hydroponic experiment designed to remove environmental variability, but there was no significant difference in L. chinensis individual size traits for the clipping comparison. (iii) Plasticity indexes of L. chinensis traits in a controlled environment were significantly lower than under field conditions indicating that plants had partial and slight memory effect to long-term grazing. (iv) The allometry of various phenotypic traits, indicated significant trade-offs between leaf and stem allocation with variations in plant size induced by defoliation, which were maintained only under grazing in the hydroponic controlled environment experiment. Taken together, our findings suggest that the morphological plasticity of L. chinensis induced by artificial clipping was different with that by livestock grazing. The miniaturization of plant size in long-term grazed grassland may reflect retained characteristics of dwarf memory for adaptation to long-term grazing by large herbivores.

[Analysis of self-rated health status of the floating population in a district of Guangzhou].

OBJECTIVE: To investigate the self-rated health status of the floating population in a district of Guangzhou. METHODS: Cluster stratified random sampling was applied to survey 219 floating people from a community in Guangzhou, who were assessed with self-rated health status was assessed with Self-Rated Health Measurement Scale. RESULTS: The scores of the floating population were significantly higher than the normal individuals in physical health sub-scales (P<0.01), while the scores of the floating population were significantly lower in psychological and social health sub-scales (P<0.05). The low score items in the subscale of physical health mainly consisted of fatigue and gastrointestinal symptoms, those in the subscale of psychological health mainly in anxiety, depression and obsession, and those in the subscale of social health mainly in participation in social activities and seeking help from others. CONCLUSION: To improve the health status of the floating population, campaigns of health education need to be launched periodically and psychological counseling should be provided for these individuals. Additionally, interactive activities should be increased in their daily social life.