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Due to the highly chemically inert nature, direct activation and transformation of dinitrogen are challenging. Here, we disclose the synthesis, isolation, and derivatization of (N2)3- supported by lutetium complex. Initially, a (N2)3- radical, in [{(C5Me5){MeC(NiPr)2}Lu}2(µ2-η2:η2-N2)][K(crypt)] (crypt = 2,2,2-cryptand) complex, was generated through the reduction of neutral lutetium dinitrogen complex [{(C5Me5){MeC(NiPr)2}Lu}2(µ2-η2:η2-N2)] with potassium metal. Subsequently, the reaction of (N2)3- complex with methyl triflate (or triflic acid) led to the formation of an N-C (or N-H) bond, yielding the corresponding [{(C5Me5){MeC(NiPr)2}Lu}2(NN-R)(OTf)][K(crypt)] (R = Me, H, OTf = CF3SO3) as the product. Both electron paramagnetic resonance spectroscopy and density functional theory analyses support the radical character of the NN-Me unit. The Lu-N bonds in the (NN-Me)â¢2- radical complex are predominantly ionic, with 77% of the unpaired electron localized on the (NN-Me) fragment. Moreover, the geometry of the pure organic radical (NN-Me)â¢2-, optimized by double-hybrid density functional theory, closely matches that of the (NN-Me)â¢2- lutetium complex.
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In dinitrogen (N2 ) fixation chemistry, bimetallic end-on bridging N2 complexes M(µ-η1 : η1 -N2 )M can split N2 into terminal nitrides and hence attract great attention. To date, only 4d and 5d transition complexes, but none of 3d counterparts, could realize such a transformation. Likewise, complexes {[Cp*Cr(dmpe)]2 (µ-N2 )}0/1+/2+ (1-3) are incapable to cleave N2 , in contrast to their Mo congeners. Remarkably, cross this series the N-N bond length of the N2 ligand and the N-N stretching frequency exhibit unprecedented nonmonotonic variations, and complexes 1 and 2 in both solid and solution states display rare thermally activated ligand-mediated two-center spin transitions, distinct from discrete dinuclear spin crossovers. In-depth analyses using wave function based ab initio calculations reveal that the Cr-N2 -Cr bonding in complexesâ 1-3 is distinguished by strong multireference character and cannot be described by solely one electron configuration or Lewis structure, and that all intriguing spectroscopic observations originate in their sophisticate multireference electronic structures. More critical is that such multireference bonding of complexesâ 1-3 is at least a key factor that contributes to their kinetic inertness toward N2 splitting. The mechanistic understanding is then used to rationalize the disparate reactivity of related 3d M(µ-η1 : η1 -N2 )M complexes compared to their 4d and 5d analogs.
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ConspectusThe activation and functionalization of N2 to form nitrogen-element bonds have long posed challenges to industrial, biological, and synthetic chemists. The first transition-metal dinitrogen complex prepared by Allen and Senoff in 1965 provoked researchers to explore homogeneous N2 fixation. Despite intensive research in the last six decades, efficient and quantitative conversion of N2 to diazenido and hydrazido species remains problematic. Relative to a plethora of reactions to generate N2 complexes, their functionalization reactions are rather rare, and the yields are often unsatisfactory, emphasizing the need for systematic investigations of the reaction mechanisms.In this Account, we summarize our recent work on the synthesis, spectroscopic features, electronic structures, and reactivities of several Cr-N2 complexes. Initially, a series of dinuclear and trinuclear Cr(I)-N2 complexes bearing cyclopentadienyl-phosphine ligands were accessed. However, they cannot achieve N2 functionalization but undergo oxidative addition reactions with phenylsilane, azobenzene, and other unsaturated organic compounds at the low-valent Cr(I) centers rather than at the N2 unit. Further reduction of these Cr(I) complexes leads to the formation of more activated mononuclear Cr(0) bis-dinitrogen complexes. Remarkably, silylation of the cyclopentadienyl-phosphine Cr(0)-N2 complex with Me3SiCl afforded the first Cr hydrazido complex. This process follows the distal pathway to functionalize the Nß atom twice, yielding an end-on η1-hydrazido complex, Cr(III)âN-N(SiMe3)2. In contrast, upon substitution of the phosphine ligand in the Cr(0)-N2 