CARD11 regulates the thymic Treg development in an NF-κB-independent manner.

Introduction: CARD11 is a lymphoid lineage-specific scaffold protein regulating the NF-κB activation downstream of the antigen receptor signal pathway. Defective CARD11 function results in abnormal development and differentiation of lymphocytes, especially thymic regulatory T cells (Treg). Method: In this study, we used patients' samples together with transgenic mouse models carrying pathogenic CARD11 mutations from patients to explore their effects on Treg development. Immunoblotting and a GFP receptor assay were used to evaluate the activation effect of CARD11 mutants on NF-κB signaling. Then the suppressive function of Tregs carrying distinct CARD11 mutations was measured by in vitro suppression assay. Finally, we applied the retroviral transduced bone marrow chimeras to rescue the Treg development in an NF-κB independent manner. Results and discuss: We found CARD11 mutations causing hyper-activated NF-κB signals also gave rise to compromised Treg development in the thymus, similar to the phenotype in Card11 deficient mice. This observation challenges the previous view that CARD11 regulates Treg lineage dependent on the NF-kB activation. Mechanistic investigations reveal that the noncanonical function CARD11, which negatively regulates the AKT/ FOXO1 signal pathway, is responsible for regulating Treg generation. Moreover, primary immunodeficiency patients carrying CARD11 mutation, which autonomously activates NF-κB, also represented the reduced Treg population in their peripheral blood. Our results propose a new regulatory function of CARD11 and illuminate an NF-κB independent pathway for thymic Treg lineage commitment.

Molecular mechanism of the transformation of oxidized lignin to N-substituted aromatics.

The cleavage of C-C bonds in oxidized lignin model compounds is a highly effective methodology for achieving lignin depolymerization, as well the generation of N-substituted aromatics. Here, density functional theory calculations were performed to understand the mechanism of the transformation of an oxidized lignin model compound (ligninox) and hydroxylamine hydrochloride to N-substituted aromatics. The reaction was proposed to proceed via an energetically viable mechanism featuring the initial production of HOAc acting as proton bridge. According to our calculations, Z-type oxime is the major intermediate of the reaction, with an energy barrier of 22.9 kcal mol-1, owing to the weak interactions between methoxy and oximino groups being stronger than that of E-type oxime. Additionally, the hydroxy addition is the rate-determining step, with an energy barrier of 27.0 kcal mol-1. Moreover, the huge net energy change of Beckmann and abnormal Beckmann rearrangements is the main overall thermodynamic driving force for producing N-substituted aromatics from oximes. The theoretical results have provided a clear picture of how ligninox transforms into N-substituted aromatics and are expected to provide valuable theoretical guidance for lignin depolymerization.

Centralized health management based on hot spring resort improves physical examination indicators and sleep quality in people at high risk of chronic diseases: a randomized controlled trial.

We study the effects of centralized health management based on hot spring resorts on the physical examination index and sleep quality of people at high risk of chronic diseases. We recruited 114 volunteers at high risk of chronic diseases. We then divided them into 57 in the intervention group and 57 in the control group. The intervention group collectively received 4 weeks (28 days) of comprehensive health management interventions at Tongjing Hotspring Resort, including regular schedules, balanced diet, appropriate exercise, targeted health education, etc. The main outcomes are physical examination indicators (height, weight, waist circumference, blood pressure, lipids, and glucose) and sleep quality. Both groups underwent a questionnaire and physical examination at baseline, 2 weeks and 4 weeks. Intragroup comparisons grouped by exposure criteria showed decreases in BMI, waist circumference, triglycerides, total cholesterol, and blood glucose in the intervention group at both 2 and 4 weeks (all P < 0.05); however, in the control group, only triglycerides decreased at 4 weeks (P < 0.05). Intergroup comparisons showed BMI and waist circumference were significantly lower in the intervention group than in the control group at 4 weeks (all P < 0.05). Intragroup comparisons of insomnia severity index (ISI) scores showed a significant decrease in the intervention group at both 2 and 4 weeks (all P < 0.001) with no significant change in the control group (P > 0.05). Intergroup comparisons showed that the insomnia severity index (ISI) scores were significantly higher in the intervention group than in the control group at baseline (P = 0.006) but became significantly lower than the control group at 2 and 4 weeks (all P < 0.001). Thus, this pattern significantly improved BMI, waist circumference, triglycerides, and sleep in the intervention group. TRIAL REGISTRATION NUMBER: Chinese Clinical Trials Registry: ChiCTR2100053201, registered 14 Nov 2021. (Retroactive Registration).

