Isomerization of surface functionalized SWCNTs and the critical influence on photoluminescence: static calculations and excited-state dynamics simulations.

Single-walled carbon nanotubes (SWCNTs) functionalized with sparse surface chemical groups are promising for a variety of optical applications such as quantum information and bio-imaging. However, the luminescence efficiencies and stability, two key aspects, undoubtedly govern their practical usage. Herein, we assess the surface migration of oxygen and triazine groups on as-modified SWCNT fragments by adopting transition state theory and explore the de-excitation of oxygen-functionalized SWCNT fragments by performing non-adiabatic excited-state dynamics simulations. According to the predicted moderate or even small reaction barriers, the migration of both oxygen and triazine groups is feasible from an sp3 defect configuration forming an energetically more stable sp2 configuration at moderate or even room temperatures. Such isomerization leads to drastically different light emission capabilities as indicated by the large or zero oscillator strengths. During the dynamics simulations, the lowest excited singlet (S1) state rapidly decays in energy within 20 fs and then fluctuates until the end, providing insights into the emission mechanism of SWCNTs. This study highlights the potential intrinsic limitations of surface-functionalized SWCNTs for luminescence applications.

Face presentation at term: incidence, risk factors and influence on maternal and neonatal outcomes.

OBJECTIVES: The incidence, diagnosis, management and outcome of face presentation at term were analysed. METHODS: A retrospective, gestational age-matched case-control study including 27 singletons with face presentation at term was conducted between April 2006 and February 2021. For each case, four women who had the same gestational age and delivered in the same month with vertex position and singletons were selected as the controls (control group, n = 108). Conditional logistic regression was used to assess the risk factors of face presentation. The maternal and neonatal outcomes of the face presentation group were followed up. RESULTS: The incidence of face presentation at term was 0.14‰. After conditional logistic regression, the two factors associated with face presentation were high parity (adjusted odds ratio [aOR] 2.76, 95% CI 1.19-6.39)] and amniotic fluid index > 18 cm (aOR 2.60, 95% CI 1.08-6.27). Among the 27 cases, the diagnosis was made before the onset of labor, during the latent phase of labor, during the active phase of labor, and during the cesarean section in 3.7% (1/27), 40.7% (11/27), 11.1% (3/27) and 44.4% (12/27) of cases, respectively. In one case of cervical dilation with a diameter of 5 cm, we innovatively used a vaginal speculum for rapid diagnosis of face presentation. The rate of cesarean section and postpartum haemorrhage ≥ 500 ml in the face presentation group was higher than that of the control group (88.9% vs. 13.9%, P < 0.001, and 14.8% vs. 2.8%, P = 0.024), but the Apgar scores were similar in both sets of newborns. Among the 27 cases of face presentation, there were three cases of adverse maternal and neonatal outcomes, including one case of neonatal right brachial plexus injury and two cases of severe laceration of the lower segment of the uterus with postpartum haemorrhage ≥ 1000 ml. CONCLUSIONS: Face presentation was rare. Early diagnosis is difficult, and thus easily neglected. High parity and amniotic fluid index > 18 cm are risk factors for face presentation. An early diagnosis and proper management of face presentation could lead to good maternal and neonatal outcomes.

Efficient wide-spectrum one-dimensional MWO4 (M = Mn, Co, and Cd) photocatalysts: Synthesis, characterization and density functional theory study.

Broadening the absorption region to near-infrared (NIR) light is critical for the photocatalysis due to the larger proportion and stronger penetration of NIR light in solar energy. In the present paper, one-dimensional (1D) MWO4 (M = Mn, Co, and Cd) materials synthesized by electrospinning technique, were studied by combining the density functional theory (DFT) with experiment results, which possessed the enhanced light absorption capability within the range of 200-2000 nm. It was proved that in the ultraviolet-visible (UV-Vis) region, the absorption bands of CoWO4 and MnWO4 samples were attributed to the metal-to-metal charge transfer mechanism, while the absorption of CdWO4 sample may be referable to the ligand-to-metal charge transfer mechanism. In the near-infrared (NIR) region, the absorption of CoWO4 and MnWO4 primarily originated from the d-d orbital transitions of Mn2+ and Co2+. The photocatalytic experimental results showed that the degradation rates for bisphenol A (BPA) over CoWO4, MnWO4, and CdWO4 photocatalysts under UV-Vis/NIR light irradiation for 140 min/12 h were 78.8 %/75.9 %, 23.8 %/21.3 %, 12.8 %/8.7 %, respectively. This research offers the novel insights into the precise construction of tungstate catalytic systems and contributes to the advancement of UV-Vis-NIR full spectrum photocatalytic technology, and lays a foundation for a cleaner and more environmental-friendly future.

