Exploring the Use of "Honorary Transition Metals" To Push the Boundaries of Planar Hypercoordinate Alkaline-Earth Metals.

The quest for planar hypercoordinate atoms (phA) beyond six has predominantly focused on transition metals, with dodecacoordination being the highest reported thus far. Extending this bonding scenario to main-group elements, which typically lack d orbitals despite their larger atomic radius, has posed significant challenges. Intrigued by the potentiality of covalent bonding formation using the d orbitals of the heavier alkaline-earth metals (Ae = Ca, Sr, Ba), the so-called "honorary transition metals", we aim to push the boundaries of planar hypercoordination. By including rings formed by 12-15 atoms of boron-carbon and Ae centers, we propose a design scheme of 180 candidates with a phA. Further systematic screening, structural examination, and stability assessments identified 10 potential clusters with a planar hypercoordinate alkaline-earth metal (phAe) as the lowest-energy form. These unconventional structures embody planar dodeca-, trideca-, tetradeca-, and pentadecacoordinate atoms. Chemical bonding analyses reveal the important role of Ae d orbitals in facilitating covalent interactions between the central Ae atom and the surrounding boron-carbon rings, thereby establishing a new record for coordination numbers in the two-dimensional realm.

Plant species and associated root nutritional traits influence soil dominant bacteria in coastal wetlands across China.

Climate and edaphic properties drive the biogeographic distribution of dominant soil microbial phylotypes in terrestrial ecosystems. However, the impact of plant species and their root nutritional traits on microbial distribution in coastal wetlands remains unclear. Here, we investigated the nutritional traits of 100 halophyte root samples and the bacterial communities in the corresponding soil samples from coastal wetlands across eastern China. This study spans 22° of latitude, covering over 2500 km from north to south. We found that 1% of soil bacterial phylotypes accounted for nearly 30% of the soil bacterial community abundance, suggesting that a few bacterial phylotypes dominated the coastal wetlands. These dominated phylotypes could be grouped into three ecological clusters as per their preference over climatic (temperature and precipitation), edaphic (soil carbon and nitrogen), and plant factors (halophyte vegetation, root carbon, and nitrogen). We further provide novel evidence that plant root nutritional traits, especially root C and N, can strongly influence the distribution of these ecological clusters. Taken together, our study provides solid evidence of revealing the dominance of specific bacterial phylotypes and the complex interactions with their environment, highlighting the importance of plant root nutritional traits on biogeographic distribution of soil microbiome in coastal wetland ecosystems.

Multiple Bonding in AeN- (Ae=Ca, Sr, Ba).

Quantum chemical calculations using ab initio methods at the MRCI+Q(8,9)/def2-QZVPPD and CCSD(T)/def2-QZVPPD levels as well as using density functional theory are reported for the diatomic molecules AeN- (Ae=Ca, Sr, Ba). The anions CaN- and SrN- have electronic triplet (3Π) ground states with nearly identical bond dissociation energies De ~57 kcal/mol calculated at the MRCI+Q(8,9)/def2-QZVPPD level. In contrast, the heavier homologue BaN- has a singlet (1Σ+) ground state, which is only 1.1 kcal/mol below the triplet (3Σ-) state. The computed bond dissociation energy of (1Σ+) BaN- is 68.4 kcal/mol. The calculations at the CCSD(T)-full/def2-QZVPPD and BP86-D3(BJ)/def2-QZVPPD levels are in reasonable agreement with the MRCI+Q(8,9)/def2-QZVPPD data, except for the singlet (1Σ+) state, which has a large multireference character. The calculated atomic partial charges given by the CM5, Voronoi and Hirshfeld methods suggest small to medium-sized Ae←N- charge donation for most electronic states. In contrast, the NBO method predicts for all species medium to large Ae→N- electronic charge donation, which is due to the neglect of the (n)p AOs of Ae atoms as genuine valence orbitals. Neither the bond orders nor the bond lengths correlate with the bond dissociation energies. The EDA-NOCV calculations show that the heavier alkaline earth atoms Ca, Sr, Ba use their (n)s and (n-1)d orbitals for covalent bonding.

Therapeutic Effect and Adverse Event Rate of Different Treatment Methods in Patients with Multiple Myeloma and Renal Insufficiency.