complex with a N-heterocyclic carbene (NHC) ligand, the corresponding reaction with Me3SiCl proceeds via the alternating pathway; the silylation occurs at both Nα and Nß atoms and generates a side-on η2-hydrazido complex, Cr(III)(η2-Me3SiN-NSiMe3). Both silylation reactions are inevitably accompanied by the formation of Cr(III) hydrazido complexes and Cr(II) chlorides with a 2:1 ratio. These processes exhibit a peculiar '3-4-2-1' stoichiometry (i.e., treating 3 equiv of Cr(0)-N2 complexes with 4 equiv of Me3SiCl yields 2 equiv of Cr(III) disilyl-hydrazido complexes and 1 equiv of Cr(II) chloride). Upon replacing the monodentate phosphine and/or NHC ligand with a bisphosphine ligand, a monodinitrogen Cr(0) complex, instead of the bis-dinitrogen Cr(0) complexes, is obtained; consequently, the silylation reactions progress via the normal two-electron route, which passes through Cr(II)-NâN-R diazenido species as an intermediate and furnishes [Cr(IV)âN-NR2]+ hydrazido as the final products. More importantly, this type of Cr(0)-N2 complex can be not only silylated but also protonated and alkylated proficiently. All of the second-order reaction rates of the first and second transformations are determined along with the lifetimes of the intervening diazenido species. Based on these findings, we have successfully carried out nearly quantitative preparations of the Cr(IV) hydrazido species with unmixed or hybrid substituents.The studies of Cr-N2 systems provide effective approaches for the activation and functionalization of N2, deepening the understanding of N2 electrophilic attack. We hope that this Account will inspire more discoveries related to the transformation of gaseous N2 to high-value-added nitrogen-containing organic compounds.
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In the domain of N2 activation, hetero-bimetallic dinitrogen complexes are garnering substantial interest due to their potential to induce polarization in nonpolar N2 gas. Herein, we present the syntheses and characterizations of three novel hetero-multimetallic dinitrogen complexes: Cp*Cr(depe)N2V(depe)Me[O, P, O] 5, Cp*Cr(depe)N2V(depe)Tipp[O, P, O] 6, and [Cp*Cr(depe)N2]2TiTipp[O, P, O] 7. These complexes were synthesized via a transmetalation process involving the treatment of [Cr0-N2]- complex 4 with vanadium and titanium chloride complexes bearing alkyl or aryl substituted bis(o-hydroxyphenyl)-phenyl phosphine R[O, P, O] ligand (alkyl = methyl, aryl = 2,4,6-tri-isopropylbenzene). X-ray analysis shows that complexes 5 and 6 exhibit heterodinuclear structures, while complex 7 exhibits a heterotrinuclear core with two N2 ligands concurrently coordinated to two chromium and one titanium atoms. Raman spectroscopic data show that the N-N stretching vibration of the N2 moiety is clearly downshifted relative to free N2 and to mononuclear [Cr0-N2]- complex 4.
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BACKGROUND: To explore the altered functional connectivity (FC) of the nucleus tractus solitarii (NTS) in patients with chronic cough after lung surgery using resting-state functional magnetic resonance imaging (rs-fMRI), and the association between abnormal FC and clinical scale scores. METHODS: A total of 22 patients with chronic cough after lung surgery and 22 healthy controls were included. Visual analog scale (VAS), Mandarin Chinese version of the Leicester Cough Questionnaire (LCQ-MC), and Hamilton anxiety rating scale (HAMA) scores were assessed, and rs-fMRI data were collected. The FC analysis was performed using the NTS as the seed point, and FC values with all voxels in the whole brain were calculated. A two-sample t-test was used to compare FC differences between the two groups. The FC values of brain regions with differences were extracted and correlated with clinical scale scores. RESULTS: In comparison to healthy controls, FC values in the NTS and anterior cingulate cortex(ACC) were reduced in patients with chronic cough after lung surgery (GRF correction, p-voxel < 0.005, p-cluster < 0.05) which were positively correlated with LCQ-MC scores (r = 0.534, p = 0.011), but with VAS (r = -0.500, p = 0.018), HAMA (r = -0.713, p < 0.001) scores were negatively correlated. CONCLUSIONS: Reduced FC of the NTS with ACC may be associated with cough hypersensitivity and may contribute to anxiety in patients with chronic cough after lung surgery.
