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1.
J Am Chem Soc ; 2024 Jun 06.
Article de Anglais | MEDLINE | ID: mdl-38843775

RÉSUMÉ

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.

2.
J Phys Chem A ; 128(24): 4806-4813, 2024 Jun 20.
Article de Anglais | MEDLINE | ID: mdl-38839423

RÉSUMÉ

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.

3.
J Vis Exp ; (207)2024 May 17.
Article de Anglais | MEDLINE | ID: mdl-38829112

RÉSUMÉ

The construction of gene expression vectors is an important component of laboratory work in experimental biology. With technical advancements like Gibson Assembly, vector construction becomes relatively simple and efficient. However, when the full-length genome of Porcine Reproductive and Respiratory Syndrome Virus (PRRSV) cannot be easily amplified by a single polymerase chain reaction (PCR) from cDNA, or it is difficult to acquire a full-length gene expression vector by homologous recombination of multiple inserts in vitro, the current Gibson Assembly technique fails to achieve this goal. Consequently, we aimed to divide the PRRSV genome into several fragments and introduce appropriate restriction sites into the reverse primer for obtaining PCR-amplified fragments. After joining the previous DNA fragment into the vector by homologous recombination technology, the new vector acquired the restriction enzyme cleavage site. Thus, we can linearize the vector by using the newly added enzyme cleavage site and introduce the next DNA fragment downstream of the upstream DNA fragment. The introduced restriction enzyme cleavage site at the 3' end of the upstream DNA fragment will be eliminated, and a new cleavage site will be introduced into the 3' end of the downstream DNA fragment. In this way, we can join DNA fragments to the vector one by one. This method is applicable to successfully construct the PRRSV expression vector and is an effective method for assembling a large number of fragments into the expression vector.


Sujet(s)
Clonage moléculaire , Vecteurs génétiques , Virus du syndrome respiratoire et reproducteur porcin , Virus du syndrome respiratoire et reproducteur porcin/génétique , Vecteurs génétiques/génétique , Clonage moléculaire/méthodes , Animaux , Réaction de polymérisation en chaîne/méthodes , Suidae , Génome viral/génétique
4.
J Chem Phys ; 160(18)2024 May 14.
Article de Anglais | MEDLINE | ID: mdl-38738611

RÉSUMÉ

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.

5.
Chemistry ; 30(34): e202400714, 2024 Jun 17.
Article de Anglais | MEDLINE | ID: mdl-38622057

RÉSUMÉ

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.

6.
Addict Behav ; 155: 108026, 2024 08.
Article de Anglais | MEDLINE | ID: mdl-38593598

RÉSUMÉ

Social anxiety is a common comorbid factor of problematic mobile phone use, but the relationship between them from the inside structure has been underexplored. This two-wave longitudinal study aims to identify the central symptoms of problematic mobile phone use and social anxiety, respectively, as well as the bridge symptoms between the two disorders. Furthermore, this study examined the time and gender differences. A total of 3,294 Chinese adolescents were recruited during two waves (T1: January 2023; T2: August 2023), and completed the questionnaires of social anxiety and problematic mobile phone use. Through network analysis, the results showed that 1) the central symptom of problematic mobile phone use was "loss of control" both at T1 and T2, 2) the central symptom of social anxiety was "fear of negative evaluation" both at T1 and T2, and 3) the bridge symptom between social anxiety and problematic mobile phone use was "withdrawal" both at T1 and T2. Moreover, the network comparison test indicated that the nodes of social anxiety were more strongly associated with "craving", "loss of control", and "negative life consequences" of problematic mobile phone use at T2 than at T1. The nodes of social anxiety were more strongly associated with "negative life consequences" of problematic mobile phone use for boys than for girls, while the "fear of negative evaluation" was more strongly associated with "loss of control" for girls than for boys. These findings provide new scientific basis for interventions targeting adolescents who are susceptible to social anxiety and problematic mobile phone use.


Sujet(s)
Anxiété , Utilisation du téléphone portable , Humains , Adolescent , Mâle , Femelle , Études longitudinales , Chine/épidémiologie , Utilisation du téléphone portable/statistiques et données numériques , Anxiété/psychologie , Anxiété/épidémiologie , Facteurs sexuels , Téléphones portables/statistiques et données numériques , Comportement de l'adolescent/psychologie , Comportement toxicomaniaque/psychologie , Comportement toxicomaniaque/épidémiologie , Peuples d'Asie de l'Est
7.
Chemphyschem ; 25(13): e202300816, 2024 Jul 02.
Article de Anglais | MEDLINE | ID: mdl-38563655

RÉSUMÉ

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.

