Synthesis and self‐assembly of thermosensitive double‐hydrophilic poly(N‐vinylcaprolactam)‐b‐poly(N‐vinyl‐2‐pyrrolidone) diblock copolymers

We report on novel diblock copolymers of poly(N‐vinylcaprolactam) (PVCL) and poly(N‐vinyl‐2‐pyrrolidone) (PVPON) (PVCL‐b‐PVPON) with well‐defined block lengths synthesized by the MADIX/reversible addition‐fragmentation chain transfer (RAFT) process. We show that the lower critical solution temperatures (LCST) of the block copolymers are controllable over the length of PVCL and PVPON segments. All of the diblock copolymers dissolve molecularly in aqueous solutions when the temperature is below the LCST and form spherical micellar or vesicular morphologies when temperature is raised above the LCST. The size of the self‐assembled structures is controlled by the molar ratio of PVCL and PVPON segments. The synthesized homopolymers and diblock copolymers are demonstrated to be nontoxic at 0.1–1 mg mL^?1 concentrations when incubated with HeLa and HEK293 cancer cells for various incubation times and have potential as nanovehicles for drug delivery. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2725–2737     

Enhanced In situ Activity of Peroxidases and Lignification of Root Tissues after Exposure to Non-Thermal Plasma Increases the Resistance of Pea Seedlings

Improving the germination of economically important crops and the condition of young plants is a major challenge currently facing agricultural practice. Pea (Pisum sativum L.) is one of the four most important cultivated legumes, along with groundnut (Arachis hypogaea L.), soybean (Glycine max L.) and beans (Phaseolus vulgaris L.). Due to the high protein content (23–33%), there is an interest in growing this crop as a source of protein for humans and animals. In this study, we focused on the effect of Cold Atmospheric Pressure Plasma (CAPP) on the decontamination and germination of pea seeds, on young seedling growth and production parameters, and on increasing their resistance and mechanical strength. We can state that germination increased by 10 to 25% after plasma treatment, and the most significant decontamination effect was detected when using non-thermal plasma generated in the ambient air (A-variants) and in the nitrogen atmosphere (N-variants). The increased in situ activity of peroxidases (POX) in the cell walls of A-variants and N-variants is also closely related to the increase in the mechanical strength of the cell walls and thus contributes to the higher resistance of these seedlings. This is also illustrated by the differences in lignin deposition among the different variants after CAPP treatment. To our knowledge, this is the first study concerning the influence of CAPP on the lignification of root tissues and on increasing the strength and resistance of plants.

     

Effect of Cold Atmospheric Pressure Plasma on Maize Seeds: Enhancement of Seedlings Growth and Surface Microorganisms Inactivation

Cold atmospheric pressure ambient air plasma generated by Diffuse Coplanar Surface Barrier Discharge (DCSBD) was investigated for inhibition of native microbiota and potentially dangerous pathogens (Aspergillus flavus, Alternaria alternata and Fusarium culmorum) on the maize surface. Moreover, the improvement of germination and growth parameters of maize seeds was evaluated. Maize (Zea mays L.; cv. Ronaldinio), one of the most important cultivated crops worldwide, was selected as the research material. Electrical measurements confirmed the high volume power density (80 W cm^?3) of DCSBD plasma. Non-equilibrium plasma state evaluated using optical emission spectroscopy showed values of vibrational and rotational temperature (2700?±?300) K and (370?±?75) K, respectively. Changes on the plasma treated seeds surface were studied by water contact angle measurement, scanning electron microscope analysis and Fourier transform infrared spectroscopy. A complete devitalisation of native microbiota on the surface of seeds was observed after a short treatment time of 60 s (bacteria) and 180 s (filamentous fungi). The plasma treatment efficiency of artificially contaminated maize seeds was estimated as a reduction of 3.79 log (CFU/g) in F. culmorum after a 60-s plasma treatment, 4.21 log (CFU/g) in A. flavus and 3.22 log (CFU/g) in A. alternata after a 300-s plasma treatment. Moreover, the obtained results show an increase in wettability, resulting in a better water uptake and in an enhancement of growth parameters. The investigated DCSBD plasma source provides significant technical advantages and application potential for seed surface finishing without the use of hazardous chemicals.     

Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging

Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.     

Effect of the immobilisation of DNA aptamers on the detection of thrombin by means of surface plasmon resonance

We report a multichannel surface plasmon resonance (SPR) sensor for detection of thrombin via DNA aptamers immobilized on the SPR sensor surface. A detailed investigation of the effect of the immobilisation method on the interaction between thrombin and DNA aptamers is presented. Three basic approaches to the immobilisation of aptamers on the surface of the SPR sensor are examined: (i) immobilisation based on chemisorption of aptamers modified with SH groups, (ii) immobilisation of biotin-tagged aptamers via previously immobilized avidin, neutravidin or streptavidin molecular linkers, and (iii) immobilisation employing dendrimers as a support layer for subsequent immobilisation of aptamers. A level of nonspecific binding of thrombin to immobilized human serum albumin (HSA) for each of the immobilisation methods is determined. Immobilisation of aptamers by means of the streptavidin–biotin system yields the best results both in terms of sensor specificity and sensitivity.     