INTRODUCTION: This study involves the collation and analysis of clinical characteristics and laboratory findings in patients with multiple myeloma (MM) combined with renal insufficiency. The objective was to assess the impact of various treatment methods on patient outcomes and the incidence of adverse events in individuals with MM and renal insufficiency. METHODS: We analyzed the correlation between clinical characteristics, gene loci, fluorescence in situ hybridization, treatment methods, and prognosis in patients with MM and renal insufficiency. The differences in hematological and therapeutic efficacy indexes between two groups subjected to different treatments were evaluated. The assessment of treatment effectiveness was based on the total effective rate, calculated as the sum of stringent CR rate, complete remission rate, very good partial remission rate, and partial remission rate. RESULTS: (1) The renal insufficiency group exhibited higher percentages of bone marrow abnormal plasma cells, lactate dehydrogenase (LDH), blood calcium, white blood cell count, percentage of neutrophils, and blood ß2-microglobulin (ß2-MG) levels compared to the normal renal function group. Conversely, hemoglobin levels and lymphocyte percentage were lower in the renal insufficiency group. Binary logistic regression analysis identified hemoglobin, blood calcium values, blood ß2-MG, and LDH as independent risk factors for the development of renal insufficiency in patients with MM (p < 0.05). (2) Based on the Durie-Salmon staging criteria, the proportion of Stage III patients was the highest (up to 81.8%), indicating that patients with MM usually suffer from insidious disease, often with high tumor load and late-disease stage at the time of consultation. International Staging System (ISS) and Revised ISS staging also revealed a higher proportion of Stage III patients in the renal insufficiency group (p < 0.05), indicating a worse long-term prognosis in patients with MM and renal insufficiency. (3) Before treatment, there was no significant difference between the two groups in the analysis of various indices. Complications such as sepsis, herpes zoster, peripheral neuropathy, thrombosis, secondary pulmonary infection, and cardiac complications were significantly lower in the BCD group (Bortezomib + Cyclophosphamide + Dexamethasone) compared to the BD group (Bortezomib + Dexamethasone) (χ2 = 6.333, p < 0.05), suggesting fewer complications with the BCD regimen. (4) The clinical treatment effects analysis indicated that the BCD group demonstrated a more significant impact than the BD group in the treatment of MM. CONCLUSION: The application of the BCD regimen in the treatment of MM has shown significant efficiency, effectively alleviating clinical symptoms with fewer adverse reactions and high safety.

MB16 - (M=Sc, Y, La): Perfect Bowl-Like Boron Clusters.

The introduction of transition-metal doping has engendered a remarkable array of unprecedented boron motifs characterized by distinctive geometries and bonding, particularly those heretofore unobserved in pure boron clusters. In this study, we present a perfect (no defects) boron framework manifesting an inherently high-symmetry, bowl-like architecture, denoted as MB16 - (M=Sc, Y, La). In MB16 -, the B16 is coordinated to M atoms along the C5v-symmetry axis. The bowl-shaped MB16 - structure is predicted to be the lowest-energy structure with superior stability, owing to its concentric (2 π+10 π) dual π aromaticity. Notably, the C5v-symmetry bowl-like B16 - is profoundly stabilized through the doping of an M atom, facilitated by strong d-pπ interactions between M and boron motifs, in conjunction with additional electrostatic stabilization by an electron transfer from M to the boron motifs. This concerted interplay of covalent and electrostatic interactions between M and bowl-like B16 renders MB16 - a species of exceptional thermodynamic stability, thus making it a viable candidate for gas-phase experimental detection.

The evolution of preexisting primary immune thrombocytopenia after COVID-19 onset: A nationally representative, prospective, multicentre, observational study.

