Ca- and Cl-containing nanoparticles are common in atmosphere, originating for example from desert dust and sea water. The properties and effects on atmospheric processes of these aerosol particles depend onthe relative humidity (RH) as they are often both hygroscopic and deliquescent. We present here a study of surface structure of free-flying CaCl2 nanoparticles (CaCl2-NPs) in the 100 nm size regime prepared at different humidity levels (RH: 11–85%). We also created mixed nanoparticles by aerosolizing a solution ofCaCl2 and phenylalanine (Phe), which is a hydrophobic amino acid present in atmosphere. Information of hydration state of CaCl2-NPs and production of mixed CaCl2 + Phe nanoparticles was obtained using soft X-ray absorption spectroscopy (XAS) at Ca 2p, Cl 2p, C 1s, and O 1s edges. We also report Ca 2p andCl 2p X-ray absorption spectra of an aqueous CaCl2 solution. The O 1s X-ray absorption spectra measured from hydrated CaCl2-NPs resemble liquid-like water spectrum, which is heavily influenced by the presence of ions. Core level spectra of Ca2+ and Cl- ions do not show a clear dependence of % RH, indicating that the first coordination shell remains similar in all measured hydrated CaCl2-NPs, but they differ from aqueous solution and solid CaCl2.
High-efficiency photocatalysts are crucial for the removal of organic pollutants and environmental sustainability. In the present work, we report on a new low-temperature hydrothermal chemical method, assisted by ultrasonication, to synthesize disruptive plasmonic ZnO/graphene/Ag/AgI nanocomposites for solar-driven photocatalysis. The plasmonic nanocomposites were investigated by a wide range of characterization techniques, confirming successful formation of photocatalysts with excellent degradation efficiency. Using Congo red as a model dye molecule, our experimental results demonstrated a photocatalytic reactivity exceeding 90% efficiency after one hour simulated solar irradiation. The significantly enhanced degradation efficiency is attributed to improved electronic properties of the nanocomposites by hybridization of the graphene and to the addition of Ag/AgI which generates a strong surface plasmon resonance effect in the metallic silver further improving the photocatalytic activity and stability under solar irradiation. Scavenger experiments suggest that superoxide and hydroxyl radicals are responsible for the photodegradation of Congo red. Our findings are important for the fundamental understanding of the photocatalytic mechanism of ZnO/graphene/Ag/AgI nanocomposites and can lead to further development of novel efficient photocatalyst materials. © 2019 Elsevier B.V.
High-efficiency photocatalysts are crucial for the removal of organic pollutants and environmental sustainability. In the present work, we report on a new low-temperature hydrothermal chemical method, assisted by ultrasonication, to synthesize disruptive plasmonic ZnO/graphene/Ag/AgI nanocomposites for solar-driven photocatalysis. The plasmonic nanocomposites were investigated by a wide range of characterization techniques, confirming successful formation of photocatalysts with excellent degradation efficiency. Using Congo red as a model dye molecule, our experimental results demonstrated a photocatalytic reactivity exceeding 90% efficiency after one hour simulated solar irradiation. The significantly enhanced degradation efficiency is attributed to improved electronic properties of the nanocomposites by hybridization of the graphene and to the addition of Ag/AgI which generates a strong surface plasmon resonance effect in the metallic silver further improving the photocatalytic activity and stability under solar irradiation. Scavenger experiments suggest that superoxide and hydroxyl radicals are responsible for the photodegradation of Congo red. Our findings are important for the fundamental understanding of the photocatalytic mechanism of ZnO/graphene/Ag/AgI nanocomposites and can lead to further development of novel efficient photocatalyst materials.