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Tos , Núcleo Solitario , Humanos , Tos/diagnóstico por imagen , Tos/etiología , Imagen por Resonancia Magnética/métodos , Pulmón/diagnóstico por imagenRESUMEN
OBJECTIVE: Exploring the correlation between bone turnover marks (BTMs) with lumbar BMD in middle-aged populations. METHODS: The cross-sectional analysis fetched data came from NHANES. The level of serum bone alkaline phosphatase (sBAP) and urinary N-telopeptide (uNTx) were regarded as representative of bone turnover. Lumbar BMD was the outcome of the study. Multivariable linear regression models were utilized to detect the correlation of sBAP and uNTx with Lumbar BMD. RESULTS: The level of sBAP and uNTx was negatively correlated with lumbar BMD in every multivariable linear regression. For sBAP, this inverse correlation was stable in both men and women (P < 0.01). uNTx indicated a negative association after all relevant covariables were adjusted (P < 0.01). The men group remained the negative correlation in gender subgroup analysis (P < 0.01). CONCLUSION: This study indicated that the increased level of sBAP and uNTx associated with lumbar BMD decreased among middle-aged adults. This correlation could prompt researchers to explore further the relationship between bone turnover rate and BMD, which may provide information for the early detection of BMD loss and provide a new strategy for clinical practice.
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Fosfatasa Alcalina , Densidad Ósea , Adulto , Masculino , Persona de Mediana Edad , Femenino , Humanos , Estudios Transversales , Encuestas Nutricionales , Remodelación ÓseaRESUMEN
BACKGROUND: Accumulating evidences have demonstrated that overwhelming inflammation occurs in the process of Coxsackievirus B3 (CVB3)-induced acute viral myocarditis (AVM). No specific therapy is available. More than an effective Janus-associated kinase (JAK) inhibiter, ruxolitinib exerts a critical role in the inflammatory diseases. In this study, we investigated the potential effect of ruxolitinib on CVB3-induced acute viral myocarditis. METHOD: In vivo, BALB/c mice were intraperitoneally injected of CVB3, treated of a successive gavage of ruxolitinib for seven days, and subjected to a series of analysis. In vitro, primary bone marrow-derived macrophages (BMDMs) and cardiac fibroblasts were isolated, cultured, treated, harvested and finally detected. RESULTS: In vivo, acute viral myocarditis was successfully induced by the injection of CVB3 characterized by impaired cardiac function, predominant infiltration of inflammatory cells, necroptosis of myocardium, great increase of cardiac troponin I (cTnI) and cytokine levels, replication of CVB3, and excessive activation of JAK-STAT pathways. Oral administration of ruxolitinib suppressed the activation of JAK-STAT pathway in a dosage-dependent way, lessened the infiltration of inflammatory cells and necroptosis of myocardium, reduced the levels of cTnI and cytokines, and finally alleviated CVB3-induced cardiac dysfunction, with the reduced production of type I interferon and no promising effect on the replication of CVB3. In vitro, the treatment of ruxolitinib inhibited the activation of JAK-STAT pathway and increase of multiple cytokines mRNA levels in BMDMs and had no protective effect against CVB3 replication in cardiac fibroblasts. CONCLUSIONS: Our study suggested that ruxolitinib ameliorated CVB3-induced AVM by inhibiting the activation of JAK-STAT pathway, infiltration of inflammatory cells and necroptosis of myocardium, which may provide a novel strategy for AVM therapy.