The symptoms in patients with primary immune thrombocytopenia (ITP) after COVID-19 onset remain largely unclear. The aim of this study was to describe the platelet count fluctuations in ITP patients following the diagnosis of COVID-19. A prospective multicentre observational study was conducted from December 15th, 2022, to January 31st, 2023 in 39 general hospitals across China. Patients with preexisting primary ITP who were newly diagnosed with COVID-19 were enrolled. A total of 1216 ITP patients with newly-diagnosed COVID-19 were enrolled. 375 (30.8%) patients experienced ITP exacerbation within eight weeks after the diagnosis of COVID-19, and most exacerbation (266/375, 70.9%) developed in the first two weeks. Immunosuppressive therapy for ITP and severe/critical COVID-19 infection were independent variables associated with ITP exacerbation. Overall the platelet count had a transient increasing trend, and the platelet peak value occurred at two weeks after COVID-19 infection. Then, the platelet count decreased to the baseline level in the following weeks. The platelet count had a transient increasing trend in ITP patients following the diagnosis of COVID-19. ITP exacerbation only occurred in less than one-third of ITP patients. Nonimmunosuppressive therapy may have an advantage to prevent ITP exacerbation during COVID-19.

Near-infrared fluorescence-assisted superficial inguinal lymph-node excision for low-risk penile cancer.

OBJECTIVE: Identification of superficial inguinal lymph nodes during low-risk penile cancer surgery using near-infrared (NIR) fluorescence to improve the accuracy of lymph-node dissection and reduce the incidence of missed micrometastases and complications. METHODS: Thirty-two cases were selected, which were under the criteria of < T1, and no lymph-node metastasis was found with magnetic resonance imaging (MRI) detection. Two groups were randomly divided based on the fluorescence technique, the indocyanine green (ICG) group and the non-ICG group. In the ICG group, the ICG preparation was subcutaneously injected into the edge of the penile tumor 10 min before surgery, and the near-infrared fluorescence imager was used for observation. After the lymph nodes were visualized, the superficial inguinal lymph nodes were removed first, and then, the penis surgery was performed. The non-ICG group underwent superficial inguinal lymph-node dissection and penile surgery. RESULTS: Among the 16 patients in the ICG group, we obtained 11 lymph-node specimens using grayscale values of images (4.13 ± 0.72 vs. 3.00 ± 0.82 P = 0.003) along with shorter postoperative healing time (7.31 ± 1.08 vs. 8.88 ± 2.43 P = 0.025), and less lymphatic leakage (0 vs. 5 P = 0.04) than the 16 patients in the non-ICG group. Out of 11, 3 lymph nodes that are excised were further grouped into fluorescent and non-fluorescent regions (G1/G2) and found to be metastasized. CONCLUSION: Near-infrared fluorescence-assisted superficial inguinal lymph-node dissection in penile carcinoma is accurate and effective, and could reduce surgical complications.

Strong and consistent effects of waterbird composition on HPAI H5 occurrences across Europe.

Since 2014, highly pathogenic avian influenza (HPAI) H5 viruses of clade 2.3.4.4 have been dominating the outbreaks across Europe, causing massive deaths among poultry and wild birds. However, the factors shaping these broad-scale outbreak patterns, especially those related to waterbird community composition, remain unclear. In particular, we do not know whether these risk factors differ from those of other H5 clades. Addressing this knowledge gap is important for predicting and preventing future HPAI outbreaks. Using extensive waterbird survey datasets from about 6883 sites, we here explored the effect of waterbird community composition on HPAI H5Nx (clade 2.3.4.4) spatial patterns in the 2016/2017 and 2020/2021 epidemics in Europe, and compared it with the 2005/2006 HPAI H5N1 (clade 2.2) epidemic. We showed that HPAI H5 occurrences in wild birds in the three epidemics were strongly associated with very similar waterbird community attributes, which suggested that, in nature, similar interspecific transmission processes operate between the HPAI H5 subtypes or clades. Importantly, community phylogenetic diversity consistently showed a negative association with H5 occurrence in all three epidemics, suggesting a dilution effect of phylogenetic diversity. In contrast, waterbird community variables showed much weaker associations with HPAI H5Nx occurrence in poultry. Our results demonstrate that models based on previous epidemics can predict future HPAI H5 patterns in wild birds, implying that it is important to include waterbird community factors in future HPAI studies to predict outbreaks and improve surveillance activities.

Transition Metal Behavior of Heavier Alkaline Earth Elements in Doped Monocyclic and Tubular Boron Clusters.

