Evidence-based trends and association between symptom disturbance and physical activity among pregnant women: A longitudinal study.

BACKGROUND: Women usually decrease their physical activity (PA) after becoming pregnant. The change in PA may influence their symptom distress (SD). The changes and correlations between SD and PA throughout pregnancy remain unclear. AIMS: The aims of this study were to describe PA and SD trajectories across all three trimesters and examine their correlations during pregnancy. METHODS: A repeated-measure longitudinal study with convenience sampling at a hospital in Northern Taiwan was performed. Participants were recruited at 8-16 weeks of gestation, and two follow-up visits were performed at 24-28 weeks of gestation (second trimester) and after 36 weeks of gestation (third trimester). A total of 225 participants completed the study. The participants completed the Pregnancy Physical Activity Questionnaire (PPAQ) and Pregnancy-related Symptom Disturbance Scale (PSD), and sociodemographic and prenatal variables were recorded. RESULTS: Throughout pregnancy, SD decreased then increased, showing an overall upward trend, whereas PA showed the opposite pattern, increasing then decreasing, with an overall downward trend. Sedentary activity was positively correlated with both physical and psychological SD during the second and third trimesters. Exceeding the Institute of Medicine's recommendations for gestational weight gain, having childcare support, sport/exercise-type, and light-intensity PA were negatively associated with the physical and psychological SD, while a history of miscarriage and sedentary-intensity PA were positively associated with the physical and psychological SD. LINKING EVIDENCE TO ACTION: While several factors, including light-intensity PA, were found negatively associated with the physical and psychological SD, sedentary-intensity PA were positively associated with the physical and psychological SD, our findings shed light on future intervention strategies to relieve SD and decrease sedentary behavior among pregnant women.

Self-Assembled Monolayers of Bi-Functionalized Porphyrins: A Novel Class of Hole-Layer-Coordinating Perovskites and Indium Tin Oxide in Inverted Solar Cells.

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs.

Thermally Stable D2h Symmetric Donor-π-Donor Porphyrins as Hole-Transporting Materials for Perovskite Solar Cells.

A series of new D2h symmetric porphyrins (MDA4, MTA4, and MDA8) with donor-π-donor structures have been synthesized as the hole-transporting materials for perovskite solar cells (PSCs). The novel porphyrin molecules feature a D2h symmetrically substituted ZnII porphyrin core and two kinds of donor systems (diarylamine (DAA) and triarylamine (TAA)), which can regulate energy level, increase thermal stability, solubility, and hydrophobicity via long alkoxyl chains. PSC devices based on MDA4 as the HTM showed impressive power-conversion efficiency (PCE) of 22.67 % under AM1.5G solar illumination. Notably, the device was sent for certification, and a PCE of 22.19 % was reported, representing the highest PCE from porphyrin-based HTMs. Furthermore, the MDA4-based PSCs showed excellent thermal stability under 60 °C and RH 60 % and preserved 88 % of initial performance after 360 hours. The strategy opens a new avenue for developing efficient and stable porphyrin HTMs for PSCs.

Double Fence Porphyrins that are Compatible with Cobalt(II/III) Electrolyte for High-Efficiency Dye-Sensitized Solar Cells.

A series of new double fence porphyrin dyes bJS1-bJS3, with eight long alkoxyl chains attached to four ß-phenyl groups, have been designed and synthesized. The single fence meso-substituted counterparts mJS1-mJS3 were also prepared as reference dyes. Dyes bJS1-bJS3 and mJS1-mJS3 exhibit power conversion efficiencies of 8.03-10.69 % and 2.33-6.69 %, respectively. Based on photovoltaic studies, the remarkable cell performance of double fence porphyrin sensitizers can be attributed to reduced dye aggregation and a decreased charge-recombination rate. Notably, porphyrins bJS2 and bJS3 exhibit better efficiency than the benchmark YD2-o-C8 (9.83 % in this work), demonstrating that the double fence structure is a promising design strategy for efficient porphyrin sensitizers in high-performance DSSCs.

Porphyrin Dye-Sensitized Zinc Oxide Aggregated Anodes for Use in Solar Cells.