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Background: Acupuncture has achieved good results in the treatment of cough, asthma, chronic obstructive pulmonary disease (COPD) and other lung diseases, but the mechanism associated with acupuncture in the treatment of chronic cough induced by lung surgery is unknown. We investigated whether acupuncture therapy could improve the symptoms of chronic cough after lung surgery through cyclic-AMp dependent protein kinase A (PKA)/cyclic-AMp dependent protein kinase C (PKC) regulation of the transient receptor potential vanilloid-1 (TRPV1) signaling pathway. Methods: The guinea pigs were divided into 5 groups: the Sham operation Group (Sham), the Model Group (Model), the Electroacupuncture + Model Group (EA + M), the H89 + Model Group (H89 + M) and the Go6983 + Model Group (Go6983 + M). The effect of treatment was determined by measuring cough symptoms (number of coughs/cough incubation period) as the outcome criterion. The levels of inflammatory cytokines in bronchoalveolar lavage fluid (BALF) and blood were determined by enzyme-linked immunosorbent assays (ELISA). Lung tissue was stained with hematoxylin and eosin (H&E). The expression of p-PKA, p-PKC and p-TRPV1 proteins was measured by Western blotting. The mRNA levels of TRPV1, Substance P (SP), calcitonin gene-related peptide (CGRP) and neurokinin-1R (NK1R) were measured by real-time polymerase chain reaction (RT-PCR). Results: Acupuncture significantly reduced the cough frequency and prolonged the cough latency of chronic cough in guinea pigs after lung surgery. In addition, acupuncture reduced the damage to lung tissue. The levels of inflammatory cytokines decreased in all treatment groups, the expression levels of p-PKA, p-PKC and p-TRPV1 were significantly inhibited and the mRNA levels of TRPV1, SP, CGRP and NK1R decreased significantly after acupuncture treatment. Conclusions: Acupuncture therapy ameliorated chronic cough in guinea pigs after lung surgery by regulating the TRPV1 signaling pathway via PKA/PKC. Our results showed that acupuncture may be an effective treatment of chronic cough after lung surgery, and also clarified the potential mechanism, which provides a theoretical basis for the clinical treatment of patients with chronic cough after lung surgery.
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Objectives: The study aims to establish a predictive nomogram of diabetic retinopathy(DR) for the middle-aged population with type 2 diabetes mellitus (T2DM). Methods: This retrospective study screened 931 patients with T2DM between 30 and 59 years of age from the 2011-2018 National Health and Nutrition Examination Survey database. The development group comprised 704 participants from the 2011-2016 survey, and the validation group included 227 participants from the 2017-2018 survey. The least absolute shrinkage and selection operator regression model was used to determine the best predictive variables. The logistic regression analysis built three models: the full model, the multiple fractional polynomial (MFP) model, and the stepwise (stepAIC) selected model. Then we decided optimal model based on the receiver operating characteristic curve (ROC). ROC, calibration curve, Hosmer-Lemeshow test, and decision curve analysis (DCA) were used to validate and assess the model. An online dynamic nomogram prediction tool was also constructed. Results: The MFP model was selected to be the final model, including gender, the use of insulin, duration of diabetes, urinary albumin-to-creatinine ratio, and serum phosphorus. The AUC was 0.709 in the development set and 0.704 in the validation set. According to the ROC, calibration curves, and Hosmer-Lemeshow test, the nomogram demonstrated good coherence. The nomogram was clinically helpful, according to DCA. Conclusion: This study established and validated a predictive model for DR in the mid-life T2DM population, which can assist clinicians quickly determining who is prone to develop DR.