Quantum chemical calculations are carried out to design highly symmetric-doped boron clusters by employing the transition metal behavior of heavier alkaline earth (Ae = Ca, Sr, and Ba) metals. Following an electron counting rule, a set of monocyclic and tubular boron clusters capped by two heavier Ae metals were tested, which leads to the highly symmetric Ae2B8, Ae2B18, and Ae2B30 clusters as true minima on the potential energy surface having a monocyclic ring, two-ring tubular, and three-ring tubular boron motifs, respectively. Then, a thorough global minimum (GM) structural search reveals that a monocyclic B8 ring capped with two Ae atoms is indeed a GM for Ca2B8 and Ba2B8, while for Sr2B8 it is a low-lying isomer. Similarly, the present search also unambiguously shows the most stable isomers of Ae2B18 and Ae2B30 to be highly symmetric two- and three-ring tubular boron motifs, respectively, capped with two Ae atoms on each side of the tube. In these Ae-doped boron clusters, in addition to the electrostatic interactions, a substantial covalent interaction, specifically the bonding occurring between (n - 1)d orbitals of Ae and delocalized orbitals of boron motifs, provides the essential driving force behind their highly symmetrical structures and overall stability.

InnTl4-nH+ (n = 0∼4): Tetracoordinate Hydrogen in a Planar Fashion?

The recent report of planar tetracoordinate hydrogen (ptH) in In4H+ is very intriguing in planar hypercoordinate chemistry. Our high-level CCSD(T) calculations revealed that the proposed D4h-symmetric ptH In4H+ is a first-order saddle point with an imaginary frequency in the out-of-plane mode of the hydrogen atom. In fact, at the CCSD(T)/aug-cc-pV5Z/aug-cc-pV5Z-PP level, the C4v isomer, with the H atom located 0.70 Å above the In4 plane, is 0.5 kcal/mol more stable than the D4h isomer. However, given the small perturbation from planarity and essentially barrierless C4v ↔ D4h ↔ C4v transition, the vibrationally averaged structure can still be considered as a planar. Extending our exploration to the InnTl4-nH+ (n = 0-3) systems, we found all these ptH structures, except for In2Tl2H+, to be the putative global minimum. The single σ-delocalized interaction between the central hydrogen atom and InnTl4-n ligand rings proves pivotal in establishing planarity and aromaticity and conferring substantial stability upon these rule-breaking ptH species.

Revisiting the Structure and Bonding in Li5H6- and the Exploration of Reactivity: Planar Pentacoordinate Hydrogen.

Recently, Guha and co-workers (Sarmah, K.; Kalita, A.; Purkayastha, S.; Guha, A. K. Pushing The Extreme of Multicentre Bonding: Planar Pentacoordinate Hydride. Angew. Chem. Int. Ed. 2024, e202318741) reported a highly intriguing bonding motif: planar pentacoordinate hydrogen (ppH) in Li5H6-, featuring C2v symmetry in the singlet state with two distinct H-Li (center-ring) bond distances. We herein revisited the potential energy surface of Li5H6- by using a target-oriented genetic algorithm. Our investigation revealed that the lowest-energy structure of Li5H6- exhibits a ppH configuration with very high D5h symmetry and a 1A1' electronic state. We did not find any electronic effect like Jahn-Teller distortion that could be responsible for lowering its symmetry. Moreover, our calculations demonstrated significant differences in the relative energies of other low-lying isomers. An energetically very competitive planar tetracoordinate hydrogen (ptH) isomer is also located, but it corresponds to a very shallow minimum on the potential energy surface depending on the used level of theory. Chemical bonding analyses, including AdNDP and EDA-NOCV, uncover that the optimal Lewis structure for Li5H6- involves H- ions stabilized by the Li5H5 crown. Surprisingly, despite the dominance of electrostatic interactions, the contribution from covalent bonding is also significant between ppH and the Li5H5 moiety, derived from H-(1s) → Li5H5 σ donation. Magnetically induced current density analysis revealed that due to minimal orbital overlap and the highly polar nature of the H-Li covalent interaction, the ppH exhibits local diatropic ring currents around the H centers, which fails to result in a global aromatic ring current. The coordination of Li5H6- with Lewis acids, BH3 and BMe3, instantly converts the ppH configuration to (quasi) ptH. These Lewis acid-bound ptH complexes show high electronic stability and high thermochemical stability against dissociation and, therefore, will be ideal candidates for the experimental realization.