Mechanistic Insight into Palladium/Brønsted Acid Catalyzed Methoxycarbonylation and Hydromethoxylation of Internal Alkene: A Computational Study.

Density functional theory (DFT) calculations were performed to study the palladium/Brønsted acid-catalyzed methoxycarbonylation and hydromethoxylation reactions of internal alkene. The calculated results show that the pyridyl group (N atom) in bidentate phosphine ligand with built-in base (L1) plays a crucial role in controlling the selectivity. With the help of the pyridyl group, the methanolysis steps in the methoxycarbonylation reaction and the hydromethoxylation reaction become easy, and both the linear ester methyl 3,4-dimethylpentanoate (P1) and the hydromethoxylation product 2-methoxy-2,3-dimethylbutane (P2) could be obtained. In contrast, the possibility of leading to branched ester P1' was ruled out according to our calculations. The steric effect could account for the observed selectivity. In the presence of the DPEphos ligand (L2) that does not bear the pyridyl group, the methanolysis step in the methoxycarbonylation reaction becomes the rate-determining step with a high overall energy barrier. Neither linear nor branched methoxycarbonylation product could be generated. The palladium/Brønsted acid co-catalyzed hydromethoxylation also become difficult without the assistance of the pyridyl group in the presence of the L2 ligand. Instead, TsOH-catalyzed hydromethoxylation reaction could take place to generate the ether product P2.

The annulation of N-hydroxyoximes and 1,3-diyne to synthesize alkynylated isoquinolines regioselectively catalyzed by ruthenium: a theoretical study.

The mechanisms of the regioselective annulation of N-hydroxyoximes and 1,3-diyne to synthesize alkynylated isoquinolines by using the catalyst [RuCl2(p-cymene)]2 have been theoretically investigated with the aid of density functional theory (DFT) calculations. The role of the additive KPF6 employed in this experiment is clarified based on our mechanistic studies. PF6- could displace one free Cl- to activate the proximal arene C-H bond via the achievable outer-sphere base-assisted concerted metalation/deprotonation mechanisms. It can be deduced that the 1,3-diyne migratory insertion mode plays a key role in controlling the regioselectivity. The origin of the regioselectivity is probed by investigating electronic effects. The stronger electron-donating effect of the phenyl group compared with the alkynyl group facilitates the generation of 4-alkynylated isoquinoline. The impact of substituent groups on the regioselectivity could also be attributed to the electronic effects. The high electron density of the proximal arene carbon and Ru atoms in the oxime moiety would restrict the formation of 4-alkynylated isoquinoline.

The Prevalence of Fear of Childbirth and Its Association With Intolerance of Uncertainty and Coping Styles Among Pregnant Chinese Women During the COVID-19 Pandemic.