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Diabetes Mellitus Tipo 2 , Retinopatía Diabética , Persona de Mediana Edad , Humanos , Diabetes Mellitus Tipo 2/complicaciones , Retinopatía Diabética/diagnóstico , Retinopatía Diabética/epidemiología , Retinopatía Diabética/etiología , Encuestas Nutricionales , Estudios Retrospectivos , InsulinaRESUMEN
BACKGROUND: To investigate the correlation between the fibrinogen combined with neutrophil-to-lymphocyte ratio (F-NLR) and the clinicopathologic features of non-small cell lung cancer (NSCLC) patients who underwent radical resection. METHODS: This study reviewed the medical records of 289 patients with NSCLC who underwent radical resection. The patients were stratified into three groups based on F-NLR as follows: patients with low NLR and fibrinogen were group A, patients with high NLR or fibrinogen were group B, and patients with high NLR and fibrinogen were group C. Receiver operating characteristic curve and Youden index were used to determine the cutoff value of the NLR and fibrinogen. Survival curves were described by Kaplan-Meier method and compared by log-rank test. The univariate and multivariate analyses were performed with the Cox proportional hazard model to identify the prognostic factors. RESULTS: A value of 3.19 was taken as the optimal cutoff value of NLR in this study. A value of 309 was used as the optimal cutoff value of fibrinogen. Cox multivariate analysis showed that tumor, nodes, metastasis (TNM) stage and F-NLR were independent prognostic factors affecting the survival rate of patients. The first-, third-, and fifth-year survival rates in group A were 99.2%, 96.6%, and 95.0%, respectively. The first-, third-, and fifth-year survival rates in group B were 98.4%, 76.6%, and 63.2%, respectively. The first-, third-, and fifth-year survival rates in group C were 91.3%, 41.1%, and 22.8%, respectively. F-NLR was significantly correlated with overall survival in patients with NSCLC (p < 0.001). CONCLUSIONS: The F-NLR level is markedly related to the prognosis of patients with NSCLC undergoing radical surgery. Therefore, closer attention should be given to patients with NSCLC with a high F-NLR before surgery to provide postoperative adjuvant therapy.
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Carcinoma de Pulmón de Células no Pequeñas , Neoplasias Pulmonares , Humanos , Neutrófilos/patología , Pronóstico , Fibrinógeno , Neoplasias Pulmonares/patología , Linfocitos/patología , Estudios RetrospectivosRESUMEN
Recent studies have shown a correlation between high-density lipoprotein cholesterol (HDL-C) and bone mineral density (BMD) in adults, but their relationship is unclear in adolescents. This study aimed to explore whether a correlation existed between them among adolescents aged 12-19. Data analyzed in our study was fetched from the National Health and Nutrition Examination Survey (NHANES) database 2011-2018. The relationship between HDL-C level and total BMD value was analyzed by multivariate logistic regression models, fitted smoothing curves, and generalized additive models. 3770 participants participated in this analysis. After adjusting for all relevant covariates involved in this study, we found a negative correlation between HDL-C levels and total bone density in male adolescents.Furthermore, the stratified analysis showed that all covariables-adjusted models retained the negative correlation excepting female, black, or Mexican American subgroups. An inverted U-shaped curve represented the correlation of HDL-C and total BMD among adolescents aged 16 to 19, and the turning point was 1.06 mmol/L. After adjusting for all relevant covariates involved in this study, the study found a negative correlation between HDL-C levels and total BMD in male adolescents aged 12 to 19, particularly among those of races other than Black and Mexican. There was a saturation effect between HDL-C level and total BMD in 16-19-year-old adolescents. The turning point was 1.06 mmol/L. Therefore, HDL-C might be a biomarker to detect bone health and further perform a more detailed examination.
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Densidad Ósea , Adulto , Humanos , Masculino , Femenino , Adolescente , Adulto Joven , HDL-Colesterol , Estudios Transversales , Encuestas Nutricionales , TriglicéridosRESUMEN
Background: Previous studies have investigated the link between fatty acid intake and bone mineral density (BMD), but the results are controversial. This study aims to examine the relationship between fatty acid intake and BMD in adults aged 20-59. Methods: The association between fatty acid consumption and BMD was analyzed using a weighted multiple linear regression model with National Health and Nutrition Examination Survey data from 2011 to 2018. The linearity relationship and saturation value of the connection between fatty acid consumption and BMD were assessed by fitting a smooth curve and a saturation effect analysis model. Results: The study included 8,942 subjects. We found a significant positive correlation between the consumption of saturated fatty acids, monounsaturated fatty acids (MUFAs), and polyunsaturated fatty acids and BMD. In subgroup analyses that were stratified by gender and race, this association was still shown to be significant. Based on the smooth curve and saturation effect analysis, we found no saturation effect for the three fatty acids and total BMD. However, there was a turning point (20.52 g/d) between MUFAs intake and BMD, and only MUFAs intake >20.52 g/d showed a positive correlation between MUFAs and BMD. Conclusion: We found that fatty acid intake is beneficial for bone density in adults. Therefore, according to our findings, it is recommended that adults consume moderate amounts of fatty acids to ensure adequate bone mass but not metabolic diseases.