Sediment properties control riverine methane emissions: A case study of the Liao river in northern China.

River and stream sediments act as biogeochemical reactors for greenhouse gases, particularly methane. However, understanding how riverbed sediment properties influence river carbon emissions remains relatively unclear. The Liao River in northern China is a typical watershed with heterogeneous water and sediment sources, characterized by varying sediment properties. In this study, we surveyed CH4 and CO2 emissions from its mainstem and tributaries during flood and dry seasons. We found consistent seasonal patterns in CH4 and CO2 emissions, with peaks occurring during the flood season. The average CH4 and CO2 fluxes were 1.64 ± 1.80 mmol m-2 d-1 and 59.66 ± 44.60 mmol m-2 d-1, respectively. Notably, the percentage of sediment silt was significantly correlated with CH4 concentration and flux (R2 = 0.12-0.30, p < 0.05). Fine particles dominated the availability of sediment organic matter and redox conditions, which were related to riverine CH4 production and emissions. Structural equation modeling revealed that both grain size and the percentage of TOC (total organic carbon) directly influenced riverine CH4 and CO2 emissions. The organic content and redox conditions of the riverbed sediment collectively explained 65% of riverine CH4 emissions, while grain size composition indirectly controlled CH4 emissions by altering sediment substrate quality and redox conditions. In contrast, river CO2 emissions were only weakly dependent on anaerobic metabolism in riverbed sediments. These findings enhance our understanding of the sources and metabolic mechanisms of riverine CH4 and CO2 emissions and offer potential improvements for estimating carbon fluxes in regional or global riverine networks by considering riverbed sediment properties.

BeM(CO)3- (M = Co, Rh, Ir) and BeM(CO)3 (M = Ni, Pd, Pt): Triply bonded terminal beryllium in zero oxidation state.

We perform detailed potential energy surface explorations of BeM(CO)3- (M = Co, Rh, Ir) and BeM(CO)3 (M = Ni, Pd, Pt) using both single-reference and multireference-based methods. The present results at the CASPT2(12,12)/def2-QZVPD//M06-D3/def2-TZVPPD level reveal that the global minimum of BeM(CO)3- (M = Co, Rh, Ir) and BePt(CO)3 is a C3v symmetric structure with an 1A1 electronic state, where Be is located in a terminal position bonded to M along the center axis. For other cases, the C3v symmetric structure is a low-lying local minimum. Although the present complexes are isoelectronic with the recently reported BFe(CO)3- complex having a B-Fe quadruple bond, radial orbital-energy slope (ROS) analysis reveals that the highest occupied molecular orbital (HOMO) in the title complexes is slightly antibonding in nature, which bars a quadruple bonding assignment. Similar weak antibonding nature of HOMO in the previously reported BeM(CO)4 (M = Ru, Os) complexes is also noted in ROS analysis. The bonding analysis through energy decomposition analysis in combination with the natural orbital for chemical valence shows that the bonding between Be and M(CO)3q (q = -1 for M = Co, Rh, Ir and q = 0 for M = Ni, Pd, Pt) can be best described as Be in the ground state (1S) interacting with M(CO)30/- via dative bonds. The Be(spσ) → M(CO)3q σ-donation and the complementary Be(spσ) ← M(CO)3q σ-back donation make the overall σ bond, which is accompanied by two weak Be(pπ) ← M(CO)3q π-bonds. These complexes represent triply bonded terminal beryllium in an unusual zero oxidation state.

Prospective associations between heterogeneous sleep profiles and depressive symptoms in adolescents: The mediating role of coping styles.