Background: Fear of childbirth (FOC) is one of the most common psychological symptoms among pregnant women and significantly relates to cesarean section, anxiety, and depression. However, it is not clear the prevalence and risk factors of FOC among Chinese pregnant women since the outbreak of the COVID-19 pandemic. Aims: The objective of this study was to examine the associations between coping styles, intolerance of uncertainty, and FOC. Method: From December 2021 to April 2022, a cross-sectional survey was conducted in two hospitals in China through convenient sampling. The cross-sectional survey was conducted among 969 pregnant women, which included the Childbirth Attitude Questionnaire (CAQ), Intolerance of Uncertainty Scale-12 (IUS-12), and Simplified Coping Style Questionnaire (SCSQ). Results: The total prevalence of FOC was 67.8%. The percentages of women with mild (a score of 28-39), moderate (40-51), and severe FOC (52-64) were 43.6, 20.2, and 4.0%, respectively. The regression results indicated that primiparas, unplanned pregnancy, few spousal support, intolerance of uncertainty, and negative coping styles were significant risk factors of FOC. Women who adopt positive coping strategies experienced a lower level of childbirth fear. Conclusion: These findings suggest that cultivating positive coping styles and obtaining sufficient childbirth information may be helpful for mothers' mental health. Regular screening assessment of perinatal psychological symptoms, such as the high level of intolerance of uncertainty and negative coping styles, should be adopted to reduce the risk of fear of childbirth.

Between Personality Traits and Postpartum Depression: The Mediated Role of Maternal Self-Efficacy.

Purpose: Postpartum depression is related to many factors, which affect the health of mothers and infants. The purpose of this study is to test the mediated effect of self-efficacy in the relationship between vulnerable personality and postpartum depression. Patients and Methods: A cross-sectional survey was conducted with pregnant women aged ≥20 years from February to April 2021 in Zhengzhou, China. We recruited 587 pregnant women, and 429 pieces of data were available. The demographic characteristics questionnaire, General Self efficacy Scale (GSES) and Vulnerable Personality Style Questionnaire (VPSQ) were distributed in the prenatal survey. The Edinburgh Postnatal Depression Scale (EPDS) was used to screen postpartum depression symptoms at one month through WeChat and telephone follow-up. A mediated model was constructed to explain the relationship of variables and test the mediated effect of self-efficacy. Results: The valid questionnaires were 429 (effective response rate: 90.7%). The vulnerable personality and low self-efficacy were related to postpartum depression (all P< 0.01). The self-efficacy of pregnant women was inversely associated with vulnerable personality (ß= -0.415) and postpartum depression (ß= -0.216). The vulnerable personality and self-efficacy can explain 29.0% of the variation in postpartum depression. It was confirmed that a partial mediating effect of self-efficacy accounted for 18.0% (0.090/0.501) of the total effect. Conclusion: Maternal self-efficacy partly mediates the relationship between vulnerable personality traits and postpartum depression. The study implies the importance of targeted interventions to improve self-efficacy for women with vulnerable personality traits to reduce the risk of postpartum depression.

Multiple Reaction Pathways of Eight-Membered Rhodacycles in Rh-Catalyzed Annulations of 2-Alkenyl Phenols/Anilides with Alkynes.

Density functional theory calculations were performed to study the competing pathways of rhodacycle intermediates generated in Rh(III)-catalyzed annulations of 2-alkenyl phenols and 2-alkenyl anilides with alkynes. The results show that the multiple pathways of eight-membered rhodacycles can be subtly tuned to give specific cyclic products. The seven-membered oxacyclic and spirocyclic products from 2-alkenyl phenols are formed by favoring the pathway of dissociating the Rh-O bond of O-contained rhodacycles, which are followed by antarafacial nucleophilic attack. The indoline product from 2-alkenyl anilides is generated through the pathway of intramolecular olefin migratory insertion of the N-contained rhodacycle.

[Acupuncture at Ciliao (BL 32) for prevention of postpartum urinary retention in elderly parturient women: a randomized controlled trial].