Effect of positive emotion intervention during late pregnancy on improving colostrum secretion: a randomised control trial protocol.

INTRODUCTION: Though evidence has revealed the beneficial effects of cognitive improvement interventions on breastfeeding, the effect of psychological interventions has rarely been studied. This study aims to test whether promoting a positive emotion intervention, 'Three Good Things' intervention, during the last trimester of pregnancy can enhance early colostrum secretion and breastfeeding behaviours by modulating the hormones associated with lactation (prolactin and insulin-like growth factor I). We will attempt to promote exclusive breastfeeding by using physiological behavioural measures. METHODS AND ANALYSIS: This study is designed as a randomised controlled trial conducted in the Women's Hospital School of Medicine at Zhejiang University and the Wuyi First People's Hospital. The participants will be randomly divided into two groups using stratified random grouping: the intervention group will receive 'Three Good Things' intervention, while the control group will write about three things that come to mind first. These interventions will be continued from enrolment until the day of delivery. Maternal blood hormone levels will be tested approaching delivery and the following day after birth. Behavioural information about breastfeeding will be collected 1 week afterwards. ETHICS AND DISSEMINATION: The study has been approved by the Ethics Committees of the Women's Hospital School of Medicine at Zhejiang University and the Wuyi First People's Hospital. Results will be disseminated through peer-reviewed journals or international academic conferences. TRIAL REGISTRATION NUMBER: ChiCTR2000038849.

High-Temperature Liquid-Liquid Phase Transition in Glass-Forming Liquid Pd43Ni20Cu27P10.

Liquid-liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT.

Steric Hindrance Governs the Photoinduced Structural Planarization of Cycloparaphenylene Materials.

Cycloparaphenylenes ([n]CPPs) and their derivatives are known for the unique size-dependent photophysical properties, which are largely attributed to the structural planarization-associated exciton localization, attracting substantial research attention. In this work, we show that the steric hindrance between neighboring structural units plays a key role in governing the photoinduced global/local structural planarization and electron-hole distribution features of [n]CPP materials, due to the tunable strength of H···H repulsion between neighboring units via structural modification or C-H distance variation as revealed by density functional theory (DFT) and time-dependent DFT calculations. According to our results, steric hindrance controls the manner and also the extent of excited-state structural planarization, where a weak (strong) steric hindrance favors (hinders) structural planarization upon relaxation in the first excited singlet (S1) state as compared to the ground (S0)-state structure. Depending on the molecular structures, steric hindrance leads to fully delocalized, partially separated, or more localized electron-hole distributions. For example, via H···H repulsion release by manually shortening the C-H distance or by chemical substitution of C-H with N atoms, the modified [10]CPP structures show fully planarized configurations (each dihedral angle can be less than 2°) and entirely delocalized electron-hole distribution upon photorelaxation. This work provides insights into the structural origin of the unusual photophysical properties of [n]CPPs and shows the promise of steric hindrance tuning in accessing diverse excited-state features in [n]CPP materials.

Revealing and Tuning the Photophysics of C=N Containing Photothermal Molecules: Excited State Dynamics Simulations.

Molecular photothermal conversion materials are recently attracting increasing attention for phototherapy applications. Herein we investigate the excitation and de-excitation processes of a photothermal molecule (C1TI) that is among the recently developed class of small-molecule-based photothermal imines with superb photothermal conversion efficiencies (PTCEs) up to 90% and a molecule (M2) that is constructed by replacing the amino group of C1TI with an H atom, via excited-state dynamics simulations based on the time-dependent density functional theory (TD-DFT). The simulations reveal fast (<150 fs of average time) nonradiative decays of the lowest excited singlet (S1) state to a conical intersection (CI) with the ground (S0) state in high yields (C1TI: 93.9% and M2: 87.1%). The fast decays, driven by C=N bond rotation to a perpendicular structural configuration, are found to be barrierless. The slight structural difference between C1TI and M2 leads to drastically different S0-S1 energy surfaces, especially M2 features a relatively much lower CI (0.8 eV in energy) and much more decay energy (1.0 eV) to approach the CI. This work provides insights into the de-excitation mechanisms and the performance tuning of C=N enabled photothermal materials.