Porphyrin YD2-o-C8-based dyes were employed to sensitize room-temperature (RT) chemical-assembled ZnO aggregated anodes for use in dye-sensitized solar cells (DSSCs). To reduce the acidity of the YD2-o-C8 dye solution, the proton in the carboxyl group of a porphyrin dye was replaced with tetrabuthyl ammonium (TBA⁺) in this work. The short-circuit current density (Jsc) of the YD2-o-C8-TBA-sensitized ZnO DSSCs is higher than that of the YD2-o-C8-sensitized cells, resulting in the improvement of the efficiency of the YD2-o-C8-based ZnO DSSCs. With an appropriate incorporation of chenodeoxycholic acid (CDCA) as coadsorbate, the Jsc and efficiency of the YD2-o-C8-TBA-sensitized ZnO DSSC are enhanced due to the improvement of the incident-photon-to-current efficiency (IPCE) values in the wavelength range of 400-450 nm. Moreover, a considerable increase in Jsc is achieved by the addition of a light scattering layer in the YD2-o-C8-TBA-sensitized ZnO photoanodes. Significant IPCE enhancement in the range 475-600 nm is not attainable by tuning the YD2-o-C8-TBA sensitization processes for the anodes without light scattering layers. Using the RT chemical-assembled ZnO aggregated anode with a light scattering layer, an efficiency of 3.43% was achieved in the YD2-o-C8-TBA-sensitized ZnO DSSC.

Synthesis of Octafluoroporphyrin.

Despite the long list of known fluoroporphyrinoids, the most fundamental 2,3,7,8,12,13,17,18-octafluoroporphyrin (OFP) has not been synthesized until now. It is achieved by condensation of two molecules of tetrafluoro-dipyrrylmethane-2-carboxaldehyde in the presence of magnesium(II) salts. The fluorinated dipyrrylmethane also gives 5,15-bis(pentafluorophenyl)-OFP (F18P) with a reasonable yield. Both Mg/OFP and Zn/F18P in the solid-state reveal an essentially flat structure. The fluoro groups impart as much as a 0.5 V anodic shift for porphyrin ring oxidation/reduction, as well as hypsochromic shifts in the Uv-vis spectra.

Air-stable molecular semiconducting iodosalts for solar cell applications: Cs2SnI6 as a hole conductor.

We introduce a new class of molecular iodosalt compounds for application in next-generation solar cells. Unlike tin-based perovskite compounds CsSnI3 and CH3NH3SnI3, which have Sn in the 2+ oxidation state and must be handled in an inert atmosphere when fabricating solar cells, the Sn in the molecular iodosalt compounds is in the 4+ oxidation state, making them stable in air and moisture. As an example, we demonstrate that, using Cs2SnI6 as a hole transporter, we can successfully fabricate in air a solid-state dye-sensitized solar cell (DSSC) with a mesoporous TiO2 film. Doping Cs2SnI6 with additives helps to reduce the internal device resistance, improving cell efficiency. In this way, a Z907 DSSC delivers 4.7% of energy conversion efficiency. By using a more efficient mixture of porphyrin dyes, an efficiency near 8% with photon confinement has been achieved. This represents a significant step toward the realization of low-cost, stable, lead-free, and environmentally benign next-generation solid-state solar cells.

Molecular engineering of push-pull porphyrin dyes for highly efficient dye-sensitized solar cells: the role of benzene spacers.

Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3-benzothiadiazole (BTD) as a π-conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75% power-conversion efficiency under simulated one-sun illumination (AM1.5G, 100 mW cm(-2)). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power-conversion efficiencies. Time-resolved fluorescence, transient-photocurrent-decay, and transient-photovoltage-decay measurements were employed to determine the electron-injection dynamics and the lifetime of the photogenerated charge carriers.

Effectiveness of corticosteroids and epinephrine use in neonates for the first extubation attempt: A retrospective study.

BACKGROUND: This study aimed to analyze the use of corticosteroids and epinephrine in neonates for the first extubation attempt and compared clinical characteristics of infants with successful and failed extubation events. METHODS: This was a retrospective cohort study conducted at a single level III neonatal intensive care unit in Taiwan. The study included 215 infants born between 2020 and 2021 who had been intubated for more than 48 h before their first extubation attempt. We compared perinatal and peri-extubation characteristics and outcomes between the two groups. Successful extubation was defined as freedom from invasive ventilatory support 72 h after extubation. The relationship between corticosteroids, local epinephrine, and successful extubation was determined using multivariate logistic regression analysis. RESULTS: In the univariate analysis, the failed extubation group received a significantly higher proportion of intravenous dexamethasone (p = 0.006) than the successful extubation group. Furthermore, the failed extubation group had a longer duration of nebulized epinephrine (p = 0.034) and more episodes of local application of epinephrine to the superior larynx (p = 0.003) than the successful extubation group. Multivariate analysis revealed that the absence of lung atelectasis, tachycardia 72 h after extubation, and lower post-extubation PCO2 were the key factors associated with successful extubation. CONCLUSIONS: There were trends toward systemic dexamethasone, local application of epinephrine to the superior larynx, and longer duration of nebulized epinephrine in the reintubation group. However, corticosteroid or local epinephrine use was not significantly associated with successful extubation. Lung atelectasis, elevated levels of carbon dioxide, and tachycardia were identified as risk factors for extubation failure.