INTRODUCTION: Extant literature has linked sleep disturbance to depressive symptoms. However, the coexistence of naturally occurring sleep profiles among adolescents and the prospective associations between sleep profiles and depressive symptoms remain poorly understood. This study aims to uncover sleep patterns in Chinese adolescents based on a comprehensive set of sleep features (e.g., latency, daytime dysfunction, etc.) derived from the Pittsburg Sleep Quality Index (PSQI) and investigate the relationship between these profiles and subsequent depressive symptoms mediated by positive and negative coping styles. METHODS: Five thousand five hundred five adolescents from Shandong province, China, enrolled (Mage = 16.83 years; 49.9% girls) in a two-wave longitudinal study (T1 in August 2023; T2 in February 2024). Latent class analysis (LCA) was conducted to identify adolescent sleep patterns. Mediation and sensitivity analyses were used to examine prospective associations between sleep patterns, coping styles, and depressive symptoms. RESULTS: Four qualitatively distinct sleep profiles emerged: Healthy Sleepers (18.9%), Latency but Functioning Sleepers (13.6%), Efficient but Dysfunctional Sleepers (57.5%), and Medicated Maladaptive Sleepers (10.0%). Using the Healthy Sleepers as a reference group, Latency but Functional Sleepers, Efficient but Dysfunctional Sleepers, and Medicated Maladaptive Sleepers all predicted subsequent depressive symptoms through positive coping styles rather than negative coping styles. The relative indirect effects were 0.19, 0.19, and 0.32, respectively. CONCLUSIONS: The study underscored that adolescents exhibit distinct sleep patterns, and specific sleep profiles may be prospectively associated with depressive symptoms mediated by positive coping styles.

The Developmental Trajectory of Chinese Adolescents' Self-Compassion and its Relationship with Parenting Styles: a Longitudinal Study.

Abundant evidence highlights the psychological and interpersonal benefits of self-compassion during adolescence, yet the developmental trajectory and influencing factors during this period remain relatively unexplored. This study investigated the developmental trajectory of self-compassion and illustrated the longitudinal relationship between parenting styles and self-compassion using latent growth curve models (LGCM), cross-lagged panel models (CLPM) and random-intercept cross-lagged panel models (RI-CLPM) in a sample of Chinese youth (N = 871; Mage = 15.21, SD = 0.73; 45.4% girls) across two years. Results demonstrated an increase developmental trend of self-compassion over two years. The parallel process LGCMs suggested that changes in parental autonomy support was positively related to the changes in self-compassion, whereas the relationship between parental psychological control and self-compassion was significant only at initial levels. CLPM consistently supported a bidirectional relationship between parental autonomy support and self-compassion in Chinese youth at between-person level. Although within-person changes in the study variables were not significant in a bidirectional manner based on the results of RI-CLPMs, changes in parental autonomy support/parental psychological control and self-compassion were concurrently associated. These results suggested that besides stable connections between parenting styles and adolescents' self-compassion, changes in parenting styles and self-compassion are developmentally linked as well. Overall, this study underscores the potentially beneficial impact of parental autonomy support on adolescent self-compassion and reveals nuanced effects of parental psychological control within the Chinese cultural context.

Planar Pentacoordinate Halogens.

Planar hypercoordinate motifs represent an intriguing frontier in chemistry, challenging traditional bonding norms. As electronegativity of the central atom increases, achieving planar hypercoordination becomes more difficult due to restricted delocalization, making the design of planar hypercoordinate halogens particularly puzzling. Here, we conduct an extensive computational survey of LinXn+1- (n = 4, 5, 6; X = F, Cl, Br, I) clusters, revealing a starlike D5h-symmetry global minimum in Li5X6- (X = F, Cl, Br) with a planar pentacoordinate halogen (ppX), where X- is located at the center of Li5X5 crown. The clusters are stabilized predominantly through electrostatic interactions between X- and Li5X5, complemented by weak covalent bonding from dative interaction. Due to the weak orbital overlap, ppX clusters exhibit localized diatropic ring currents around X and Li.

Functional traits explain waterbirds' host status, subtype richness, and community-level infection risk for avian influenza.

Species functional traits can influence pathogen transmission processes, and consequently affect species' host status, pathogen diversity, and community-level infection risk. We here investigated, for 143 European waterbird species, effects of functional traits on host status and pathogen diversity (subtype richness) for avian influenza virus at species level. We then explored the association between functional diversity and HPAI H5Nx occurrence at the community level for 2016/17 and 2021/22 epidemics in Europe. We found that both host status and subtype richness were shaped by several traits, such as diet guild and dispersal ability, and that the community-weighted means of these traits were also correlated with community-level risk of H5Nx occurrence. Moreover, functional divergence was negatively associated with H5Nx occurrence, indicating that functional diversity can reduce infection risk. Our findings highlight the value of integrating trait-based ecology into the framework of diversity-disease relationship, and provide new insights for HPAI prediction and prevention.