Theoretical Prediction and Experimental Validation of the Glass-Forming Ability and Magnetic Properties of Fe-Si-B Metallic Glasses from Atomic Structures.

Developing new soft magnetic amorphous alloys with a low cost and high saturation magnetization (Bs) in a simple alloy system has attracted substantial attention for industrialization and commercialization. Herein, the glass-forming ability (GFA), thermodynamic properties, soft magnetic properties, and atomic structures of Fe80+xSi5-xB15 (x = 0-4) amorphous soft magnetic alloys were investigated by ab initio molecular dynamics (AIMD) simulations and experiments. The pair distribution function (PDF), Voronoi polyhedron (VP), coordination number (CN), and chemical short- range order (CSRO) were analyzed based on the AIMD simulations for elucidating the correlations between the atomic structures with the glass-forming ability and magnetic properties. For the studied compositions, the Fe82Si3B15 amorphous alloy was found to exhibit the strongest solute-solute avoidance effect, the longest Fe-Fe bond, a relatively high partial CN for the Fe-Fe pair, and the most pronounced tendency to form more stable clusters. The simulation results indicated that Fe82Si3B15 was the optimum composition balancing the saturation magnetization and the GFA. This prediction was confirmed by experimental observations. The presented work provides a reference for synthesizing new Fe-Si-B magnetic amorphous alloys.

Revealing the tunability of electronic structures and optical properties of novel SWCNT derivatives, phenine nanotubes.

Single-walled carbon nanotubes (SWCNTs) have evoked great interest for various luminescent applications, but the large emission heterogeneity resulting from the structural complexity of the samples seriously restricts their further development. Herein we theoretically explore the electronic structures and optical properties of phenine nanotubes (pNTs), which are typical luminescent SWCNT derivatives with determined molecular structures that have been synthesized recently (Z. Sun, K. Ikemoto, T. M. Fukunaga, T. Koretsune, R. Arita, S. Sato and H. Isobe, Science, 2019, 363, 151-155; K. Ikemoto, S. Yang, H. Naito, M. Kotani, S. Sato and H. Isobe, Nat. Commun., 2020, 11, 1807). Interestingly, pNTs are found to feature different semiconducting properties to SWCNTs, as indicated by a spatial separation trend in the HOMO and LUMO resulting from periodic structural vacancies. The HOMO-LUMO and optical gaps of pNTs depend inversely on their lengths and diameters, but diameter variation should be an ineffective method for property tuning due to its negligible influence. By contrast, chemical modifications via N doping or hydrogenation highly affect the HOMO-LUMO gaps and their distributions and greatly broaden the light absorption/emission range, and importantly, low-dose hydrogenation is predicted to be a feasible strategy to enhance luminescence. This work, by studying the fundamental photophysical properties of pNTs and making comparisons to SWCNTs, shows the promise of structural vacancy engineering and surface functionalization in acquiring multifunctional tube-like materials.

Risk Factors of Intra-Amniotic Infection Related to Induction with Single-Balloon Catheter: A Case-Control Study.

AIMS: To investigate the risk factors of intra-amniotic infection (IAI) related to induction with single-balloon catheter (SBC). METHODS: A retrospective, case-control study including 58 cases of IAI patients who underwent induction with SBC was conducted in Women's Hospital, School of Medicine, Zhejiang University. For each case, 8 women who delivered during the same month and had no infection after SBC induction were selected for control. RESULTS: Compared with the control group, the IAI group had a higher rate of nulliparity (87.93 vs. 70.69%; p = 0.006), BMI > 30 kg/m2 (29.31 vs. 15.95%; p = 0.011), and amniotic fluid index (AFI) < 8 cm (32.8 vs. 15.1%; p = 0.001). The diameter of cervical dilatation when membranes ruptured in IAI group was smaller than that in the control group (2.0 [1.5] vs. 3.0 [8.0] cm; p < 0.001). Time from start of induction to vaginal delivery was longer than that in the control group (47.0 [19.75] vs. 27.0 [16.0] h; p < 0.001). After logistic regression, the 5 factors associated with IAI for those who underwent SBC induction were nulliparity, BMI > 30 kg/m2, AFI < 8 cm, diameter of cervical dilatation < 3 cm when membranes ruptured and time from start of induction to vaginal delivery of more than 48 h. CONCLUSIONS: Focus on these risk factors could result in earlier prophylaxis so that the incidence of IAI could be reduced.