OBJECTIVE: To explore the preventive effect of acupuncture at Ciliao (BL 32) on postpartum urinary retention as well as the time and volume of the first urination after delivery in elderly parturient women undergoing vaginal delivery. METHODS: A total of 180 elderly parturient women (≥35 years old) undergoing vaginal delivery were randomly divided into a blank control group, a conditional control group and an observation group, 60 cases in each group. The patients in the blank control group were treated with routine nursing plan; based on the treatment of the blank control group, the patients in the conditional control group were treated with additional intervention measures such as applying hot towel on the bladder and fingers pressing to stimulate urination; based on the treatment of the blank control group, the patients in the observation group were treated with acupuncture at bilateral Ciliao (BL 32) one hour after delivery for 20 min (the acupuncture was given only once). The incidence rate of postpartum urinary retention as well as the time and volume of the first urination among the women without urinary retention were observed; the satisfaction rate of the 3 groups was recorded. RESULTS: The incidence rate of postpartum urinary retention in the observation group was 5.0% (3/60), which was significantly lower than 26.7% (16/60) in the blank control group (P<0.01) and 16.7% (10/60) in the conditional control group (P<0.05); the incidence rate of postpartum urinary retention in the conditional control group was significantly lower than that in the blank control group [16.7% (10/60) vs 26.7%(16/60), P<0.05]. In the elderly women without urinary retention, the first urination time in the observation group was significantly earlier than that in the blank control group and conditional control group (P<0.01), and the first urination time in the conditional control group was earlier than that in the blank control group (P<0.01). The volume of first urination in the observation group was higher than that in the blank control group and the conditional control group (P<0.05, P<0.01). The satisfaction rates in the observation group and conditional control group were higher than that in the blank control group (P<0.01). CONCLUSION: Acupuncture at Ciliao (BL 32) could effectively prevent the postpartum urinary retention, improve the time and volume of the first urination in elderly parturient women undergoing vaginal delivery.

Distinct Roles of Ag(I) and Cu(II) as Cocatalysts in Achieving Positional-Selective C-H Alkenylation of Isoxazoles: A Theoretical Investigation.

For C-H alkenylation of aryl-substituted diarylisoxazoles, one mode is N-directed C-H alkenylation and the other is C-H alkenylation in the isoxazole ring. In this study, selective C-H alkenylations of 3,5-diarylisoxazoles have been investigated theoretically with the aid of density functional theory (DFT) calculations. With Cp*RhIII as the catalyst, the N-directed C-H alkenylation is preferred as a result of the stronger interaction energy caused by the nitrogen-directing effect. With Pd(OAc)2 as the catalyst and Ag2CO3 as the cocatalyst, their combination switches the regioselectivity to the C-H alkenylation in the isoxazole ring. The strong structural distortion involved in the competing N-directed olefin insertion transition state was found to suppress N-directed C-H alkenylation. With Pd(OAc)2 as the catalyst and Cu(OTf)2 as the cocatalyst, the N-directed C-H alkenylation becomes preferred due to the strong coordination of the nitrogen atom to the copper center. In particular, the structural and mechanistic information involved in the above two heterodimetallic Pd/Ag and Pd/Cu catalytic systems will help toward understanding and designing novel relevant heterodimetallic-catalyzed reactions.

Substituent-dependent generation of tricyclic frameworks by the rhodium-catalyzed cycloisomerization of homopropargyl allene-alkynes: a theoretical study.

Polycyclic compounds having biological activities can be modified by employing different substituents. Substituent-dependent generation of tricyclic frameworks by the rhodium-catalyzed cycloisomerization of homopropargyl allene-alkynes was investigated by using density functional theory calculations. A mechanistic study revealed that all the three reactions, A (Z = Me, X = tBu), B (Z = Me, X = Me), and C (Z = H, X = Me), underwent initial oxidative cyclization, from which the divergent cycloisomerization was triggered when different substituents were employed. It was found from our calculations that reactions A and B underwent alkyne insertion into the Rh-C(sp2) bond and resulted in a key metal carbenoid intermediate. From the metal carbenoid species, reaction A bearing a more hindered tert-butyl group prefers 1,2-hydrogen migration to produce a 6/5/4 tricyclic product, while reaction B bearing a less hindered methyl group prefers 1,2-carbon migration leading to ring expansion and producing a 6/5/5 tricyclic product. The origins of the distinct selectivity were disclosed, which are beneficial for the development of novel related reactions. For reaction C (Z=H, Z=H or Z=H, Z=Me), the ß-hydrogen elimination was found to be favored over the alkyne insertion into the Rh-C(sp2) bond and thus the monocyclic product is delivered. The E/Z effects involved in the above two cases were also discussed.