Dynamic and controlled rate thermal analysis of hydrozincite and smithsonite

The understanding of the thermal stability of zinc carbonates and the relative stability of hydrous carbonates including hydrozincite and hydromagnesite is extremely important to the sequestration process for the removal of atmospheric CO₂. The hydration-carbonation or hydration-and-carbonation reaction path in the ZnO-CO₂-H₂O system at ambient temperature and atmospheric CO₂ is of environmental significance from the standpoint of carbon balance and the removal of green house gases from the atmosphere. The dynamic thermal analysis of hydrozincite shows a 22.1% mass loss at 247°C. The controlled rate thermal analysis (CRTA) pattern of hydrozincite shows dehydration at 38°C, some dehydroxylation at 170°C and dehydroxylation and decarbonation in a long isothermal step at 190°C. The CRTA pattern of smithsonite shows a long isothermal decomposition with loss of CO₂ at 226°C. CRTA technology offers better resolution and a more detailed interpretation of the decomposition processes of zinc carbonate minerals via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. The CRTA technology offers a mechanism for the study of the thermal decomposition and relative stability of minerals such as hydrozincite and smithsonite.     

XRD,TEM and thermal analysis of yttrium doped boehmite nanofibres and nanosheets

Yttrium doped boehmite nanofibres with varying yttrium content have been prepared at low temperatures using a hydrothermal treatment in the presence of poly(ethylene oxide) surfactant (PEO). The resultant nanofibres were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM images showed the resulting nanostructures are predominantly nanofibres when Y-doping is less than 5%; in contrast Y-rich phases were formed when doping was around 10%. The doped boehmite and the subsequent nanofibres/nanotubes were analyzed by thermogravimetric and controlled rate thermal analysis methods. The boehmite nanofibres produced in this research thermally transform at higher temperatures than boehmite crystals and boehmite platelets. Boehmite nanofibres decompose at higher temperatures than non-hydrothermally treated boehmite.     

The first entry to pyrrolo[2,3-c]quinoline-2,4(3aH,5H)-diones

Wittig olefination of 3-aminoquinoline-2,4(1H,3H)-diones 1 with ethyl (triphenylphosphoranylidene)acetate (Ph₃PCHCO₂Et) afforded (E)-3-amino-4-ethoxycarbonylmethylene-1,2,3,4-tetrahydro-2-quinolones (E)-2 and pyrrolo[2,3-c]quinoline-2,4(3aH,5H)-diones 3. An alternative approach for the synthesis of 3 via 3-bromoacetamidoquinoline-2,4(1H,3H)-diones 7, their corresponding triphenylphosphonium salts 8, and ylides A that undergo intramolecular Wittig reaction, was investigated. Under the applied reaction conditions, the phosphonium salts 8 and ylides A are so unstable that they partly decompose to 3-acetamidoquinoline-2,4(1H,3H)-diones 9 during the synthesis of 3.     

How to generate peak capacity in column liquid chromatography. The Halász nomograms revised

For the separation of complex samples it is necessary to run the analyses on a chromatographic set-up with high peak capacity. The concept of peak capacity is broader than the one of the theoretical plate numbers because it covers both the column characteristics and the run time of the separation. Therefore, a desired peak capacity can be obtained with many combinations of particle diameter, column length, pressure, and analysis time: either with a short column, small-diameter packing, short analysis time, and high pressure; or with less pressure at the expense of a longer column, larger-diameter packing, and longer analysis time. These combinations can be presented in the form of nomograms with the analysis time as x-axis and the peak capacity as y-axis and including particle diameter, column length, and pressure as parameters. The practical limits of the peak capacity are given by the maximum pressure delivered by the pump in use. These considerations are valid for isocratic and gradient separations as well. They are based on a 1982 paper by Halász and G?rlitz and apply the concept of HPLC columns used at their Van Deemter optimum.     

Syntheses of octasubstituted zinc azaphthalocyanines with thiophene or thiophene combined with sulfanyl,amino or imido substituents: Influence of the substituents on photochemical and photophysical properties

Several octasubstituted zinc azaphthalocyanines (ZnAzaPcs) of the tetrapyrazinoporphyrazine type have been synthesized as potential sensitizers for photodynamic therapy (PDT). Octasubstituted complexes, with thiophen-2-yl, thiophen-3-yl or benzo[b]thiophen-3-yl peripheral groups, were synthesized and characterized. Octa(thiophen-2-yl) ZnAzaPc is a better singlet oxygen producer and has a red shifted UV absorption Q-band compared to both thiophen-3-yl and benzo[b]thiophen-3-yl substituted ZnAzaPcs. Thus, the thiophen-2-yl substituent is better suited for our purpose. Unsymmetrically substituted ZnAzaPcs were synthesized by cyclotetramerisations of pyrazine-2,3-dicarbonitriles attached to one thiophen-2-yl group and one alkylsulfanyl, thiomorpholinyl or imide group. Constitutional isomers were detected by NMR spectroscopy for some of these complexes. Compared to unsubstituted ZnAzaPc, red shifted Q-bands were observed for all these complexes, due to the presence of thiophen-2-yl groups. The least promising complexes are ZnAzaPcs with thiomorpholine or imide peripheral substituents, i.e. where the peripheral substituents are attached to the macrocycle through nitrogen atoms. Low singlet oxygen quantum yields (Φ_Δ) and also low fluorescence quantum yields (Φ_F) were observed for these ZnAzaPcs. In the case of combined thiophen-2-yl and alkylsulfanyl substituents, the values of Φ_Δ were the highest and reached values of approximately 0.69.