Clinical characteristics and outcome of twin pregnancies complicated by single intrauterine death.

AIM: To investigate the clinical characteristics and outcome of twin pregnancies complicated by single intrauterine death and how to improve the outcomes of surviving twins. Three thousand three hundred and eighty-four women who delivered twin pregnancies at Women's Hospital, Zhejiang University, School of Medicine were included. Clinical and demographic data on gestational age, etiology, morbidity and mortality for mothers and fetuses were collected. RESULTS: The median gestational age for detecting a single intrauterine death in twin pregnancy was 29 weeks and the average gestational age of pregnancy termination was 32 weeks. At least one complication occurred in 93 of 134 mothers (69.4%). The leading causes of a single intrauterine death were umbilical cord abnormality (21.6%), congenital anomalies (17.9%), twin-twin transfusion syndrome (TTTS) (8.2%) and velamentous placenta (7.4%). Of the 134 cases, in 115 cases the remaining twin survived. The birth weight of the surviving twin was significantly higher in pregnancies that continued for more than 1 week after single intrauterine death compared to that ended within 1 week after intrauterine death. CONCLUSIONS: Extension of gestation for the surviving twin fetus as long as possible in ensuring the health of the surviving twin and mother, will improve the prognosis of surviving twin after a single intrauterine death.

Early second trimester maternal serum markers in the prediction of gestational diabetes mellitus.

AIMS/INTRODUCTION: To determine whether maternal serum markers in the early second trimester are useful for prediction of gestational diabetes mellitus (GDM). MATERIALS AND METHODS: A total of 876 singleton pregnancies were recruited in the present study. Blood samples were collected during 16-20 gestational weeks. GDM women were diagnosed by an oral glucose tolerance test during 24-28 gestational weeks. A total of 56 women with GDM and 73 healthy pregnant women were selected. Maternal serum concentrations of placental protein 13 (PP13), pentraxin 3 (PTX3), soluble fms-like tyrosine kinase-1 (sFlt-1), myostatin and follistatin (FST) were detected at 16-20 weeks' gestation. All of these markers concentrations were expressed as multiples of the medians. The Mann-Whitney U-test was used for comparison of the multiples of the medians of different concentrations of these five serum markers between the GDM group and the control group. Receiver operating characteristic curve analysis was applied to assess the sensitivity and specificity of significant serum markers from a Mann-Whitney U-test comparison. RESULTS: Compared with healthy pregnancies, the serum levels of PP13, PTX3, sFlt-1, myostatin and FST in the early second trimester were significantly increased in patients who had developed GDM late. In screening for GDM by PP13, PTX3, sFlt-1, myostatin and FST, the detection rates were 92.3, 94.9, 94.9, 92.5 and 92.3%, respectively at 80% specificity. PTX3 and sFlt-1 were the most sensitive markers. CONCLUSIONS: Maternal serum markers including PP13, PTX3, sFlt-1, myostatin and FST increase in the early second trimester of women with GDM. These five markers, especially PTX3 and sFlt-1, could have the value of prediction for those patients who would develop GDM in the late second trimester.

Second-trimester maternal serum markers in the prediction of preeclampsia.

AIM: To determine whether late second-trimester maternal serum biomarkers are useful for the prediction of preeclampsia during the third trimester, a case-control study including 33 preeclamptic and 71 healthy pregnancies was conducted. Maternal serum concentrations of placental protein 13 (PP13), pregnancy-associated plasma protein (PAPP-A), pentraxin3 (PTX3), soluble FMS-like tyrosine kinase-1 (sFlt-1), myostatin and follistatin-like-3 (FSLT-3) were measured at 24-28 weeks' gestation. All the concentrations of these markers were compared between the preeclamptic and control groups. Receiver operating characteristic (ROC) curve analysis was applied to assess sensitivity and specificity of serum markers with significant difference. RESULTS: The levels of PP13 and sFlt-1 were significantly increased and FSLT3 was significantly decreased in patients with preeclampsia. However, the concentration of PAPPA, PTX3 and myostatin did not differ significantly. In screening for preeclampsia during the third trimester by PP13, sFlt-1 and FSLT3, the detection rate was 61.3%, 48.1% and 39.1%, respectively, at 80% specificity, and the detection rate increased to 69.8% by combination of these three markers. CONCLUSION: Maternal serum levels of PP13, sFlt-1 and FSLT3 play an important role in predicting late-onset preeclampsia, and the combination of these three markers significantly increases the detection rate for prediction.

