Optically Matched Semiconductor Quantum Dots Improve Photophosphorylation Performed by Chloroplasts

A natural–artificial hybrid system was constructed to enhance photophosphorylation. The system comprises chloroplasts modified with optically matched quantum dots (chloroplast–QD) with a large Stokes shift. The QDs possess a unique optical property and transform ultraviolet light into available and highly effective red light for use by chloroplasts. This favorable feature enables photosystem II contained within the hybrid system to split more water and produce more protons than chloroplasts would otherwise do on their own. Consequently, a larger proton gradient is generated and photophosphorylation is improved. At optimal efficiency activity increased by up to 2.3 times compared to pristine chloroplasts. Importantly, the degree of overlap between emission of the QDs and absorption of chloroplasts exerts a strong influence on the photophosphorylation efficiency. The chloroplast–QD hybrid presents an efficient solar energy conversion route, which involves a rational combination of a natural system and an artificial light‐harvesting nanomaterial.     

One‐step electrochemical deposition to achieve superhydrophobic cobalt incorporated amorphous carbon‐based film with self‐cleaning and anti‐corrosion

Exploiting a superhydrophobic surface is very significant due to its excellent water repellency which has many practical applications in various fields. In this work, the cobalt incorporated amorphous carbon‐based (Co/a‐C:H) film was prepared successfully on Si substrate via a simple 1‐step electrochemical deposition where electrochemical deposition technology was using cobalt (II) acetylacetonate methanol solution as electrolyte under high voltage, atmospheric pressure, and low temperature. Surprisingly, the as‐prepared film showed a superior superhydrophobic surface with a water contact angle of 153 ± 1° and a sliding angle of 7.6° without any further modification of low surface energy materials. Especially, the tape adhesive, corrosion resistance, and self‐cleaning tests demonstrated that the as‐prepared carbon‐based film could possess fairly well adhesion, superior anti‐corrosion resistance, and self‐cleaning ability, respectively. It indicated that the superhydrophobic Co/a‐C:H film might have potential promising applications in the field of anti‐fouling, anti‐corrosion, and drag resistance, such as the above‐deck structures on icebreaker vessels, ship hulls, and offshore wind turbine blades.     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

Anti‐inflammatory activities and glycerophospholipids metabolism in KLA‐stimulated RAW 264.7 macrophage cells by diarylheptanoids from the rhizomes of Alpinia officinarum

Alpinia officinarum is used for its anti‐inflammatory activity historically in China. Diarylheptanoids isolated from A. officinarum play important biological roles in the prevention and treatment of inflammatory disorders. Seven diarylheptanoids (1–7) were isolated from A. officinarum. The cell viabilities and anti‐inflammatory activities of diarylheptanoids were evaluated by MTT assay and tumor necrosis factor‐α production in Kdo2‐lipid A‐stimulated RAW 264.7 cells in vitro. The relationships between their anti‐inflammatories and structure‐activities are discussed. The results indicated that compounds 1 and 3–7 had significant anti‐inflammatory activities. The relationships between inflammation and phospholipids metabolism were elucidated by multivariate data analysis. Twenty‐two potential biomarkers were identified in inflammatory group vs. blank group, and 11 potential biomarkers were identified for inflammatory group vs. drug‐treatment groups. Ten common phospholipids were characterized. On the basis of a previous study in our laboratory, we found that phosphatidylethanolamine (18:0/18:1) might be the important glycerophospholipid biomarker in inflammation. In this study, we firstly combined anti‐inflammatory activities and glycerophospholipids changes of traditional Chinese medicine. This work suggests that the anti‐inflammatory activities of diarylheptanoids might be significantly related to glycerophospholipids and could provide a useful database for investigating the anti‐inflammatory effects of traditional Chinese medicine.     

Preparation of dummy template‐imprinted polymers for the rapid extraction of nonsteroidal anti‐inflammatory drugs residues in aquatic environmental samples

A molecularly imprinted polymer was synthesized and applied as a sorbent in the solid‐phase extraction device. The imprinted polymer was characterized by fourier‐transform infrared spectroscopy and scanning electron microscope. The results revealed that imprinted polymer possess sensitive selectivity and reliable adsorption properties for five NSAIDs. The imprinted polymer was successfully applied to the pre‐concentration for five NSAIDs in different water samples prior to UPLC‐MS/MS. In the early studies, several factors were investigated, including pH adjustment, the kind of elution solvent and the volume of elution solvent. Finally, we found that the pH 5 and an aliquot of 2 mL methanol were suitable for the water samples. The limits of detection and limits of quantitation of five nonsteroidal anti‐inflammatory drugs varied from 0.007 to 0.480 μg L⁻¹ and 0.03 to 1.58 μg L⁻¹, respectively. The spiking recoveries of the target analytes were 50.33‐127.64% at the levels of 0.2 μg L⁻¹, 2 μg L⁻¹ and 5 μg L⁻¹. The precision and accuracy of this method showed a great increase compared with traditional solid‐phase extraction. The developed method was successfully applied to extraction and analysis of NSAIDs in different water samples with satisfactory results which could help us better understand their environmental fate and risk to ecological health.     

