Interfacial Engineering of CdO–CdSe 3D Microarchitectures with in situ Photopolymerized PEDOT for an Enhanced Photovoltaic Performance

In the present work, porous 3D CdO‐microstructured electrode obtained by pyrolysis of 3D CdCO₃ microstructures is self‐sensitized with CdSe using an ion exchange reaction. After sensitization, an interfacial treatment of the CdO–CdSe interface is performed by depositing a thin film of PEDOT using a photoinduce polymerization route. The microstructured electrode before and after interfacial treatment is characterized using field‐emission scanning microscope, energy dispersive X‐ray analyzer, contact angle measurement, UV–Visible absorption spectrophotometer and X‐ray photoelectron spectrometer. After constructing a liquid junction solar cell with a Pt counter electrode, the photovoltaic performance and interfacial charge transfer kinetics across the CdO–CdSe interface before and after PEDOT treatment are investigated. The results exhibit an improved interfacial charge‐transfer resistance after the PEDOT treatment, which leads to enhance the short‐circuit current by 15.81% and the power conversion efficiency by 19.82%.     

Effect of Fluorine Substitution on the Charge Carrier Dynamics of Benzothiadiazole‐Based Solar Cell Materials

The femtosecond transient absorption (TA) characterization of a new benzothiadiazole (BT)‐based donor–acceptor conjugated copolymer, poly[(2,6‐dithieno[3,2‐b:2′,3′‐d]thiophene)‐alt‐(4,7‐di(4‐octyldodecylthiopen‐2‐yl)‐2,1,3‐benzo[c][1,2,5]thiadiazole (PBT), as well as its fluorinated derivatives, PFBT and PDFBT, is carried out. Additionally, bulk heterojunction (BHJ) films consisting of the copolymers and [6,6]‐phenyl‐C₇₁‐butylic acid methyl ester (PC₇₀BM) are examined using TA spectroscopy. Both the singlet excited state dynamics in the copolymers and the charge transfer state dynamics in the BHJs are investigated in terms of fluorination dependency; the fluorinated copolymers exhibit less singlet exciton recombination rate than the fluorine‐free copolymer, and the BHJs including the fluorinated copolymers display slower monomolecular recombination than the fluorine‐free analogue. Furthermore, the excitation‐intensity‐dependent TA dynamics of the copolymers and BHJs is investigated, revealing that, when sufficiently high excitation intensity is used to induce annihilation processes, the fluorinated copolymers and BHJs incorporating the fluorinated copolymers show more rapid TA decay ascribable to morphological enhancement. These TA spectroscopic findings are found to correlate with the device characteristics with respect to fluorinated content in the polymer solar cells. In particular, both the short‐circuit current density and fill factor of BHJ solar cells correspond closely with the fast decay parameters of the BHJ films under high excitation intensity.

     

Detailed Structural Characterization of Sphingolipids via 193 nm Ultraviolet Photodissociation and Ultra High Resolution Tandem Mass Spectrometry

Sphingolipids serve not only as components of cellular membranes but also as bioactive mediators of numerous cellular functions. As the biological activities of these lipids are dependent on their structures, and due to the limitations of conventional ion activation methods employed during tandem mass spectrometry (MS/MS), there is a recognized need for the development of improved structure-specific methods for their comprehensive identification and characterization. Here, positive-ionization mode 193 nm ultraviolet photodissociation (UVPD)-MS/MS has been implemented for the detailed structural characterization of lipid species from a range of sphingolipid classes introduced to the mass spectrometer via electrospray ionization as their lithiated or protonated adducts. These include sphingosine d18:1(4E), dihydrosphingosine (sphinganine) d18:0, sphingadiene d18:2(4E,11Z), the isomeric sphingolipids ceramide d18:1(4E)/18:0 and dihydroceramide d18:0/18:1(9Z), ceramide-1-phosphate d18:1(4Z)/16:0, sphingomyelin d18:1(4E)/18:1(9Z) the glycosphingolipids galactosyl ceramide d18:1(4E)/24:1(15Z) and lactosyl ceramide d18:1(4E)/24:0, and several endogenous lipids present within a porcine brain total lipid extract. In addition to the product ions formed by higher energy collision dissociation (HCD), UVPD is shown to yield a series of novel structurally diagnostic product ions resulting from cleavage of both sphingosine carbon–carbon and acyl chain carbon–carbon double bonds for direct localization of site(s) of unsaturation, as well as via diagnostic cleavages of the sphingosine backbone and N–C amide bond linkages. With activation timescales and dissociation efficiencies similar to those found in conventional MS/MS strategies, this approach is therefore a promising new tool in the arsenal of ion activation techniques toward providing complete structural elucidation in automated, high-throughput lipid analysis workflows.

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Graphical Abstract ?

     

Fixed point approach for weakly asymptotic stability of fractional differential inclusions involving impulsive effects

We prove the global solvability and weakly asymptotic stability for a semilinear fractional differential inclusion subject to impulsive effects by analyzing behavior of its solutions on the half-line. Our analysis is based on a fixed point principle for condensing multi-valued maps, which is employed for solution operator acting on the space of piecewise continuous functions. The obtained results will be applied to a lattice fractional differential system.     