Biobased graphene oxide quantum dots (GOQD) were derived from cellulose via carbon nanospheres (CN) as intermediate products. Solid CN were synthesized from cellulose through microwave-assisted hydrothermal degradation of alpha-cellulose with H2SO4 as a catalyst at 160 degrees C. The obtained CN were further utilized for the synthesis of GOQD by a two-step reaction including 30 minutes of sonication followed by heating at 90 degrees C under O-rich acidic conditions (HNO3). This process broke down the 3D CN to 2D GOQD. The size of the synthesized GOQD was controlled by the heating time, reaching a dot diameter of 3.3 nm and 1.2 nm after 30 and 60 minutes of heating, respectively. The synthesis process and products were characterized by multiple analytical techniques including FTIR, TGA, SEM, TEM, XPS, XRD, BET, DLS and AFM. Interesting optical properties in aqueous solutions were demonstrated by UV/Vis and fluorescence spectroscopy. Finally we demonstrated that corresponding GOQD can be synthesized from waste paper. This production route thus uses renewable and cheap starting materials and relatively mild synthesis procedures leads to instant nanometric production of 2D dots. In addition it enables recycling of low quality waste to value-added products.
There are many challenges associated with the fabrication of efficient, inexpensive, durable and very stable nonprecious metal catalysts for the hydrogen evolution reaction (HER). In this study, we have designed a facile strategy by tailoring the concentration of precursors to successfully obtain nickel-cobalt bimetallic sulfide (NiCo2S4) using a simple hydrothermal method. The morphology of the newly prepared NiCo(2)S(4)comprised a mixture of microparticles and nanorods, which were few microns in dimension. The crystallinity of the composite sample was found to be excellent with a cubic phase. The sample that contained a higher amount of cobalt compared to nickel and produced single-phase NiCo(2)S(4)exhibited considerably improved HER performance. The variation in the salt precursor concentration during the synthesis of a material is a simple methodology to produce a scalable platinum-free catalyst for HER. The advantageous features of the multiple active sites of cobalt in the CN-21 sample as compared to that for pristine CoS and NiS laid the foundation for the provision of abundant active edges for HER. The composite sample produced a current density of 10 mA cm(-2)at an overpotential of 345 mV. Also, it exhibited a Tafel value of 60 mV dec(-1), which predominantly ensured rapid charge transfer kinetics during HER. CN-21 was highly durable and stable for 30 hours. Electrochemical impedance spectroscopy showed that the charge transfer resistance was 21.88 ohms, which further validated the HER polarization curves and Tafel results. CN-21 exhibited a double layer capacitance of 4.69 mu F cm(-2)and a significant electrochemically active surface area of 134.0 cm(2), which again supported the robust efficiency for HER. The obtained results reveal that our developed NiCo(2)S(4)catalyst has a high density of active edges, and it is a non-noble metal catalyst for the hydrogen evolution reaction. The present findings provide an alternative strategy and an active nonprecious material for the development of energy-related applications.
The shells of linguloid brachiopods such as Lingula and Discinisca are inorganic–organic nanocomposites with a mineral phase of calcium phosphate (Ca-phosphate). Collagen, the main extracellular matrix in Ca-phosphatic vertebrate skeletons, has not previously been clearly resolved at the molecular level in organophosphatic brachiopods. Here, modern and recently-alive linguliform brachiopod shells of Lingula and Discinisca have been studied by microRaman spectroscopy, Fourier transform infrared spectroscopy, field emission gun scanning electron microscopy, and thermal gravimetric analysis. For the first time, biomineralized collagen matrix and Ca-phosphate components were simultaneously identified, showing that the collagen matrix is an important moiety in organophosphatic brachiopod shells, in addition to prevalent chitin. Stabilized nanosized apatitic biominerals (up to ∼50 nm) permeate the framework of organic fibrils. There is a ∼2.5-fold higher wt% of carbonate (CO32−) in Lingula versus Discinisca shells. Both microRaman spectroscopy and infrared spectra show transient amorphous Ca-phosphate and octacalcium phosphate components. For the first time, trivalent moieties at ∼1660 cm−1 and divalent moieties at ∼1690 cm−1 in the amide I spectral region were identified. These are related to collagen cross-links that are abundant in mineralized tissues, and could be important features in the biostructural and mechanical properties of Ca-phosphate shell biominerals. This work provides a critical new understanding of organophosphatic brachiopod shells, which are some of the earliest examples of biomineralization in still-living animals that appeared in the Cambrian radiation.
