Metal complex as p-type dopant-based organic spiro-OMeTAD hole-transporting material for free-Li-TFSI perovskite solar cells.

Lithium bis(fluorosulfonyl)imide (Li-TFSI) is an efficient p-dopant that has been used to enhance the conductivity of perovskite solar cells (PSCs). However, the performance of the corresponding devices is still not satisfactory due to the impact of Li-TFSI on the fill factor and the short-circuit current density of these PSCs. Herein, a new Mn complex [(Mn(Me-tpen)(ClO4)2-)]2+ was introduced as a p-type dopant into spiro-OMeTAD and was successfully applied as a hole transport material (HTM) for PSCs. Analytical studies used for device characterization included scanning electron microscopy, UV-Vis spectroscopy, current-voltage (IV) characteristics, incident photon to current efficiency, power conversion efficiency (PCE), and electrochemical impedance spectroscopy. The UV-Vis spectra displayed oxidation in the HTM by the addition of a dopant. Moreover, the movement of electrons from the higher orbital of the spiro-OMeTAD to the dopant stimulates the generation of the hole carriers in the HTM, enhancing its conductivity with outstanding long-term stability under mild conditions in a humid (RH ∼ 30%) environment. The incorporation of the Mn complex into the composite improved the material's properties and the stability of the fabricated devices. The Mn complex as a p-type dopant for spiro-OMeTAD exhibits a perceptible PCE of 16.39% with an enhanced conductivity of 98.13%. This finding may pave a rational way for developing efficient and stable PSCs in real environments.

Enhanced adsorptive removal of rifampicin and tigecycline from single system using nano-ceria decorated biochar of mango seed kernel.

Pharmaceutically active compounds (PhACs) represent an emerging class of contaminants. With a potential to negatively impact human health and the ecosystem, existence of pharmaceuticals in the aquatic systems is becoming a worrying concern. Antibiotics is a major class of PhACs and their existence in wastewater signifies a health risk on the long run. With the purpose of competently removing antibiotics from wastewater, cost-effective, and copiously available waste-derived adsorbents were structured. In this study, mango seeds kernel (MSK), both as a pristine biochar (Py-MSK) and as a nano-ceria-laden (Ce-Py-MSK) were applied for the remediation of rifampicin (RIFM) and tigecycline (TIGC). To save time and resources, adsorption experiments were managed using a multivariate-based scheme executing the fractional factorial design (FrFD). Percentage removal (%R) of both antibiotics was exploited in terms of four variables: pH, adsorbent dosage, initial drug concentration, and contact time. Preliminary experiments showed that Ce-Py-MSK has higher adsorption efficiency for both RIFM and TIGC compared to Py-MSK. The %R was 92.36% for RIFM compared to 90.13% for TIGC. With the purpose of comprehending the adsorption process, structural elucidation of both sorbents was performed using FT-IR, SEM, TEM, EDX, and XRD analyses which confirmed the decoration of the adsorbent surface with the nano-ceria. BET analysis revealed that Ce-Py-MSK has a higher surface area (33.83 m2/g) contrasted to the Py-MSK (24.72 m2/g). Isotherm parameters revealed that Freundlich model best fit Ce-Py-MSK-drug interactions. A maximum adsorption capacity (qm) of 102.25 and 49.28 mg/g was attained for RIFM and TIGC, respectively. Adsorption kinetics for both drugs conformed well with both pseudo-second order (PSO) and Elovich models. This study, therefore, has established the suitability of Ce-Py-MSK as a green, sustainable, cost-effective, selective, and efficient adsorbent for the treatment of pharmaceutical wastewater.

Biodegradable Preformed Particle Gel (PPG) Made of Natural Chitosan Material for Water Shut-Off Application.

Oil and gas extraction frequently produces substantial volumes of produced water, leading to several mechanical and environmental issues. Several methods have been applied over decades, including chemical processes such as in-situ crosslinked polymer gel and preformed particle gel, which are the most effective nowadays. This study developed a green and biodegradable PPG made of PAM and chitosan as a blocking agent for water shutoff, which will contribute to combating the toxicity of several commercially used PPGs. The applicability of chitosan to act as a crosslinker has been confirmed by FTIR spectroscopy and observed by scanning electron microscopy. Extensive swelling capacity measurements and rheological experiments were performed to examine the optimal formulation of PAM/Cs based on several PAM and chitosan concentrations and the effects of typical reservoir conditions, such as salinity, temperature, and pH. The optimum concentrations of PAM with 0.5 wt% chitosan were between 5-9 wt%, while the optimum chitosan amount with 6.5 wt% PAM was in the 0.25-0.5 wt% range, as these concentrations can produce PPGs with high swellability and sufficient strength. The swelling capacity of PAM/Cs is lower in high saline water (HSW) with a TDS of 67.2976 g/L compared with fresh water, which is related to the osmotic pressure gradient between the swelling medium and the PPG. The swelling capacity in freshwater was up to 80.37 g/g, while it is 18.73 g/g in HSW. The storage moduli were higher in HSW than freshwater, with ranges of 1695-5000 Pa and 2053-5989 Pa, respectively. The storage modulus of PAM/Cs samples was higher in a neutral medium (pH = 6), where the fluctuation behavior in different pH conditions is related to electrostatic repulsions and hydrogen bond formation. The increase in swelling capacity caused by the progressive increment in temperature is associated with the amide group's hydrolysis to carboxylate groups. The sizes of the swollen particles are controllable since they are designed to be 0.63-1.62 mm in DIW and 0.86-1.00 mm in HSW. PAM/Cs showed promising swelling and rheological characteristics while demonstrating long-term thermal and hydrolytic stability in high-temperature and high-salinity conditions.