8.
World J Urol ; 42(1): 206, 2024 Apr 01.
Article de Anglais | MEDLINE | ID: mdl-38561548

RÉSUMÉ

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.


Sujet(s)
Tumeurs du pénis , Humains , Mâle , Agents colorants , Vert indocyanine , Lymphadénectomie/méthodes , Noeuds lymphatiques/imagerie diagnostique , Noeuds lymphatiques/chirurgie , Noeuds lymphatiques/anatomopathologie , Métastase lymphatique/anatomopathologie , Tumeurs du pénis/imagerie diagnostique , Tumeurs du pénis/chirurgie , Tumeurs du pénis/anatomopathologie , Biopsie de noeud lymphatique sentinelle/méthodes
9.
Int Arch Allergy Immunol ; 185(7): 659-667, 2024.
Article de Anglais | MEDLINE | ID: mdl-38467118

RÉSUMÉ

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.


Sujet(s)
Myélome multiple , Insuffisance rénale , Humains , Myélome multiple/traitement médicamenteux , Myélome multiple/complications , Myélome multiple/diagnostic , Insuffisance rénale/étiologie , Mâle , Femelle , Adulte d'âge moyen , Sujet âgé , Résultat thérapeutique , Pronostic , Protocoles de polychimiothérapie antinéoplasique/usage thérapeutique , Protocoles de polychimiothérapie antinéoplasique/effets indésirables , Dexaméthasone/usage thérapeutique , Adulte
10.
Ann Hematol ; 103(5): 1549-1559, 2024 May.
Article de Anglais | MEDLINE | ID: mdl-38526649

RÉSUMÉ

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.


Sujet(s)
COVID-19 , Purpura thrombopénique idiopathique , Humains , Purpura thrombopénique idiopathique/diagnostic , Études prospectives , Numération des plaquettes , Plaquettes
12.
Behav Sci (Basel) ; 14(1)2024 Jan 20.
Article de Anglais | MEDLINE | ID: mdl-38275356

RÉSUMÉ

School bullying among primary and secondary school students has received increasing attention, and identifying relevant factors is a crucial way to reduce the risk of bullying victimization. Machine learning methods can help researchers predict and identify individual risk behaviors. Through a machine learning approach (i.e., the gradient boosting decision tree model, GBDT), the present longitudinal study aims to systematically examine individual, family, and school environment factors that can predict the risk of bullying victimization among primary and secondary school students a year later. A total of 2767 participants (2065 secondary school students, 702 primary school students, 55.20% female students, mean age at T1 was 12.22) completed measures of 24 predictors at the first wave, including individual factors (e.g., self-control, gender, grade), family factors (family cohesion, parental control, parenting style), peer factor (peer relationship), and school factors (teacher-student relationship, learning capacity). A year later (i.e., T2), they completed the Olweus Bullying Questionnaire. The GBDT model predicted whether primary and secondary school students would be exposed to school bullying after one year by training a series of base learners and outputting the importance ranking of predictors. The GBDT model performed well. The GBDT model yielded the top 6 predictors: teacher-student relationship, peer relationship, family cohesion, negative affect, anxiety, and denying parenting style. The protective factors (i.e., teacher-student relationship, peer relationship, and family cohesion) and risk factors (i.e., negative affect, anxiety, and denying parenting style) associated with the risk of bullying victimization a year later among primary and secondary school students are identified by using a machine learning approach. The GBDT model can be used as a tool to predict the future risk of bullying victimization for children and adolescents and to help improve the effectiveness of school bullying interventions.

14.
Inorg Chem ; 63(1): 653-660, 2024 Jan 08.
Article de Anglais | MEDLINE | ID: mdl-38146259

RÉSUMÉ

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.

15.
Front Plant Sci ; 14: 1184618, 2023.
Article de Anglais | MEDLINE | ID: mdl-37794939

RÉSUMÉ

Nutrient heterogeneity in soil widely exists in nature and can have significant impacts on plant growth, biomass allocation, and competitive interactions. However, limited research has been done to investigate the interspecific competitive intensity between two clonal species in a heterogeneous habitat. Therefore, this greenhouse experiment was conducted with two clonal species, Phragmites australis and Scirpus planiculumis, exposed to heterogeneous and homogeneous patches of soil nutrients at five different planting ratios (0:4, 1:3, 2:2, 3:1 and 4:0), to assess the effects of both soil heterogeneity and interspecific competition on plant growth. It was found that soil nutrient heterogeneity significantly enhanced P. australis' interspecific competitive capacity and biomass by promoting a 20% increase in belowground allocation. Interestingly, the planting ratio did not affect the magnitude of this net outcome. In contrast, the superior competitor S. planiculumis did not exhibit significant change of growth indicators to the heterogeneous soil patches. These findings imply that the uncertainties associated with human-induced redistribution of plant species may lead to a shift in dominance from other species to those like P. australis, which have strong nutrient foraging abilities in response to heterogeneity in emergent wetland plant communities.