This study reports the potential of TEMPO-oxidized cellulose nanofibrils (T-CNF)/poly(vinyl alcohol) (PVA) coatings to develop functionalized membranes in the ultrafiltration regime with outstanding antifouling performance and dimensional/pH stability. PVA acts as an anchoring phase interacting with the polyethersulfone (PES) substrate and stabilizing for the hygroscopic T-CNF via crosslinking. The T-CNF/PVA coated PES membranes showed a nano-textured surface, a change in the surface charge, and improved mechanical properties compared to the original PES substrate. A low reduction (4%) in permeance was observed for the coated membranes, attributable to the nanometric coating thickness, surface charge, and hydrophilic nature of the coated layer. The coated membranes exhibited charge specific adsorption driven by electrostatic interaction combined with rejection due to size exclusion (MWCO 530 kDa that correspond to a size of similar to 35-40 nm). Furthermore, a significant reduction in organic fouling and biofouling was found for T-CNF/PVA coated membranes when exposed to BSA and E. coli. The results demonstrate the potential of simple modifications using nanocellulose to manipulate the pore structure and surface chemistry of commercially available membranes without compromising on permeability and mechanical stability.
Concerns regarding poor aqueous solubility, high toxicity and lack of specificity impede the translation of many hydrophobic anticancer agents into safe and effective anticancer drugs. The application of colloidal drug delivery systems, and in particular the use of lipid-based nanocarriers, has been identified as a promising means to overcome these issues. PEG-stabilized lipid nanodisks (lipodisks) have lately emerged as a novel type of biocompatible, nontoxic and adaptable drug nanocarrier. In this study we have explored the potential of lipodisks as a platform for formulation and tumour targeted delivery of hydrophobic anticancer agents. Using curcumin as a model compound, we show that lipodisks can be loaded with substantial amounts of hydrophobic drugs (curcumin/lipid molar ratio 0.15). We demonstrate moreover that by deliberate choice of preparation protocols the lipodisks can be provided with relevant amounts of targeting proteins, such as epidermal growth factor (EGF). Data from in vitro cell studies verify that such EGF-decorated curcumin-loaded lipodisks are capable of EGF-receptor specific targeting of human A-431 tumour cells, and strongly suggest that the interaction between the lipodisks and the tumour cells results in receptor-mediated internalization of the disks and their cargo.
Since its discovery, graphene and its oxidized form, graphene oxide (GO), have attracted interest in a wide range of technical applications. Concerns about their potential toxicity calls for scrutinized studies, but hitherto conflicting results have been reported which partly may be due to variations of synthesis and exposure procedures. Here we report on the attachment and toxicity of contamination-free graphene oxide nanoparticles (GONP) in living lung epithelial cells. The synthesis of chemically pure GONP was made by an improvement of the Hummer's method based on graphene exfoliated from graphite using high-intensity ultrasonication, resulting in two dimensional sheets with a lateral dimension in the range 200 nm to 3 mu m and thickness of 0.9 nm. Confocal Raman spectroscopy combined with multivariate analysis was used to study the interaction of GONP and living cells. It is shown that overlapping Raman bands due to GONPs and biomolecules in the cells can clearly be separated with this approach. Orthogonal partial least squares discriminant analysis was used to compare spectral data collected from cells exposed to GONP with spectral data collected from non-exposed control cells, and spectral data from cells exposed to a surfactant known to induce apoptosis. Our analyses show that GONP readily attach to the cells, forming sheets which cover a large fraction of the cell surfaces, and induce small chemical changes. In particular, chemical modifications of proteins and lipids in lung epithelial cells are inferred. GONPs do not, however, decrease cell viability. In contrast, enhanced cell proliferation is observed. Our results shed new light on the interactions of GO, and in contrast to some previous reports, suggest that GO is not toxic. The hyperspectral Raman spectroscopy analysis employed here should be applicable for other fields in nanomedicine as a label-free non-perturbing analytical method.
