Anisotropic Pair Correlations and Structure Factors of Confined Hard-Sphere Fluids: An Experimental and Theoretical Study

We address the fundamental question: how are pair correlations and structure factors of hard-sphere fluids affected by confinement between hard planar walls at close distance? For this purpose, we combine x-ray scattering from colloid-filled nanofluidic channel arrays and first-principles inhomogeneous liquid-state theory within the anisotropic Percus-Yevick approximation. The experimental and theoretical data are in remarkable agreement at the pair-correlation level, providing the first quantitative experimental verification of the theoretically predicted confinement-induced anisotropy of the pair-correlation functions for the fluid. The description of confined fluids at this level provides, in the general case, important insights into the mechanisms of particle-particle interactions in dense fluids under confinement

Multiple Scale Reorganization of Electrostatic Complexes of PolyStyrene Sulfonate and Lysozyme

We report on a SANS investigation into the potential for these structural reorganization of complexes composed of lysozyme and small PSS chains of opposite charge if the physicochemical conditions of the solutions are changed after their formation. Mixtures of solutions of lysozyme and PSS with high matter content and with an introduced charge ratio [-]/[+]intro close to the electrostatic stoichiometry, lead to suspensions that are macroscopically stable. They are composed at local scale of dense globular primary complexes of radius ~ 100 {\AA}; at a higher scale they are organized fractally with a dimension 2.1. We first show that the dilution of the solution of complexes, all other physicochemical parameters remaining constant, induces a macroscopic destabilization of the solutions but does not modify the structure of the complexes at submicronic scales. This suggests that the colloidal stability of the complexes can be explained by the interlocking of the fractal aggregates in a network at high concentration: dilution does not break the local aggregate structure but it does destroy the network. We show, secondly, that the addition of salt does not change the almost frozen inner structure of the cores of the primary complexes, although it does encourage growth of the complexes; these coalesce into larger complexes as salt has partially screened the electrostatic repulsions between two primary complexes. These larger primary complexes remain aggregated with a fractal dimension of 2.1. Thirdly, we show that the addition of PSS chains up to [-]/[+]intro ~ 20, after the formation of the primary complex with a [-]/[+]intro close to 1, only slightly changes the inner structure of the primary complexes. Moreover, in contrast to the synthesis achieved in the one-step mixing procedure where the proteins are unfolded for a range of [-]/[+]intro, the native conformation of the proteins is preserved inside the frozen core

Polypyrrole Nanopipes as a Promising Cathode Material for Li-ion Batteries and Li-ion Capacitors : Two-in-One Approach

Lithium ion capacitor (LIC) is a promising energy storage system that can simultaneously provide high energy with high rate (high power). Generally, LIC is fabricated using capacitive cathode (activated carbon, AC) and insertion-type anode (graphite) with Li-ion based organic electrolyte. However, the limited specific capacities of both anode and cathode materials limit the performance of LIC, in particular energy density. In this context, we have developed "two in one" synthetic approach to engineer both cathode and anode from single precursor for high performance LIC. Firstly, we have engineered a low cost 1D polypyrrole nanopipes (PPy-NPipes), which was utilized as cathode material and delivered a maximum specific capacity of 126 mAh/g, far higher than that of conventional AC cathodes (35 mAh/g). Later, N doped carbon nanopipes (N-CNPipes) was derived from direct carbonization of PPy-NPipes and successfully applied as anode material in LIC. Thus, a full LIC was fabricated using both pseudo-capacitive cathode (PPy-NPipes) and anode (N-CNPipes) materials, respectively. The cell delivered a remarkable specific energy of 107 Wh/kg with maximum specific power of 10 kW/kg and good capacity retention of 93 % over 2000 cycles. Thus, this work provide a new approach of utilization of nanostructured conducting polymers as a promising pseudocapacitive cathode for high performance energy storage systems

Synthetic approach from polypyrrole nanotubes to nitrogen doped pyrolyzed carbon nanotubes for asymmetric supercapacitors

Pseudocapacitive materials are highly capable to achieve high energy density integrated with high power electrostatic capacitive materials. However, finding a suitable electrostatic capacitive material to integrate with pseudocapacitive material in order to achieve high energy density with good rate capability is still a challenge. Herein, we are providing a novel synthetic approach starting from the synthesis of polypyrrole nanotubes (PPy-NTs) and ending up at the carbonization of PPy-NTs to obtain N-doped carbon nanotubes (N-CNTs). With highly porous nature of PPy-NTs and great graphitic texture with copious heteroatom functionalities, N-CNTs significantly promoted the faradic pseudo-capacitors, demonstrating high single-electrode capacitance over 332 F/g and 228 F/g in 1 M HSO aqueous solution. Further, a novel asymmetric supercapacitor with PPy-NTs as positive and N-CNTs as negative electrode has been fabricated. This PPy-NTs//N-CNTs cell effectively provides high operation voltage (1.4 V) and hence high energy density over 28.95 W h/kg (0.41 mW h/cm) with a high power density of 7.75 kW/kg (113 mW/cm) and cyclic stability of 89.98% after 2000 cycles