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Electrophilic functionalization of N2 moieties in metal dinitrogen complexes typically initiates the catalytic synthesis of N-containing molecules directly from N2. Despite intensive research in the last six decades, how to efficiently and even quantitatively convert N2 into diazenido and hydrazido species still poses a great challenge. In this regard, systematic and comprehensive investigations to elucidate the reaction intricacies are of profound significance. Herein, we report a kinetic dissection on the first and second electrophilic functionalization steps of a new Cr0-N2 system with HOTf, MeOTf, and Me3SiOTf. All reactions pass through fleeting diazenido intermediates and furnish long-lived final hydrazido products, and both steps are quantitative conversions at low temperatures. All of the second-order reaction rates of the first and second transformations were determined as well as the lifetimes of the intervening diazenido species. Based on these findings, we succeeded in large-scale and near-quantitative preparation of all hydrazido species.
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Objectives: The prevalence of obesity is on the rise and is connected to numerous factors. However, the relationship between obesity and nickel has never been investigated. Our study aimed to explore the association between urinary nickel and obesity Status in adults. Methods: From the 2017-2018 National Health and Nutrition Examination Surveys (NHANES), 1,705 participants ≥18 years of age were enrolled. To explore further the relationship among urinary nickel, body mass index (BMI), and waist circumference(WC), Weighted multivariate linear regression analyses and further subgroup analyzes were conducted. Results: Urinary nickel does not correlate with BMI level but positively correlates with WC. In the subgroup analyzed according to sex, Urinary nickel has a positive correlation with BMI and WC in males but has a negative correlation in females. Secondary stratification analysis according to sex and race, Urinary nickel positively correlates with BMI in White males. It also positively correlates with WC in both White and Black males. Conclusions: A correlation was found between urinary nickel levels and BMI and WC in adult males. Adult men, especially those already obese, may need to reduce nickel exposure.
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Níquel , Obesidad , Adulto , Femenino , Humanos , Masculino , Estudios Transversales , Níquel/orina , Encuestas Nutricionales , Obesidad/epidemiología , Obesidad/orinaRESUMEN
Isolation of key intermediate complexes in dinitrogen functionalization is crucial for elucidating the mechanistic details and further investigation. Herein, the synthesis and characterization of (µ-η1:η1-N2)(η1-N2)-Cr(I) 3 and (η1-N2)2-Cr(0) complexes 4 supported by Cp* (Cp* = C5Me5) and NHC ligands were reported. Further functionalization of Cr(0)-N2 complex 4 with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex 5 and the chromium side-on η2-hydrazido complex 6. Protonation of 6 led to the quantitative formation of N2H4. Moreover, the [η2-Me3SiNNSiMe3]2- unit in 6 enabled N-C bond formation reactions with CO2 and tBuNCO, giving the corresponding N,O-chelating hydrazidochromium complexes 7 and 8, respectively.
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By reacting the semi-rigid PNP ligand with CoBr2, the corresponding complex PNPCoBr (1) was obtained. The reduction of 1 with excess amounts of KC8 in THF under a N2 atmosphere yielded a binuclear cobalt dinitrogen anion complex [Co(µ-Cy2P)PCyN2]2K (2) via the C-P bond cleavage of the PNP ligand. By adding 2,2,2-cryptand into complex 2, an ion pair Co complex, [Co(µ-Cy2P)PCyN2]2K(crypt-222) (3), could be effectively prepared. The structures of 1, 2, and 3 have been determined by single-crystal X-ray diffraction analysis, and N2 is moderately activated in complexes 2 and 3. There is a Co-Co bond in 2 and 3 suggested by DFT calculations. Compounds 1 and 2 display catalytic activity for the transformation of N2 into N(SiMe3)3.