Metal-assisted chemical etching (MACE) reaction parameters were investigated for the fabrication of specially designed silicon-based X-ray zone plate nanostructures using a gold catalyst pattern and etching solutions composed of HF and H2O2. Etching depth, zone verticality and zone roughness were studied as a function of etching solution composition, temperature and processing time. Homogeneous, vertical etching with increasing depth is observed at increasing H2O2 concentrations and elevated processing temperatures, implying a balance in the hole injection and silica dissolution kinetics at the gold-silicon interface. The etching depth decreases and zone roughness increases at the highest investigated H2O2 concentration and temperature. Possible reasons for these observations are discussed based on reaction chemistry and zone plate design. Optimum MACE conditions are found at HFH2O2 concentrations of 4.7 M:0.68 M and room temperature with an etching rate of ≈0.7 μm min-1, which is about an order of magnitude higher than previous reports. Moreover, our results show that a grid catalyst design is important for successful fabrication of vertical high aspect ratio silicon nanostructures.
Monoliths of microporous aluminophosphates (AlPO4-17 and AlPO4-53) were structured by binder-freepulsed current processing. Such monoliths could be important for carbon capture from flue gas. TheAlPO4-17 and AlPO4-53 monoliths exhibited a tensile strength of 1.0 MPa and a CO2 adsorption capacityof 2.5 mmol g1 and 1.6 mmol g1, respectively at 101 kPa and 0 C. Analyses of single component CO2and N2 adsorption data indicated that the AlPO4-53 monoliths had an extraordinarily high CO2-over-N2selectivity from a binary gas mixture of 15 mol% CO2 and 85 mol% N2. The estimated CO2 capturecapacity of AlPO4-17 and AlPO4-53 monoliths in a typical pressure swing adsorption (PSA) process at 20C was higher than that of the commonly used zeolite 13X granules. Under cyclic sorption conditions,AlPO4-17 and AlPO4-53 monoliths were regenerated by lowering the pressure of CO2. Regeneration wasdone without application of heat, which would regenerate them to their full capacity for CO2 adsorption.
Monoliths of microporous aluminophosphates (AlPO4-17 and AlPO4-53) were structured by binder-free pulsed current processing. Such monoliths could be important for carbon capture from flue gas. The AlPO4-17 and AlPO4-53 monoliths exhibited a tensile strength of 1.0 MPa and a CO2 adsorption capacity of 2.5 mmol g-1 and 1.6 mmol g-1, respectively at 101 kPa and 0°C. Analyses of single component CO2 and N2 adsorption data indicated that the AlPO4-53 monoliths had an extraordinarily high CO2-over-N2 selectivity from a binary gas mixture of 15 mol% CO2 and 85 mol% N2. The estimated CO2 capture capacity of AlPO4-17 and AlPO4-53 monoliths in a typical pressure swing adsorption (PSA) process at 20°C was higher than that of the commonly used zeolite 13X granules. Under cyclic sorption conditions, AlPO4-17 and AlPO4-53 monoliths were regenerated by lowering the pressure of CO2. Regeneration was done without application of heat, which would regenerate them to their full capacity for CO2 adsorption.
This article proposes a strategy to functionalize cellulose nanocrystals by means of plasma-surface modification utilizing monomers of different nature: caprolactone, styrene and farnesene. The surface characteristics of the nanocrystals were studied by different techniques including XPS, FTIR and STEM, demonstrating that this technique allows a successful functionalization, yielding homogenous functionalization which does not alter the rod-like shape of the nanocrystals, and therefore their anisotropic behavior. We have furthermore studied the employment of the modified nanocrystals as reinforcement additive of ABS, which significantly enhanced the impact resistance of the thermoplastic, which could have great implications for industrial applications.
In this study, we have used cotton silk as a source of abundant hydroxyl groups for the fast nucleation/growth of cobalt oxide (Co3O4) nanowires via a hydrothermal method. The crystal planes of the Co3O4 nanowires well matched the cubic phase. The as-synthesized Co3O4 nanowires mainly contained cobalt and oxygen elements and were found to be highly sensitive towards uric acid in 0.01 M phosphate buffer solution at pH 7.4. Importantly, the Co3O4 nanowires exhibited a large surface area, which was heavily utilized during the immobilization of the enzyme uricase via a physical adsorption method. The potentiometric response of the uricase-immobilizing Co3O4 nanowires was measured in the presence of uric acid (UA) against a silver/silver chloride (Ag/AgCl) reference electrode. The newly fabricated uric acid biosensor possessed a low limit of detection of 1.0 +/- 0.2 nM with a wide linear range of 5 nM to 10 mM and sensitivity of 30.6 mV dec(-1). Additionally, several related parameters of the developed uric acid biosensor were investigated, such as the repeatability, reproducibility, storage stability, selectivity, and dynamic response time, and these were found to be satisfactory. The good performance of the Co3O4 nanowires was verified based on the fast charge-transfer kinetics, as confirmed via electrochemical impedance spectroscopy. The successful practical use of the uric acid biosensor was demonstrated based on the recovery method. The observed performance of the uricase-immobilizing Co3O4 nanowires revealed that they could be considered as a promising and alternative tool for the detection of uric acid under both in vitro and in vivo conditions. Also, the use of cotton silk as a source of abundant hydroxyl groups may be considered for the remarkably fast nucleation/growth of other metal-oxide nanostructures, thereby facilitating the fabrication of functional electrochemical devices, such as batteries, water-splitting devices, and supercapacitors.