Children with autism spectrum disorder perform comparably to their peers in a parent-child cooperation task.

This study investigates whether and how parent's cooperation affects child's cooperation, and whether that differs between children with/without autism spectrum disorder (ASD). The experiment involved a cooperative key-pressing task completed first by parent-parent dyads and then by parent-child dyads, meanwhile brain activity in the right frontal-parietal cortex of dyad partners was measured synchronously. The results showed the following: ASD children exhibited performance comparable to those of their peers, as was the level of brain synchronization with their parents, which was mainly due to parents with ASD children tending to adjust their own response patterns to match those of their children. These findings suggest that parents can somewhat actively mitigate the lower interpersonal synchronization ability of ASD children, in behavioral or/and neural level.

Mimicking the C2 molecule: M2B2 and M3B2+ clusters (M = Li, Na) and the reactivity of the N-heterocyclic carbene bound Li2B2 complex.

C2 has attracted considerable attention from the scientific community for its debatable bonding situation. Herein, we show that the global minima of M2B2 and M3B2+ (M = Li, Na) possess similar covalent bonding patterns to C2. Because of strong charge transfer from M2/M3 to B2 dimer, they can be better described as [M2]2+[B2]2- and [M3]3+[B2]2- salt complexes with the B22- core surrounded perpendicularly by two and three M+ atoms, respectively. The energy decomposition analyses in combination with the natural orbital for chemical valence theory give four bonding components in C2, M2B2, and M3B2+ clusters. However, the fourth component does not arise from a bonding interaction but from polarization/hybridization. Considering the effect of Pauli repulsion in σ-space, the attractive covalent interaction in these molecules mainly comes from the two π-bonds. We further presented stable N-heterocyclic carbene (NHC) and triphenylphosphine (PPh3) ligands bound Li2B2(NHC)2 and Li2B2(PPh3)2 complexes. A comparative study of reactivity towards L = CO2, CO, and N2 between Li2B2(NHC)2 and B2(NHC)2 is also performed. L-Li2B2(NHC)2 is highly stable against L dissociation at room temperature for L = CO2 and CO, and the stability is markedly higher than that in L-B2(NHC)2. The larger B2→L π-backdonation in L-Li2B2(NHC)2 also makes L more activated than in L-B2(NHC)2.

Coupled patterns of natural and anthropogenic resources in typical ecosystems in coastal areas of China.

The coastal area of Yancheng, China, is one of the hotspots for ecological research. Under the coupling of human and natural ecosystems, the region has gradually evolved into a coexistence of aquatic, agricultural and mudflat ecosystems. What are the patterns of natural and artificial resource inputs and patterns of change in ecosystems? How can ecological flows be analyzed at a uniform scale? Here, we selected six typical local ecosystems, namely, rice‒wheat for enterprises (RWE), rice‒wheat for smallholder households (RWS), chrysanthemum‒wheat (CW), fish polyculture (FP), juvenile crab farming (JF) and clam polyculture (CP), and analyzed their energy flow flux and sustainability based on emergy theory. The results showed that anthropogenic resource inputs were higher than natural resource inputs in all ecosystems, and the inputs of aquatic ecosystems were greater than those of agroecosystems. The greatest total input was 2.0 E+17 seJ/ha/yr for FP, and the lowest was 1.9 E+16 seJ/ha/yr for RWE. The proportions of renewable and artificial inputs for RWE, RWS, CW, FP, JF and CP were 32.8% vs. 96.1%, 40.3% vs. 96.5%, 34.7% vs. 97.0%, 32.6% vs. 99.4%, 55.1% vs. 98.5%, and 62.5% vs. 98.6%, respectively. The highest input to agroecosystems was nitrogen fertilizer, while in JF and CP, it was water, and feed (63.3%) accounted for the highest percentage of input in FP. JF and CP had lower environmental loads and higher sustainability than other ecosystems, but this still represents a high input compared to agroecosystems. Human-led resource coupling profoundly affects ecosystem sustainability, and various thresholds of energy use and ecological sustainability need to be studied in depth. Continuous exploration of methods and mechanisms for the maintenance and evolution of ecosystems with low total inputs and low inputs of non-renewable resources can contribute to high-quality sustainable development of an area or region.