How and Why a Protic Ionic Liquid Efficiently Catalyzes Chemical Fixation of CO2 to Quinazoline-2,4-(1H,3H)-diones: Electrostatically Controlled Reactivity.

A density functional theory study has been conducted to gain insight into the intriguing experimental observations on the synthesis of quinazoline-2,4-(1H,3H)-diones from 2-aminobenzonitriles reacting with CO2 catalyzed by protic ionic liquids (ILs). We explored the molecular mechanism of the titled reaction, as well as the origin and catalytic nature of different ILs toward the reaction in detail. The calculated energetically viable mechanism involves CO2 attack, intramolecular rearrangement, and intramolecular cyclization stages. This mechanism features the initial polarization of the C≡N triple bond with the assistance of the real catalytic species, [HDBU+][TFECOO-], where the cation [HDBU+] acts as Brønsted acid and the anion [TFECOO-], the adduct of anion [TFE-] and CO2, acts as a nucleophile. The calculated results present the electrostatically controlled character of the reaction, where the reactivity relies on the electrostatic interaction of the IL cation with the anion. The reactivity can be controlled and regulated by the basicity of the deprotonated counterpart of the IL cation as well as the CO2 adsorption ability of the IL anion. The best catalytic performance of [HDBU+][TFE-] is attributed to its strongest basicity of the deprotonated counterpart of [HDBU+] and its most efficient CO2 adsorption property of [TFE-]. These theoretical results are expected to provide guidance for designing efficient IL-based catalysts in preparing quinazoline-2,4-(1H,3H)-diones by reacting 2-aminobenzonitriles with CO2.

Spa therapy (balneotherapy) relieves mental stress, sleep disorder, and general health problems in sub-healthy people.

To investigate the relieving effects of hot spring balneotherapy on mental stress, sleep disorder, general health problems, and women's health problems in sub-healthy people, we recruited 500 volunteers in sub-health in Chongqing, and 362 volunteers completed the project, including 223 in the intervention group and 139 in the control group. The intervention group underwent hot spring balneotherapy for 5 months, while the control group did not. The two groups took questionnaire investigation (general data, mental stress, emotional status, sleep quality, general health problems, as well as some women's health problems) and physical examination (height, weight, waist circumference, blood pressure, blood lipid, blood sugar) 5 months before and after the intervention, respectively. After intervention, sleep disorder (difficulty in falling asleep (P = 0.017); dreaminess, nightmare suffering, and restless sleep (P = 0.013); easy awakening (P = 0.003) and difficulty in falling into sleep again after awakening(P = 0.016); and mental stress (P = 0.031) and problems of general health (head pain (P = 0.026), joint pain(P = 0.009), leg or foot cramps (P = 0.001), blurred vision (P = 0.009)) were relieved significantly in the intervention group, as compared with the control group. While other indicators (fatigue, eye tiredness, limb numbness, constipation, skin allergy) and women's health problems (breast distending pain; dysmenorrhea, irregular menstruation) were relieved significantly in the self-comparison of the intervention group before and after intervention (P < 0.05), but showed no statistically significant difference between two groups (P > 0.05). All indications (except bad mood, low mood, and worry or irritability) in the intervention group significantly improved, with effect size from 0.096 to 1.302. Multiple logistic regression analysis showed that the frequency, length, and location of balneotherapy in the intervention group were the factors influencing emotion, sleep, and health condition (P < 0.05). Relief of insomnia, fatigue, and leg or foot cramps was greater in old-age group than in young-aged group (P < 0.05). Physical examination found that waist circumferences in women of various ages under 55 years were significantly reduced in the intervention group (P < 0.05), while that in men did not significantly change (P > 0.05). Spa therapy (balneotherapy) relieves mental stress, sleep disorder, general health, and reduces women's waist circumferences in sub-healthy people.

Theoretical investigation of the impact of ligands on the regiodivergent Rh-catalyzed hydrothiolation of allyl amines.