Tumor associated macrophages (TAM) are key pathogenic factors in neoplastic diseases. They are known to have plasticity and can polarize into two opposing phenotypes, including the tumoricidal M1 and the protumoral M2 phenotypes with high prevalence of M2-phentoypes in patients with poor prognosis. Strategies for targeting M2-TAM may consequently increase the efficacy of therapeutic strategies for cancer treatment. Gold nanorod-assisted plasmonic photothermal therapy (PPTT) has emerged as a promising treatment for cancer but the effects of macrophage polarization parameters in the performance of this new treatment modality is still unknown. Herein, human monocytic THP-1 cells were polarized into two opposite phenotypic macrophages (M1-TAM and M2-TAM) and their response to PPTT was examined. M2-TAM exhibits a three-fold increase in AuNP uptake compared to M1-TAM. Laser irradiation results in selective killing of pro-tumoral M2-TAM after treatment with AuNPs with limited effects on anti-tumoral M1-TAM. A positive correlation between the expression of CD206 marker and the AuNP uptake may indicate the role of CD206 in facilitating AuNP uptake. Our findings also suggest that the differences in AuNP avidity and uptake between the M1-TAM and M2-TAM phenotypes may be the rationale behind the effectiveness of PPTT in the treatment of solid tumors.
This study presents the development of a highly selective and sensitive electrochemical sensor for the determination of melamine from aqueous environments. The sensor system is based on functionalised marigold-like CuO nanostructures fabricated using a controlled hydrothermal process, where the utilised succinic acid is considered to play a dual role as a functionalising and growth controlling agent (modifier). The fabricated nanostructures exhibit sharp and well-ordered structural features with dimensions (thickness) in the range of 10-50 nm. The sensor system exhibits strong linearity within the concentration range of 0.1 x 10(-9) to 5.6 x 10(-9) M and demonstrates an excellent limit of detection up to 0.1 x 10(-10) M. The extreme selectivity and sensing capability of the developed sensor is attributed to the synergy of selective interaction between succinic acid and melamine moieties, and the high surface area of marigold-like CuO nanostructures. In addition to this, the developed sensor was also utilised for the determination of melamine from real milk samples collected from different regions of Hyderabad, Pakistan. The obtained excellent recoveries proved the feasibility of the sensor for real life applications. The sensor system offers an operative measure for detecting extremely low melamine content with high selectivity in food contents.
Colloidal dispersions of cerium oxide nanoparticles are of importance for numerous applications including as catalysts, chemical mechanical polishing agents and additives for UV protective and anticorrosion coatings. Here, concentrated oleate-coated cerium oxide nanoparticles (CeO2 NPs) with a uniform size have been produced by solventless thermolysis of cerium-oleate powder under low pressure at 320 degrees C and subsequently dispersed in hexane. Unlike any previously reported colloidal synthesis process for ceria nanoparticles, this process does not involve any toxic high boiling point organic solvent that requires subsequent removal at high cost. Although the process is very simple, highly concentrated cerium oxide nanoparticles with more than 17 wt% solid content and 70% of the theoretical yield can be easily obtained. Moreover, the size, shape and crystallinity of cerium oxide nanoparticles can be tailored by changing the thermal decomposition temperature and reaction time. Moreover, the new synthesis route developed in this study allows the synthesis of clean and dispersible ceria nanoparticles at a relatively low cost in a single step. The prepared ceria nanoparticles have an excellent UV absorption property and remain transparent to visible light, thus having the potential to replace potentially hazardous organic compounds in UV absorbing clear coatings. As a proof of concept, the prepared dispersions of cerium oxide nanoparticles in hexane were formulated into a solvent borne binder base to develop clear UV protecting coatings for light sensitive substrates. The general synthesis strategy presented in this study is generally applicable for the low-cost production of a concentrated dispersion of metal oxide nanoparticles with minimal environmental impact.