Heterociklički derivati progesterona s antimikrobnim djelovanjem

The aim of this work was to synthesize steroidal heterocycles and to elucidate the potential role of these compounds as antimicrobial agents. The synthesis of steroidal heterocycles containing the pyrazole, isoxazole, thiazole, pyrane, pyridine, pyridazine, or benzopyrane ring attached to the pregnene nucleus is reported. Progesterone (1) reacts with dimethyl formamide dimethyl acetal to form enamine 2. Heterocyclization of 2 with hydrazines, hydroxylamine, glycine, ethylacetoacetate or cyanomethylene afforded novel steroidal heterocyclic derivatives. The in vitro antimicrobial evaluation showed that all synthesized compounds show activity against the used strains of Gram positive bacteria and fungi.U radu je opisana sinteza steroidnih heterocikličkih spojeva i evaluacija njihovog antimikrobnog djelovanja. Sintetizirani spojevi sadrže pirazol, izoksazol, tiazol, piran, piridin, piridazin ili benzopiran na pregnenskoj jezgri. Progesteron (1) je prvo u reakciji s dimetil formamid dimetil acetalom dao enamin 2. Novi steroidni heterociklički derivati dobiveni su heterociklizacijom spoja 2 s hidrazinima, hidroksilaminom, glicinom, etilacetoaceatom i cijanometilenom. Antimikrobno vrednovanje in vitro pokazalo je da su svi sintetizirani spojevi aktivni protiv testiranih Gram pozitivnih bakterija i gljivica

Ulipristal acetate versus levonorgestrel-releasing intrauterine system for heavy menstrual bleeding (UCON):a randomised controlled phase III trial

BackgroundHeavy menstrual bleeding affects one in four women and negatively impacts quality of life. Ulipristal acetate is prescribed to treat symptoms associated with uterine fibroids. We compared the effectiveness of ulipristal acetate and the levonorgestrel-releasing intrauterine system at reducing the burden of heavy menstrual bleeding, irrespective of the presence of fibroids.MethodsThis randomised, open-label, parallel group phase III trial enrolled women over 18 years with heavy menstrual bleeding from 10 UK hospitals. Participants were centrally randomised, in a 1:1 ratio, to either three, 12-week treatment cycles of 5 mg ulipristal acetate daily, separated by 4-week treatment-free intervals, or a levonorgestrel-releasing intrauterine system. The primary outcome, analysed by intention-to-treat, was quality of life measured by the Menorrhagia Multi-Attribute Scale at 12 months. Secondary outcomes included menstrual bleeding and liver function. The trial is registered with ISRCTN, 20426843.FindingsBetween June 5th, 2015 and February 26th, 2020, 236 women were randomised, either side of a recruitment suspension due to concerns of ulipristal acetate hepatoxicity. Subsequent withdrawal of ulipristal acetate led to early cessation of recruitment but the trial continued in follow-up. The primary outcome substantially improved in both groups, and was 89, (interquartile range [IQR] 65 to 100, n = 53) and 94, (IQR 70 to 100, n = 50; adjusted odds ratio 0.55, 95% confidence interval [CI] 0.26–1.17; p = 0.12) in the ulipristal and levonorgestrel-releasing intrauterine system groups. Rates of amenorrhoea at 12 months were higher in those allocated ulipristal acetate compared to levonorgestrel-releasing intrauterine system (64% versus 25%, adjusted odds ratio 7.12, 95% CI 2.29–22.2). Other outcomes were similar between the two groups and there were no cases of endometrial malignancy or hepatotoxicity due to ulipristal acetate use.InterpretationOur findings suggested that both treatments improved quality of life. Ulipristal was more effective at inducing amenorrhoea. Ulipristal has been demonstrated to be an effective medical therapeutic option but currently its use has restrictions and requires liver function monitoring.FundingUK Medical Research Council and National Institute of Health Research EME Programme (12/206/52)

E-cadherin expression and bromodeoxyuridine incorporation during development of ovarian inclusion cysts in age-matched breeder and incessantly ovulated CD-1 mice