The influence of electron injection and charge recombination kinetics on the performance of porphyrin-sensitized solar cells: effects of the 4-tert-butylpyridine additive.

The effects of the 4-tert-butylpyridine (TBP) additive in the electrolyte on photovoltaic performance of two push-pull porphyrin sensitizers (YD12 and YD12CN) were examined. Addition of TBP significantly increased the open-circuit voltage (VOC) for YD12 (from 550 to 729 mV) but it was to a lesser extent for YD12CN (from 544 to 636 mV); adding TBP also had the effect of reducing the short-circuit current density (JSC) slightly for YD12 (from 17.65 to 17.19 mA cm(-2)) but it led to a significant reduction for YD12CN (from 16.45 to 9.78 mA cm(-2)). The resulting power conversion efficiencies of the YD12 devices increase from 6.2% to 8.5% whereas those of the YD12CN devices decrease from 5.8% to 4.5%. Based on measurements of temporally resolved photoelectric transients of the devices and femtosecond fluorescence decays of thin-film samples, the poor performance of the YD12CN device in the presence of TBP can be understood as being due to the enhanced charge recombination, decreased electron injection, and a lesser extent of inhibition of the intermolecular energy transfer.

Porphyrin sensitizers with π-extended pull units for dye-sensitized solar cells.

New π-extended porphyrin dyes YD26-YD29 with long alkoxyl chains at the ortho positions of the meso-phenyls, and meta di-tert-butylphenyl-substituted porphyrins YD12-CN, and YD13-CN were synthesized for dye-sensitized solar cells, and their optical, electrochemical and photovoltaic properties were investigated and compared with those of YD12 and YD13. The absorption spectra of YD26-YD29 showed a slight red shift of Soret bands and blue shift of Q bands as compared to the meta-substituted porphyrins due to the electron-donating effects of dioctyloxy substituents at the ortho-positions of the meso-phenyl rings. Replacement of the carboxyl with a cyanoacrylic acid as the anchoring group results in significant broadening and red shifts of the absorptions, which is due to the strong electronic coupling between the pull unit and the porphyrin ring facilitated by the C≡C triple bond. The electrochemical studies and quantum-chemical calculations (DFT) indicated that the ortho alkoxy-substituted sensitizers exhibit lower oxidation potential, i.e. a higher HOMO energy level, and their HOMO-LUMO gaps are comparable to the meta-substituted analogues. The photovoltaic measurements confirmed that the ortho-octyloxy groups in the two meso-phenyls of YD26 and YD27 play a significant role in preventing dye aggregation thereby enhancing the corresponding short-circuit current density and open-circuit voltage. The power conversion efficiency (η) of YD26 is 8.04%, which is 11% higher than that of YD12, whereas the efficiency of YD27 is 6.03%, which is 135% higher than that of YD13. On the other hand, the poor performance of YD28 and YD29 is due to the floppy structural nature and limited molecular rigidity of the cyanoacrylic acid anchor.

tert-Butylpyridine Coordination with [Cu(dmp)2]2+/+ Redox Couple and Its Connection to the Stability of the Dye-Sensitized Solar Cell.

Cu(I)/(II) complex redox couples in dye-sensitized solar cell (DSSC) are of particular interest because of their low reorganization energy between Cu(I) and Cu(II), which minimizes the potential loss during sensitizer regeneration, thus allowing the open-circuit voltage of the device to go over 1.0 V. However, Cu(I)/(II)-based redox couples are reported to coordinate with 4-tert-butylpyridine (TBP), which is a standard additive in the electrolyte, and this is believed to account for the poor durability of a Cu(I)/(II)-based DSSCs. Despite TBP coordination on Cu(I)/(II) complexes are confirmed in the literature, its detailed mechanism is yet to be directly proven. In addition, how TBP coordination with Cu(I)/(II) complexes affects the stability of the device is never reported. Here, we choose bis(2,9-dimethyl-1,10-phenanthroline) copper(I)/(II) ([Cu(dmp)22+/+]) as the modeling redox couple to investigate its interaction with TBP. It is found that [Cu(dmp)2+] is resistive to TBP coordination but could form three new TBP-coordinated compounds. Moreover, it is also confirmed their electrochemical activity on Pt catalyst and mass transfer capability are both demoted significantly. As a result, serious fill factor loss is observed on the stability trail while short-circuit current density and open-circuit voltage are relatively unaffected. This unique degradation pattern may resemble a feature of Cu(I)/(II)-based redox couple after TBP poisoning.