Synergistic combination of histone deacetylase inhibitor suberoylanilide hydroxamic acid and oncolytic adenovirus ZD55-TRAIL as a therapy against cervical cancer.

Oncolytic adenoviruses (OA) have been investigated as virotherapeutic agents for the treatment of cervical cancer and thus far results are promising. However, the cytotoxicity of the viruses requires improvement. The present study demonstrated that this can be achieved by combining ZD55-TRAIL, an OA containing the tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) gene, with the histone deacetylase inhibitor suberoylanilide hydroxamic acid (SAHA). It was demonstrated that these agents act synergistically to kill HeLa cells by inducing G2 growth arrest and apoptosis. Notably, in a mouse xenograft model, ZD55-TRAIL/SAHA combination inhibited tumor growth. At the molecular level, it was found that upregulation of IκBα and the p50 and p65 subunits of nuclear factor-κB induced by ZD55-TRAIL, can be abrogated by SAHA treatment. These data strongly suggested that ZD55-TRAIL/SAHA co-treatment may serve as an effective therapeutic strategy against cervical cancer.

PI3K inhibitor LY294002 inhibits activation of the Akt/mTOR pathway induced by an oncolytic adenovirus expressing TRAIL and sensitizes multiple myeloma cells to the oncolytic virus.

Recently, much progress has been achieved in the treatment of multiple myeloma (MM). However, the major challenge of chemotherapeutic drugs is acquired resistance. Oncolytic virotherapies offer promising alternatives; with the possibility of their integration with current therapeutic strategies. In the present study, we assessed the potential of ZD55-TRAIL (an oncolytic adenovirus expressing tumor necrosis factor-related apoptosis-inducing ligand) as an oncolytic agent for MM. Our results clearly indicated that ZD55 armed with TRAIL was more cytotoxic to drug-sensitive as well as drug-resistant MM cell lines, than the virus alone. Furthermore, it was also observed that ZD55-TRAIL induced apoptosis through the activation of the caspase pathway. In particular, ZD55-TRAIL significantly inhibited insulin-like growth factor-1 receptor (IGF-1R) and NFκB. However, IGF did not abrogate ZD55­TRAIL-induced cell death. Combination of ZD55-TRAIL with the PI3K inhibitor LY294002 in RPMI­8226 cells inhibited the virus­mediated activation of mTOR and AKT, thus, promoting cell death. Combined treatment of ZD55-TRAIL and MG132 (a proteasome inhibitor) robustly increased the expression of death receptor 5 (DR5), which enhanced the apoptosis response without significant toxicity to normal liver cells. Collectively, our results suggest that combined treatment of TRAIL-armed oncolytic adenovirus and a PI3K inhibitor or a proteosome inhibitor may serve as a promising therapy for MM.

Serum Follistatin-like-3 was elevated in second trimester of pregnant women who subsequently developed preeclampsia.

OBJECTIVE: To determine whether serum Follistatin-like-3 was enhanced in second trimester of pregnant women who subsequently developed preeclampsia. METHODS: Thirty-nine pregnant women subsequently developed preeclampsia and 73 normal pregnancy women were included. Serum samples taken in 24-28 weeks gestation were used for assay of Follistatin-like-3. RESULTS: Follistatin-like-3 was significantly elevated in preeclampsia group compared with control. However, there was no significant difference of Follistatin-like-3 in women with mild or severe preeclampsia. CONCLUSION: The elevation of Follistatin-like-3 was demonstrated in late second trimester of pregnancy destined to developing preeclampsia, suggesting its causal role in the pathogenesis and prediction of preeclampsia.

Structure analysis methods for crystalline solids and supercooled liquids.

The three most widely used methods for analyzing atomic structures are evaluated by simulating crystalline solids and supercooled liquids. The local order parameter approach due to Volkov [Phys. Rev. E 66, 061401 (2002)] fails in randomly perturbed body-centered-cubic environments, while the pair analysis method behaves as an approximate approach depending on how the neighborhood is defined. As to the Voronoi analysis method, we improve the procedure of Brostow [Phys. Rev. B 57, 13448 (1998)] to eliminate distorted Voronoi faces and edges which originate from thermal vibrations and computational rounding errors. The improved procedure works robustly in face-centered-cubic, body-centered-cubic, and hexagonal close-packed environments. When the pair analysis technique and the Voronoi analysis method are applied to detect the microstructure and its evolution in supercooled liquids, qualitatively consistent results are attained.