Simple-direct-modules

A right R-module M is called simple-direct-injective if, whenever, A and B are simple submodules of M with A?B, and B?^⊕M, then A?^⊕M. Dually, M is called simple-direct-projective if, whenever, A and B are submodules of M with M∕A?B?^⊕M and B simple, then A?^⊕M. In this paper, we continue our investigation of these classes of modules strengthening many of the established results on the subject. For example, we show that a ring R is uniserial (artinian serial) with J²(R) = 0 iff every simple-direct-projective right R-module is an SSP-module (SIP-module) iff every simple-direct-injective right R-module is an SIP-module (SSP-module).     

An investigation on the lift force of a wing pitching in dynamic stall for a comfort control vessel

On the basis of a comfort control system for ocean vessels, the control forces and moments in the form of lift forces from active wings are of important interest. In an ocean vessel comfort control system, active wings or fins are commonly used and constantly adjust their angles of attack to produce optimal sea-keeping conditions. The unsteady nature of the flow field around a wing, and the behaviour of the generated lift force must be understood in order to optimize the comfort control system. This paper presents experimental data on the flow past a pitching wing, paying particular attention to the lagging effects between the fluid dynamic lift force and the motion of the wing at large angles of attack as a function of peak angle of attack and reduced frequency of oscillation. The range of motion investigated has been chosen according to the applicability of a comfort control wing surface. Numerical data is also included to aid explanation on some of the witnessed phenomena.     

Investigation of Cs(I) adsorption on densely crosslinked poly(sodium methacrylate) from aqueous solutions

In this study, a crosslinked copolymer bearing sodium methacrylate functional groups has been proposed to remove Cs(I) ions from aqueous solutions. For this purpose, the crosslinked copolymer of ethylene glycol dimethacrylate (EGDM) and methacrylic acid (MA) containing 25% MA as weight percentage was synthesized by using benzoyl peroxide (BPO)-N,N-dimethyl aniline initiator system. The available carboxyl groups in copolymer were converted to the groups of sodium methacrylate using 2 N NaOH. The adsorption behavior of cesium ions on the densely crosslinked poly(sodium methacrylate) from aqueous solutions were investigated by the technique of ICP-MS measurements of cesium ions in solutions. Batch adsorption method was used to analyze the Cs(I) adsorption as a function of parameters such as the amount of adsorbent, contact time, pH of solution, initial Cs(I) concentration and temperature. The adsorption data were evaluated by the Freundlich, Langmuir and Dubinin–Radushkevich (D–R) isotherms. The adsorption capacity and free energy change were calculated by using D–R isotherm. The adsorption data obtained from experimental results have been tested by the fractional power, the Elovich, the pseudo-first order and the pseudo-second order kinetic models.     

Novel route to size-controlled Fe-MIL-88B-NH2 metal-organic framework nanocrystals

A new approach for the synthesis of uniform metal-organic framework (MOF) nanocrystals with controlled sizes and aspect ratios has been developed using simultaneously the non-ionic triblock co-polymer F127 and acetic acid as stabilizing and deprotonating agents, respectively. The alkylene oxide segments of the triblock co-polymer can coordinate with metal ions and stabilize MOF nuclei in the early stage of the formation of MOF nanocrystals. Acetic acid can control the deprotonation of carboxylic linkers during the synthesis and, thus, enables the control of the rate of nucleation, leading to the tailoring of the size and aspect ratio (length/width) of nanocrystals. Fe-MIL-88B-NH(2), as an iron-based MOF crystal, was selected as a typical example to illustrate our approach. The results reveal that this approach is used for not only the synthesis of uniform nanocrystals but also the control of the size and aspect ratio of the materials. The size and aspect ratio of nanocrystals increase with an increase in the concentration of acetic acid in the synthetic mixture. The non-ionic triblock co-polymer F127 and acetic acid can be easily removed from the Fe-MIL-88B-NH(2) nanocrystal products by washing with ethanol, and thus, their amine groups are available for practical applications. The approach is expected to synthesize various nanosized carboxylate-based MOF members, such as MIL-53, MIL-89, MIL-100, and MIL-101.     

Comparison between 2-hydroxypropyl-��-cyclodextrin and 2-hydroxypropyl-��-cyclodextrin for inclusion complex formation with danazol

Complexation in solution between danazol and two different cyclodextrins [2-hydroxypropyl-??-cyclodextrin (HP-??-CD) and 2-hydroxypropyl-??-cyclodextrin (HP-??-CD)] was studied using phase solubility analysis, and one- and two-dimensional ¹H-NMR. The increase of danazol solubility in the aqueous cyclodextrin solutions showed a linear relationship (A_L profile). The apparent stability constant, K _1:1, of each complex was calculated and found to be 51.7 × 10³ and 7.3 × 10³ M^?1 for danazol?CHP-??-CD and danazol?CHP-??-CD, respectively. ¹H-NMR spectroscopic analysis of varying ratios of danazol and the different cyclodextrins in a mixture of EtOD?CD₂O confirmed the 1:1 stoichiometry. Cross-peaks, from 2D ROESY ¹H-NMR spectra, between protons of danazol and H3?? and H5??of cyclodextrins, which stay inside the cyclodextrin cavity, proved the formation of an inclusion complex between danazol and the cyclodextrins. For HP-??-CD, the inclusion complex is formed by entrance of the isooxazole and the A rings of danazol in the cyclodextrin cavity. For HP-??-CD, two different inclusion structures may exist simultaneously in solution: one with the isooxazole and A ring in the cavity and the other with the C and D ring inside the cavity. DLS showed that self-aggregation of the CD??s was absent in the danazol HP-??-CD system up to a CD concentration of 10% and in the danazol HP-??-CD system up to a CD concentration of 5%.