Nanofibrous cosmetic face mask for transdermal delivery of nano gold: synthesis, characterization, release and zebra fish employed toxicity studies.

This study involves the generation of gold nanoparticles (Au NPs) via a novel natural/non-toxic methodology using tea and orange-peel extracts. These were then embedded into a novel blend composed of a polyethylene oxide and gelatin (PEO-Gel) fibre mat. The scanning electron microscopy results indicated that the addition of both collagen (COL) and ascorbic acid (AA) into the PEO-Gel system (PEO-Gel-AA-COL system) enhances the Au NP incorporation into nanofibres leading to a diameter of 164.60 ± 20.95 and 192.43 ± 39.14 nm in contrast to the spraying observed with the Au PEO-Gel system alone. Releasing studies conducted over 30 min indicated that the PEO-Gel-AA-COL-orange peel Au (OpAu) system accounts for a higher content of Au release than the green tea Au (GtAu) NP system where a maximum release could be attained within 10-30 min depending on the amount of Au NPs that have been incorporated. Moreover, the transdermal diffusion studies conducted using Strat membrane indicated that Au NPs from both formulations (PEO-Gel-AA-COL-GtAu nanofibre, PEO-Gel-AA-COL-OpAu nanofibre) have diffused through the stratum corneum and trapped in the dermis and epidermis indicating its transdermal deliverability. Additionally, 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay revealed that nanofibres have similar radical scavenging activity like AA standard. Toxicity evaluation on a zebra fish embryo model confirmed that both GtAu NPs and OpAu NPs do not induce any teratogenic activity and are safe to be used in the range of 1.0-167 µg ml-1.

A waterwheel-shaped meso-meso-linked porphyrin pentamer.

Wheels on water? A waterwheel-shaped porphyrin pentamer has been synthesized by palladium-catalyzed cross-coupling reactions. The key intermediate is a boronate porphyrin, in which four boronic ester groups are directly attached to the meso-positions.

Novel zinc porphyrin sensitizers for dye-sensitized solar cells: synthesis and spectral, electrochemical, and photovoltaic properties.

Novel meso- or beta-derivatized porphyrins with a carboxyl group have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSCs). The position and nature of a bridge connecting the porphyrin ring and carboxylic acid group show significant influences on the spectral, electrochemical, and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins with a phenylethynyl bridge show that both Soret and Q bands are red-shifted with respect to those of porphyrin 6. This phenomenon is more pronounced for porphyrins 3 and 4, which have a pi-conjugated electron-donating group at the meso position opposite the anchoring group. Upon introduction of an ethynylene group at the meso position, the potential at the first oxidation alters only slightly whereas that for the first reduction is significantly shifted to the positive, thus indicating a decreased HOMO-LUMO gap. Quantum-chemical (DFT) results support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino-substituted porphyrin 5, which exhibits the best photovoltaic performance among all the porphyrins under investigation. From a comparison of the cell performance based on the same TiO(2) films, the devices made of porphyrin 5 coadsorbed with chenodeoxycholic acid (CDCA) on TiO(2) in ratios [5]/[CDCA] = 1:1 and 1:2 have efficiencies of power conversion similar to that of an N3-based DSSC, which makes this green dye a promising candidate for colorful DSSC applications.

Design and characterization of highly efficient porphyrin sensitizers for green see-through dye-sensitized solar cells.

YD12 (eta = 6.7%) is a green sensitizer remarkable for its outstanding cell performance beyond that of N719 (eta = 6.1%) with no added scattering layer; the additional scattering layer assists N719 in promoting the efficiency in the red shoulder of the spectrum, but has only a small effect on the improvement of the cell performance for porphyrins.

The Effect of Nb-Content on the Microstructures and Corrosion Properties of CrFeCoNiNbx High-Entropy Alloys.