Colloidal dispersions of cerium oxide nanoparticles are of importance for numerous applications including as catalysts, chemical mechanical polishing agents and additives for UV protective and anticorrosion coatings. Here, concentrated oleate-coated cerium oxide nanoparticles (CeO2 NPs) with a uniform size have been produced by solventless thermolysis of cerium-oleate powder under low pressure at 320 °C and subsequently dispersed in hexane. Unlike any previously reported colloidal synthesis process for ceria nanoparticles, this process does not involve any toxic high boiling point organic solvent that requires subsequent removal at high cost. Although the process is very simple, highly concentrated cerium oxide nanoparticles with more than 17 wt% solid content and 70% of the theoretical yield can be easily obtained. Moreover, the size, shape and crystallinity of cerium oxide nanoparticles can be tailored by changing the thermal decomposition temperature and reaction time. Moreover, the new synthesis route developed in this study allows the synthesis of clean and dispersible ceria nanoparticles at a relatively low cost in a single step. The prepared ceria nanoparticles have an excellent UV absorption property and remain transparent to visible light, thus having the potential to replace potentially hazardous organic compounds in UV absorbing clear coatings. As a proof of concept, the prepared dispersions of cerium oxide nanoparticles in hexane were formulated into a solvent borne binder base to develop clear UV protecting coatings for light sensitive substrates. The general synthesis strategy presented in this study is generally applicable for the low-cost production of a concentrated dispersion of metal oxide nanoparticles with minimal environmental impact.
We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo2O4) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 mu M) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo2O4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo2O4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo2O4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co3O4. The GCE-modified electrode is highly sensitive towards urea, with a linear response (R-2 = 0.99) over the concentration range 0.01-5 mM and with a detection limit of 1.0 mu M. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.
We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo 2 O 4 ) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 μM) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo 2 O 4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo 2 O 4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo 2 O 4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co 3 O 4 . The GCE-modified electrode is highly sensitive towards urea, with a linear response (R 2 = 0.99) over the concentration range 0.01-5 mM and with a detection limit of 1.0 μM. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.
We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo2O4) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 μM) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo2O4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo2O4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo2O4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co3O4. The GCE-modified electrode is highly sensitive towards urea, with a linear response (R2 = 0.99) over the concentration range 0.01–5 mM and with a detection limit of 1.0 μM. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.
Gold surface-bound hyperbranched polyethyleneimine (PEI) films decorated with palladium nanoparticles have been used as efficient catalysts for a series of Suzuki reactions. This thin film-format demonstrated good catalytic efficiency (TON up to 3.4 x 10(3)) and stability. Incorporation into a quartz crystal microbalance (QCM) instrument illustrated the potential for using this approach in lab-on-a-chip-based synthesis applications.
The preparation of superparamagnetic thin fibers by electrospinning dispersions of nanosized magnetite (Fe3O4, SPIO/USPIO) in a PMMA/PEO polymer solution is reported. The saturation magnetization and coercivity were not affected by the concentration (0, 1, 10, 20 wt%) or fiber orientation, showing hysteresis loops with high magnetization (64 A m(2) kg(-1) @ 500 kA m(-1)) and record low coercivity (20 A m(-1)). AC susceptibility measurements vs. temperature at frequencies from 60 to 2 kHz confirmed superparamagnetism. The mechanical properties were only slightly dependent on the particle concentration because the nanoparticles were separately encapsulated by the polymer. A uniform fibre fracture cross section was found at all the investigated particle contents, which suggests a strong interaction at the polymer/particle interface. A theoretical value of the magnetic low field susceptibility was calculated from the Langevin function and compared with measured values. The results show a distinct but concentration-independent anisotropy, favoring magnetization along the fiber orientation with no sign of exchange interaction, explained by complete nanoparticle separation. Superparamagnetism cannot be inferred from particle size alone, so a relevant interpretation and criterion for superparamagnetism is presented, in accordance with Neel's original definition. From the measurements, it can be concluded that magnetic characterization can be used to elucidate the material morphology beyond the resolution of available microscopy techniques (TEM and SEM).