The reaction mechanisms of the Rh-catalyzed regiodivergent hydrothiolation of allyl amines have been theoretically investigated with the aid of density functional theory (DFT) calculations. The impact of ligands on the regioselectivity was rationalized. The origin of the regioselectivity involved in these reactions was probed by investigating the electronic and steric effects. The regioselectivity is derived from the stability of related intermediates. Among them, the steric effect plays an important role in controlling the regioselectivity. The origin of the regioselectivity could also be interpreted through the electronic effect on the corresponding transition states.

Factors Associated with Activities of Daily Life Disability among Centenarians in Rural Chongqing, China: A Cross-Sectional Study.

OBJECTIVE: This study aims to ascertain the health and lifestyle factors associated with the activities of daily living (ADL) disability of centenarians in rural Chongqing, China. METHOD: 564 centenarians living in rural Chongqing were selected for this cross-sectional study. Demographic characteristics and self-reported lifestyle factors were obtained from face-to-face interviews. ADL disability was measured using the Katz Activities of Daily Living Scale. RESULT: Among the respondents, 65.7% were considered ADL disability centenarians. Multivariable logistic regression analysis showed that preference for salt, drinking habits, social activities, physical activity, and failure to follow good diet habits were significantly associated with the ADL disability of centenarians. CONCLUSION: ADL disability of centenarians was associated with certain lifestyle habits. This outcome suggested that target intervention may help maintain ADL independence even among the oldest of the elderly population.

A theoretical study on the palladium-catalyzed oxidative carbocyclization-alkoxycarbonylation of bisallenes to construct seven-membered carbocycles assisted by olefins.

The reaction mechanisms of the Pd(ii)-catalyzed oxidative carbocyclization-alkoxycarbonylation of bisallenes to construct seven-membered carbocycles have been theoretically investigated with the aid of density functional theory (DFT) calculations. Our calculation results account for the experimental fact that the product should be the seven-membered carbocycle P1 instead of the spiro-type product P2. Our calculations indicate that CO coordination should occur prior to the ring closing step, which determines the regioselectivity. Through investigating the corresponding natural bond orbital (NBO) charges, we find that an electron withdrawing carbonyl group would decrease the electron density and lower the activation barrier. Therefore, the regioselectivity is dominated by the electronic effect.

Mechanistic insights into the selective cyclization of indolines with alkynes and alkenes to produce six- and seven-membered 1,7-fused indolines via Rh(iii) catalysis: a theoretical study.

The coupling reaction mechanisms of the Rh(iii)-catalyzed redox-neutral C7-selective aryl C-H functionalization of indolines with alkynes and alkenes have been theoretically investigated with the aid of the density functional theory (DFT) calculations. Our calculation results indicate that the active catalyst in this system is the cationic species [Cp*Rh(OAc)]+ (2cat) instead of the neutral species Cp*Rh(OAc)2 (1cat). The origin of forming different products associated with using different coupling partners was also rationalized in detail. For the coupling reaction of N-methoxycarbamoyl-protected indoline (1a) with alkyl alkyne (4a), the electronic effect plays a dominant role and causes the six-membered ring product to be the main product. For the coupling reaction of 1a with aryl alkyne (2a), through the replacement of alkyl alkyne with aryl alkyne, the steric effect serves as a crucial factor, compared with the electronic effect, and leads to the main seven-membered ring product. For the coupling reaction of 1a with acrylate (6a), the chemoselectivity is dictated by the steric effect and electronic effect.

Dietary attitudes and behaviours of women in China after the 2008 Wenchuan earthquake in three seismically different zones.