This work studied the effect of niobium-content on the microstructures, hardness, and corrosion properties of CrFeCoNiNbx alloys. Results indicated that the microstructures of these alloys changed from granular structures (CrFeCoNi alloy) to the hypereutectic structures (CrFeCoNiNb0.2 and CrFeCoNi0.4 alloys), and then to the hypoeutectic microstructures (CrFeCoNiNb0.6 and CrFeCoNi alloys). The lattice constants of the major two phases in these alloys, fcc and Laves phases (hcp), increased with the increasing of Nb-content because of solid-solution strengthening. The hardness of CrFeCoNiNbx alloys also had the same tendency. Adding niobium would slightly lessen the corrosion resistance of CrFeCoNiNbx alloys in 1 M deaerated sulfuric acid and 1 M deaerated sodium chloride solutions, but the CrFeCoNiNbx alloys still had better corrosion resistance in comparison with commercial 304 stainless steel. In these dual-phased CrFeCoNiNbx alloys, the fcc phase was more severely corroded than the Laves phase after polarization tests in these two solutions.

Cs2SnI6-Encapsulated Multidye-Sensitized All-Solid-State Solar Cells.

The design of a dye-sensitized solar cell (DSSC) based on the simultaneous incorporation of multiple dyes is examined. By investigating the use of the porphyrin-based YD2-o-C8 and YDD6, and the organic chromophore TTAR, which can act as complementary absorbers, we are able to enhance the capture of incoming light across the solar spectrum. This is demonstrated first by using a conventional DSSC architecture with a liquid electrolyte and performed a power conversion efficiency (PCE) of 11.2%, representing an improvement over cells based on each of the independent dyes. Next, we used Cs2SnI6 as an encapsulating layer over the sensitizing molecules to reduce charge leakage across the dye layers and also added to the absorption of longer wavelengths up to one micron. Finally, we fabricated a cell utilizing a Cs2SnI6/succinonitrile solid hole-transport electrolyte and achieved a PCE of ∼8.5%. It is expected that the all solid-state design will go a long way toward improving long-term device stability.

Extended metal-atom chains with an inert second row transition metal: [Ru5(mu5-tpda)4X2] (tpda2- = tripyridyldiamido dianion, X = Cl and NCS).

EMACs (extended metal-atom chains) offer a unique platform for the exploration of metal-metal interactions. There has been significant advances on the synthesis of EMACs, such as lengthening the chains up to 11 metal atoms thus far, integrating naphthyridine moieties for tuning the charge carried at metal centers, and manipulation of metal-metal interactions. However, the metal centers in EMACs hitherto are limited to first row transition metals which are more labile than those relatively inert ones with electrons filled in the 4d and 5d shells. In this Communication, the synthesis, crystallographic, magnetic, and electrical conducting studies of [Ru5(mu5-tpda)4Cl2] and [Ru5(mu5-tpda)4(NCS)2], the first pentanuclear EMACs of second-row transition metal, are reported.

Structure-property relationship for two-photon absorbing multiporphyrins: supramolecular assembly of highly-conjugated multiporphyrinic ladders and prisms.

Two-photon absorption (TPA) phenomena of a series of single-strand as well as supramolecular self-assembled ladders and prisms of highly conjugated ethyne bridged multiporphyrin dimer, trimer, and star shaped pentamer have been investigated. The ligand mediated self-assembled supramolecular structures were characterized by UV-visible spectroscopy and small- and wide-angle X-ray scattering (SAXS/WAXS) analysis. The TPA cross section values of multiporphyrins increase nonlinearly from approximately 100 to approximately 18000 GM with an increased number of porphyrin units and elongated pi-conjugation length by virtue of charge transfer and excited-state cumulenic configurations. The observed opposite TPA behavior between their supramolecular ladder and prism configurations necessitates the importance of interstrand interactions between the multiporphyrinic units and the overall shape of the assembly. Furthermore, the diminished TPA cross section of the pentamer, despite the increased pi-conjugation resulting from duplex formation suggests that destabilizing the essential functional configurations at the cost of elongation of pi-delocalization pathway must cause unfavorable effects. We have also shown that one- and two-photon allowed energy-levels of linear multiporphyrins are nearly isoenergetic and the latter transition originates exclusively from the extent of pi-delocalization within the molecule. The identical TPA maximum position of the trimer and pentamer indicates that the TPA of the pentamer arises only from its basic trimer unit in spite of its extended two-dimensional pi-conjugation pathway involving five porphyrinic units.