16.
Environ Res ; 239(Pt 2): 117411, 2023 Dec 15.
Article de Anglais | MEDLINE | ID: mdl-37839532

RÉSUMÉ

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.


Sujet(s)
Conservation des ressources naturelles , Écosystème , Animaux , Humains , Conservation des ressources naturelles/méthodes , Surveillance de l'environnement/méthodes , Agriculture/méthodes , Chine , Triticum
17.
Phys Chem Chem Phys ; 25(36): 24853-24861, 2023 Sep 20.
Article de Anglais | MEDLINE | ID: mdl-37672278

RÉSUMÉ

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.

18.
Bioeng Transl Med ; 8(5): e10409, 2023 Sep.
Article de Anglais | MEDLINE | ID: mdl-37693055

RÉSUMÉ

Developing a living prosthetic breast to inhibit potential breast cancer recurrence and simultaneously promote breast reconstruction would be a promising strategy for clinical treatment of breast cancer after mastectomy. Here, a living prosthetic breast in the form of injectable gelatin methacryloyl microspheres is prepared, where they encapsulated zeolitic imidazolate framework (ZIF) nanoparticles loaded with small molecules urolithin C (Uro-C) and adipose-derived stem cells (ADSCs). Taking advantage of the acidic tumor microenvironment, the ZIF triggered a pH-sensitive drug release in situ so that Uro-C can induce tumor cell apoptosis via reactive oxygen species (ROS) generation. Meanwhile, the ADSCs proliferate in situ to promote tissue regeneration. Using such a design, our data showed that the ADSCs maintained viable and proliferate under the inhibitory effect of Uro-C in vitro. Through ROS generation, Uro-C also activated a suppressive tumor microenvironment in mice by both re-polarizing M2 macrophages to M1 macrophages for elevated inflammatory responses, and increasing the ratio between CD8 and CD4 T cells for tumor recurrence inhibition, significantly promoting new adipose tissue formation. Altogether, our results demonstrate that the prepared living prosthetic breast with bifunctional properties can be a promising candidate in clinic involving tumor treatment and tissue engineering in synergy.

19.
Ecol Lett ; 26(10): 1780-1791, 2023 Oct.
Article de Anglais | MEDLINE | ID: mdl-37586885

RÉSUMÉ

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.


Sujet(s)
Grippe chez les oiseaux , Animaux , Grippe chez les oiseaux/épidémiologie , Écologie , Europe/épidémiologie
20.
Chemosphere ; 335: 139080, 2023 Sep.
Article de Anglais | MEDLINE | ID: mdl-37263510

RÉSUMÉ

Important functions of constructed wetland related to biogeochemical processes are mediated by soil microbes and low-temperature damage is the main limiting factor for microbes in winter. However, the response thresholds for active microbial community and enzyme activities to continuous decreases in temperature remain unclear. In this study, total 90 soil samples were collected every week over a 6-week period to track the dynamics of four enzymes involved in cycles of C, N, P and active bacterial community as field soil temperature decreased continuously from 6.62 °C to 0.55 °C. Enzyme activity changed suddenly when the temperature decreased to 4.83 °C, the nitrite reductase activity reduced by 36.2%, while alkaline phosphatase activity is increased by 396%. The cellulase and urease were only marginally influenced by cold stress. Decreased nitrite reductase activities corresponded with loss of nir-type denitrifiers important for nitrite reduction. For cold stress, N-related bacteria were sensitive species. Whereas increased alkaline phosphatase activity may be due to the fact that P-related bacteria were opportunistic species. Key functional taxa connected with degradation of cellulose promoted species coexistence and microbial network stability. The lower and upper temperature thresholds for community change were 4.85 °C and 6.30 °C, respectively. Collectively, these results revealed that microbial taxa involved in C, N and P cycling respond differently to continuous decreases in temperature and higher than 4.85 °C is an ideal environment to prevent loss of microbial diversity and functions in winter, providing a scientific reference for the targeted isolation and cultivation of key microbial taxa in rhizosphere soil and adjusting temperature range to improve the purification capacity of wetlands during low temperature periods.


Sujet(s)
Microbiote , Zones humides , Température , Phosphatase alcaline/métabolisme , Bactéries/métabolisme , Sol/composition chimique , Nitrite reductases/métabolisme , Microbiologie du sol
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