BACKGROUND AND OBJECTIVES: The sudden occurrence of the 2008 Wenchuan Earthquake not only devastated people's health, but also may have impacted on the psychological and dietary attitudes and behaviours of the survivors. Although the influence of natural disaster on people's health has been extensively investigated, there is a lack of information about the effects on people's dietary attitudes and behaviours. Our aim was to evaluate the influence of the Wenchuan earthquake on the dietary attitudes and behaviours of adult women from different zones of China in July 2008. METHODS AND STUDY DESIGN: 736 women, aged 18-55 years old, were randomly selected and interviewed after the earthquake. Women were selected from three zones: the earthquake zone (n=206), the shaking zone (n=326), and the non-seismic zone (n=204). RESULTS: Although nutrition knowledge mean scores of women in the three zones were relatively low, the women in the earthquake zone became more vigilant about the nutritional value and acceptability of food than women in the other two zones. Nevertheless, women in the earthquake zone also developed some arguably untoward, if understandable, behaviour after the disaster. They increased their consumption and tendency to stock instant food and snack items. That said, these findings were modulated by other factors such as age, residence, Body Mass Index (BMI), and nutrition knowledge itself, as were post-earthquake eating behaviours, as judged by the ordinal logistic regression analyses performed. CONCLUSIONS: The major Wenchuan earthquake was associated with differentials in dietary attitudes and behaviours among women by seismic zone.

Associations of neonatal high birth weight with maternal pre-pregnancy body mass index and gestational weight gain: a case-control study in women from Chongqing, China.

OBJECTIVES: To examine the associations of maternal pre-pregnancy body mass index (BMI) and gestational weight gain (GWG) with neonatal high birth weight (HBW) in a sample of Chinese women living in southwest China. METHODS: A hospital-based case-control study was conducted in Chongqing, China. A total of 221 mothers who delivered HBW babies (>4.0 kg) were recruited as cases and 221 age-matched (2-year interval) mothers with normal birth weight babies (2.5-4.0 kg) were identified as controls. ORs were estimated using conditional logistic regression analysis. For the analysis, pre-pregnancy BMI was categorised as underweight/normal weight/overweight and obesity and GWG was categorised as inadequate/appropriate/excessive. RESULTS: Among the cases, mean pre-pregnancy BMI was 21.8±2.8 kg/m(2), mean GWG was 19.7±5.1 kg and mean neonatal birth weight was 4.2±0.2 kg. In the controls, the corresponding values were 21.1±3.1 kg/m(2), 16.4±5.0 kg and 3.3±0.4 kg, respectively. More cases than controls gained excessive weight during pregnancy (80.1% vs 48.4%, p<0.001). No significant association was found between pre-pregnancy BMI and HBW babies (OR=1.04, 95% CI 0.97 to 1.11; p>0.05). GWG was positively related to HBW after adjustment for gravidity, gestational age, newborns' gender and family income (OR=1.18, 95% CI 1.12 to 1.25; p<0.001). The adjusted OR of delivering HBW babies was 5.39 (95% CI 2.94 to 9.89; p<0.001) for excessive GWG versus appropriate GWG. This OR was strengthened among pre-pregnancy normal weight women (OR=10.27, 95% CI 3.20 to 32.95; p<0.001). CONCLUSIONS: Overall, the findings suggest a significantly positive association between GWG and HBW. However, pre-pregnancy BMI shows no independent relationship with HBW.

Theoretical estimation of kinetic parameters for nucleophilic substitution reactions in solution: an application of a solution translational entropy model.

The kinetic parameters, such as activation entropy, activation enthalpy, activation free-energy, and reaction rate constant, for a series of nucleophilic substitution (SN) reactions in solution, are investigated using both a solution-phase translational entropy model and an ideal gas-phase translational entropy model. The results obtained from the solution translational entropy model are in excellent agreement with the experimental values, while the overestimation of activation free-energy from the ideal gas-phase translational entropy model is as large as 6.9 kcal mol(-1). For some of the reactions studied, such as and in methanol, and and in aqueous solution, the explicit + implicit model, namely, a cluster-continuum type model, should be employed to account for the strong solvent-solute interactions. In addition, the explicit + implicit models have also been applied to the DMSO-H2O mixtures, which would open up a door to investigate the reactions in a mixed solvent using density functional theory (DFT) methods.