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Background: The effect of obesity status on bone mineral density (BMD) in adolescents and whether there is a saturation effect is still insufficient. A cross-sectional study of adolescents aged 12-19 was conducted to investigate them. Methods: Weighted multivariate linear regression models were used to assess the relationship between obesity status and BMD via datasets from the National Health and Nutrition Examination Survey 2011-2018. The nonlinear relationships and saturation values were ascertained by fitting smooth curves and analyzing saturation effects. At the same time, the subgroup stratified analysis was also performed. Results: 4056 adolescents were included in this study. We found that body mass index (BMI) and waist circumference (WC) were significantly associated with total BMD, which remained significant in subgroups stratified by age, gender, standing height, and ethnicity. We also noticed an inverse correlation between left leg fat/lean mass and left leg BMD, which was only significant in males and other races. Fitting smooth curve and saturation effect analysis showed that BMI, WC, left leg fat/lean mass, and BMD had a specific saturation effect. There was a saturation effect on bone mineral density in adolescents with a BMI of 22 kg/m2, a WC of 70.5 cm, or a left leg fat/lean mass of 0.2994. Conclusions: We found a positive saturation effect of BMI and WC with BMD and a negative saturation effect of left leg fat/lean mass with BMD. Appropriate obesity status allows adolescents to have better bone mass development but not excessive obesity.
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Composición Corporal , Densidad Ósea , Masculino , Adolescente , Humanos , Estudios Transversales , Encuestas Nutricionales , Obesidad/complicaciones , Obesidad/epidemiologíaRESUMEN
By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl2 , the corresponding cobalt chlorides (1, LCoII Cl) were prepared. By reducing complexes 1 with KHBEt3 under a N2 atmosphere, bridging end-on complexes, LCoI -N2 -CoI L (2 a and 2 b), were successfully obtained. 15 N2 -labeled [15 N2 ]-2 a was prepared under 15 N2 /14 N2 exchange in THF solution. LCoI -N2 -CoI L complex 2 a could react with P4 molecules to release N2 and generate a Co-P4 -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel µ-PCy2 -bridged Co0 -N2 complex 5. DFT calculations confirmed the experimental observations.
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Nitrógeno , Fosfinas , Modelos Moleculares , Nitrógeno/química , Fosfinas/química , Cobalto/química , LigandosRESUMEN
OBJECTIVES: The objective of this research aimed to investigate the correlation involving serum albumin with diabetic retinopathy (DR) in patients with type 2 diabetes mellitus (T2DM). METHODS: From 2011 to 2020, the National Health and Nutrition Examination Survey (NHANES) surveyed 45462 participants. We used the relevant data to conduct descriptive statistics, linear regression, and Logistic regression analysis. RESULTS: After adjusting for age, sex, and race, as well as all other variables, serum albumin was significantly negatively related to DR (P<0.001). Furthermore, after controlling for confounding factors, the third quartile (Q3) and the fourth quartile (Q4) had quite a negative significant relationship with the incidence of DR (P<0.01). The second quartile had a significant positive correlation with DR, whereas the observed negative correlations were not statistically meaningful (P>0.05). CONCLUSION: Albumin levels in the serum have a quantitatively significant negative correlation with DR. Serum albumin levels in the blood can be used as a reference point for protracted follow-up of people with T2DM.
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Diabetes Mellitus Tipo 2 , Retinopatía Diabética , Retinopatía Diabética/diagnóstico , Humanos , Encuestas Nutricionales , Factores de Riesgo , Albúmina SéricaRESUMEN
The element nitrogen and nitrogenous compounds are vital to life. The synthesis of nitrogen-containing compounds using dinitrogen as the nitrogen source, not through ammonia, is of great interest and great value but remains a grand challenge. Herein, we describe a strategy to realize this transformation by combining the heterogeneous approach with the homogeneous methodology. The N2 molecule was first fixed with carbon and LiH through a one-pot heterogeneous process, forming Li2CN2 as an 'activated' nitrogen source with high efficiency. Then subsequent homogeneous treatments of Li2CN2 to construct the organic synthon carbodiimide and the RNA/DNA building block pyrimidines were fulfilled. By using 15N2 as the feedstock, their corresponding 15N-labeled carbodiimide and pyrimidines were readily obtained. This homogeneous-heterogeneous synergy strategy will open a new chapter for N2 transformation.