BACKGROUND: Female CD-1/Swiss Webster mice subjected to incessant ovulation for 8 months and 12-month breeder mice both developed ovarian inclusion cysts similar to serous cystadenomas. The majority of cysts appeared to be dilated rete ovarii tubules, but high ovulation number resulted in more cortical inclusion cysts. We hypothesized that comparison of inclusion cyst pathology in animals of the same age, but with differences in total lifetime ovulation number, might allow us to determine distinguishing characteristics of the two types of cyst. METHODS: Ovaries from breeder mice (BR) or females subjected to incessant ovulation (IO) were compared at 6-, 9- and 12-months of age. Ovaries were serially sectioned and cysts characterized with regard to location and histology, E-cadherin immunoreactivity and rates of BrdU incorporation. RESULTS: Inclusion cysts developed with age in BR and IO ovaries. The majority of cysts were connected to the ovarian hilus. Two cortical inclusion cysts were observed in ten IO ovaries and one in ten BR ovaries. Low or no E-cadherin immuno-staining was seen in the OSE of all mice studied. Conversely, strong membrane immuno-staining was observed in rete ovarii epithelial cells. Variable E-cadherin immunoreactivity was seen in cells of hilar inclusion cysts, with strong staining observed in cuboidal ciliated cells and little or no staining in flat epithelial cells. Two of the three cortical cysts contained papillae, which showed E-cadherin immuno-staining at the edge of cells. However hilar and cortical cysts were not distinguishable by morphology, cell type or E-cadherin immunoreactivity. BrdU incorporation in cyst cells (1.4% [95% CI: 1.0 to 2.1]) was greater than in OSE (0.7% [95% CI: 0.4 to 1.2]) and very few BrdU-labeled cells were observed in rete ovarii at any age. Incessant ovulation significantly increased BrdU incorporation in OSE of older animals. CONCLUSION: These experiments confirm ovarian inclusion cysts develop with age in the CD-1 mouse strain, irrespective of total ovulation burden. We conclude longer periods of incessant ovulation do not lead to significant changes in inclusion cyst formation or steroidogenesis in CD-1 mice and inclusion cyst type can not be distinguished by morphology, cell proliferation rate or E-cadherin immunoreactivity

Electrolyte ions-matching hierarchically porous biochar electrodes with an extended potential window for next-generation supercapacitors

Engineering high-performance carbonaceous electrode materials from earth-abundant biomass has attracted substantial attention for its applicability in next-generation supercapacitors (SCs). However, these materials exhibit low specific energy due to the dominance of mesopores and a limited potential window. To overcome these shortcomings, herein, we synthesize Miscanthus sinensis (silver grass)-derived hierarchically-porous activated carbons (SHACs) via pyrolysis, carbonization, and KOH activation. We test the SHAC electrodes with different electrolytes, showing how an electrolyte–electrode pair can be tuned to boost energy and power densities. Owing to the synergetic effect of the size-balanced proportion of micropores matched with the size of electrolyte ions, in KOH electrolyte, the SHAC electrode produces a high specific capacitance (592 F g/1) while, simultaneously, providing faster charging compared to Na2SO4 electrolyte. We rationalize these findings with molecular dynamics simulations, demonstrating the avoidance of power-density trade-off, typical for microporous SCs. Upon adding K3Fe(CN)6 redox species to KOH electrolyte (hybrid electrolyte), capacitance increases 2.53 fold (380 to 963 F g/1 at 5 A g/1) due to the synergy of capacitive and faradaic energy storage mechanisms. In the hybrid electrolyte, a SHAC electrode-embedded symmetric SC (SSC) offers a high cycling stability (97%) with 1.6 V wide operational voltage and permits energy storage and power density higher than those reported so far for aqueous electrolyte-based SSCs and asymmetric SCs. In addition, these SSCs provide long-lasting operational capabilities that are useful for driving various portable electronic devices. The obtained results demonstrate a feasible methodology to utilize the maximum available surface area of carbonaceous materials for electrochemical energy storage applications.This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (2021R1F1A1064174, 2021R1A5A6002853 and 2022R1A2C2008968). S. K. acknowledges the financial support by NCN grant no. 2021/40/Q/ST4/00160. This work was also supported by the Technology Innovation Program (RS-2022-00156080, Development of electrical double layer capacitors for power supplement of hydrogen forklift) funded by the Ministry of Trade, Industry and Energy, and the Natural Science Foundation of Inner Mongolia (2023SHZR1182)

Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel

This work is licensed under a Creative Commons Attribution 4.0 International License.The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0–1V and 0–2V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92Fg−1, about 2-fold of higher energy density (41.8Wh kg−1) than symmetric SC and excellent mechanical flexibility. Furthermore, the “real-life” demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC.One of the authors GSG is thankful to DAE-BRNS, BARC Mumbai, India for the award of, “JRF”. Authors are also grateful to Department of Science and Technology (DST) for financial support through PURSE and FIST & University Grant Commission (UGC) India through DSA-I scheme. Authors are also thankful to UGC-DAE CSR, Indore centre for providing Raman facility. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295).Peer Reviewe