Synthesis,characterization and biological screening studies of mixed ligand complexes using flavonoids as precursors

Flavonoids are a group of plant phenolics that provide various health benefits through cell signalling pathways and antioxidant effects. In the present study, a new series of mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) were synthesized by incorporating curcumin and quercetin flavonoid precursors. The structural features of the synthesized complexes were explored using elemental analysis, thermogravimetric analysis, UV–visible, infrared, NMR, mass and electron paramagnetic resonance spectral analyses and conductivity measurements. These data support an octahedral geometry of the synthesized complexes. In silico biological activity score for the ligand was predicted using PASS online software. ADMET properties were studied using VLS3D online software. Anti‐inflammatory and antioxidant activities were experimentally validated which prove that theoretical predictions are in agreement with the experimental results. Interestingly the synthesized complexes interact with calf thymus DNA through groove binding mode. Moreover, they have good potential to cleave pUC19 DNA. Minimum inhibitory concentration values of the synthesized complexes reveal that they have better antimicrobial efficacy than the ligands.     

A Zero‐Dimensional Organic Seesaw‐Shaped Tin Bromide with Highly Efficient Strongly Stokes‐Shifted Deep‐Red Emission

The synthesis and characterization is reported of (C₉NH₂₀)₂SnBr₄, a novel organic metal halide hybrid with a zero‐dimensional (0D) structure, in which individual seesaw‐shaped tin (II) bromide anions (SnBr₄^2?) are co‐crystallized with 1‐butyl‐1‐methylpyrrolidinium cations (C₉NH₂₀⁺). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep‐red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr₄^2? species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.     

A non-conforming monolithic finite element method for problems of coupled mechanics

In this study, a Lagrange multiplier technique is developed to solve problems of coupled mechanics and is applied to the case of a Newtonian fluid coupled to a quasi-static hyperelastic solid. Based on theoretical developments in [57], an additional Lagrange multiplier is used to weakly impose displacement/velocity continuity as well as equal, but opposite, force. Through this approach, both mesh conformity and kinematic variable interpolation may be selected independently within each mechanical body, allowing for the selection of grid size and interpolation most appropriate for the underlying physics. In addition, the transfer of mechanical energy in the coupled system is proven to be conserved. The fidelity of the technique for coupled fluid–solid mechanics is demonstrated through a series of numerical experiments which examine the construction of the Lagrange multiplier space, stability of the scheme, and show optimal convergence rates. The benefits of non-conformity in multi-physics problems is also highlighted. Finally, the method is applied to a simplified elliptical model of the cardiac left ventricle.     

Structure‐cytotoxicity relationship for apoptotic inducers organotin(IV) derivatives of mandelic acid and L‐proline and their mixed ligand complexes having enhanced cytotoxicity

Structure‐cytotoxicity relationship of di?/tri‐organotin(IV) derivatives of mandelic acid ( 1 – 4 ), L‐proline ( 5 – 7, 15, 16 ), and mixed ligand complexes of latter with 1,10‐phenanthroline ( 8 – 14 ) investigated on the basis of MTT assay against human cancer cell lines, viz. MCF‐7 (mammary cancer), HepG2 (liver cancer) and PC‐3 (prostate cancer) in vitro indicated that all complexes except methyl‐ and octyl‐ analogues displayed potential cytotoxicity. The most active one is dibutyltin(IV) mandelate ( 2 ) exhibiting IC₅₀ 2.03 ± 0.40, 0.98 ± 0.23 and 3.86 ± 1.68 μM against MCF‐7, HepG2 and PC‐3, respectively, which is ≈ 15 and 2.5 times against MCF‐7, 20 and 5 times against HepG2 and 5 and ≈ 3 times against PC‐3 more cytotoxic than cis‐platin and 5‐fluorouracil, respectively. Diorganotin(IV) derivatives of mandelic acid are more cytotoxic than triorganotin analogues. Organotin(IV) derivatives of L‐proline (except Bu₃Sn(Pro) 16 ) are less cytotoxic than those of mandelic acid but their cytotoxicity is enhanced by complexion with 1,10‐phenanthroline. This may be due to the structural planarity and extended π system of 1,10‐phenanthroline which facilitates their transportation across the cell membrane and enhances the possibility of DNA intercalation over the planar L‐proline ring, and eventually, their DNA binding affinity so as to interfere with the cellular functions of DNA leading to apoptosis. Various biophysical experiments such as DNA fragmentation, acridine orange and comet assays, and flow cytometry assay using annexin V–fluorescein isothiocyanate (FITC) and propidium iodide (PI) have been carried out in order to ascertain their mode of action. The observed results indicated that the major cause of cancer cell death is apoptosis, but a minor role played by necrosis cannot be excluded. It is concluded on the basis of the observed results that the nature and number of organic groups bonded to tin as well as the nature of counter anions play an important role in determining the cytotoxicity of organotin(IV) compounds.