Electrochemically stable tunnel-type α-MnO2-based cathode materials for rechargeable aqueous zinc-ion batteries.

The purpose of this study is the synthesis of α-MnO2-based cathode materials for rechargeable aqueous zinc ion batteries by hydrothermal method using KMnO4 and MnSO4 as starting materials. The aim is to improve the understanding of Zn2+ insertion/de-insertion mechanisms. The as-prepared solid compounds were characterized by spectroscopy and microscopy techniques. X-ray diffraction showed that the hydrothermal reaction forms α-MnO2 and Ce4+-inserted MnO2 structures. Raman spectroscopy confirmed the formation of α-MnO2 with hexagonal MnO2 and Ce-MnO2 structures. Scanning electron microscopy (SEM) confirmed the formation of nanostructured MnO2 (nanofibers) and Ce-MnO2 (nanorods). The electrochemical performance of MnO2 was evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) tests in half-cells. CV results showed the reversible insertion/de-insertion of Zn2+ ions in MnO2 and Ce-MnO2. GCD cycling tests of MnO2 and Ce-MnO2 at 2500 mA/g demonstrated an impressive electrochemical performance, excellent cycling stability throughout 500 cycles, and high rate capability. The excellent electrochemical performance and the good cycling stability of MnO2 and Ce-MnO2 nanostructures by simple method makes them promising cathode materials for aqueous rechargeable zinc-ion batteries.

Computational Screening of Potential Inhibitors of Desulfobacter postgatei for Pyrite Scale Prevention in Oil and Gas Wells.

Sulfate-reducing bacteria (SRB), such as Desulfobacter postgatei are found in oil wells. However, they lead to the release of hydrogen sulfide. This in turn leads to the iron sulfide scale formation (pyrite). ATP sulfurylase is an enzyme present in SRB, which catalyzes the formation of adenylyl sulfate (APS) and inorganic pyrophosphatase (PPi) from ATP and sulfate. This reaction is the first among many in hydrogen sulfide production by D. postgatei . Consensus scoring using molecular docking and machine learning was used to identify three potential inhibitors of ATP sulfurylase from a database of about 40 million compounds. These selected hits ((S,E)-1-(4-methoxyphenyl)-3-(9-((m-tolylimino)methyl)-9,10-dihydroanthracen-9-yl)pyrrolidine-2,5-dione; methyl 2-[[(1S)-5-cyano-2-imino-1-(4-phenylthiazol-2-yl)-3-azaspiro[5.5]undec-4-en-4-yl]sulfanyl]acetate; and (4S)-4-(3-chloro-4-hydroxy-phenyl)-1-(6-hydroxypyridazin-3-yl)-3-methyl-4,5-dihydropyrazolo[3,4-b]pyridin-6-ol), known as A, B, and C, respectively) all had good binding affinities with ATP sulfurylase and were further analyzed for their toxicological properties. Compound A had the highest docking score. However, based on the physicochemical and toxicological properties, only compound C was predicted to be both safe and effective as a potential inhibitor of ATP sulfurylase, hence the preferred choice. The molecular interactions of compound C revealed favorable interactions with the following residues: LEU213, ASP308, ARG307, TRP347, LEU224, GLN212, MET211, and HIS309.

Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.

Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L(2)), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [Fe(II)(CH3CN)(L)](2+) (L = L(1) (1); L(2) (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [Fe(IV)(O)(L)](2+) (L = L(1) (3); L(2) (4)), which were characterized by UV-vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L(1)) and 2.5 h (L = L(2)). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([Fe(IV)(O)(N4Py)](2+)), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [Fe(IV)(O)(L(2))](2+) exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C-H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.

A novel platinum complex of the histone deacetylase inhibitor belinostat: rational design, development and in vitro cytotoxicity.

The successful design and synthesis of a novel Pt complex of the histone deacteylase inhibitor belinostat are reported. Molecular modelling assisted in the identification of a suitable malonate derivative of belinostat (mal-p-Bel) for complexation to platinum. Reaction of [Pt(NH3)2(H2O)2](NO3)2 with the disodium salt of mal-p-Bel gave cis-[Pt(NH3)2(mal-p-Bel-2H)] (where -2H indicates that mal-p-Bel is doubly deprotonated) in excellent yield. An in vitro cytotoxicity study revealed that cis-[Pt(NH3)2(mal-p-Bel-2H)] possesses (i) considerable cytotoxicity against reported ovarian cancer cell lines, (ii) enhanced cytotoxicity relative to the previously reported Pt histone deacetylase inhibitor conjugate, cis-[Pt(II)(NH3)2(malSAHA-2H)] and (iii) favourable cyto-selective properties as compared to cisplatin and belinostat.

A novel dizinc bridged hydroxamate model for hydroxamate inhibited zinc hydrolases.

Reaction of Zn(OAc)(2).2H2O with tmen leads to the formation of [Zn(tmen)(OAc)2] (I) which reacts with benzohydroxamic acid to form Zn(BA)2.H2O (II) and the novel dizinc hydroxamate bridged complex [Zn2(mu-OAc)2(OAc)(mu-BA)(tmen)] (III), which may also be prepared by self-assembly and whose structure closely mimics that of the native hydroxamate inhibited Aeromonas proteolytica aminopeptidase.