In this study, NiO nanostructures were synthesized via a hydrothermal process using ascorbic acid as doping agent in the presence of ammonia. As prepared nanostructures were characterized using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area analysis, and thermogravimetric analysis (TGA). These analyses showed that these nanostructures are in the form of cotton-like porous material and crystalline in nature. Furthermore, the average size of these NiO crystallites was estimated to be 3.8 nm. These nanostructures were investigated for their potential to be a highly sensitive and selective enzyme-free sensor for detection of urea after immobilizing on a glassy carbon electrode (GCE) using 0.1% Nafion as binder. The response of this as developed amperometric sensor was linear in the range of 100-1100 mu M urea with a R-2 value of 0.990 and limit of detection (LOD) of 10 mu M. The sensor responded negligibly to various interfering species including glucose, uric acid, and ascorbic acid. This sensor was applied successfully for determining urea in real water samples such as mineral water, tap water, and river water with acceptable recovery.
Vehicle gas is often compressed to about 200 bar at the refueling station prior to charging to the vehicle's tank. If a high amount of oil is carried over to the gas, it may cause damage to the vehicles; it is therefore necessary to accurately measure oil carryover. In this paper, three analytical methods for accurate quantification of the oil content are presented whereby two methods are based on gas chromatography and one on FTIR. To better evaluate the level of complexity of the matrix, 10 different compressor oils in use at different refueling stations were initially collected and analysed with GC and FTIR to identify their analytical traces. The GC traces could be divided into three different profiles: oils exhibiting some well resolved peaks, oils exhibiting globally unresolved peaks with some dominant peaks on top of the hump and oils exhibiting globally unresolved peaks. After selection of three oils; one oil from each type, the three methods were evaluated with regards to the detection and quantification limits, the working range, precision, trueness and robustness. The evaluation of the three measurement methods demonstrated that any of these three methods presented were suitable for the quantification of compressor oil for samples. The FTIR method and the GC/MS method both resulted in measurement uncertainties close to 20% rel. while the GC/FID method resulted in a higher measurement uncertainty (U = 30% rel.).
The activity and adsorption of three variants of human carbonic anhydrase (HCA) with similar topology but variation in charge and stability were studied in the presence of carboxyl-modified polystyrene nanoparticles of different sizes ranging from 25 nm to 114 nm. The balance of forces driving the adsorption of carbonic anhydrase variants is affected by the physicochemical properties of the protein and the nanoparticle size. All enzymes are totally inhibited upon adsorption due to the transition towards a molten globule like state that lacks enzymatic activity. The size of the particle affects the adsorption of human carbonic anhydrase I and N-terminal truncated human carbonic anhydrase II. Investigations on pH effects indicate that the size of the particle modulates the lateral interactions at the protein layer for these particular variants whose adsorption is mainly driven by electrostatic forces. A third variant, human carbonic anhydrase II, instead shows no strong influence of nanoparticle size which supports an adsorption process mainly driven by the hydrophobic effect.
Supercritical carbon dioxide (scCO<inf>2</inf>) has been investigated for the generation of valuable waxy compounds and as an added-value technology in a holistic maize stover biorefinery. ScCO<inf>2</inf> extraction and fractionation was carried out prior to hydrolysis and fermentation of maize stover. Fractionation of the crude extracts by scCO<inf>2</inf> resulted in wax extracts having different compositions and melting temperatures, enabling their utilisation in different applications. One such fraction demonstrated significant potential as a renewable defoaming agent in washing machine detergent formulations. Furthermore, scCO<inf>2</inf> extraction has been shown to have a positive effect on the downstream processing of the maize stover. Fermentation of the scCO<inf>2</inf> extracted maize stover hydrolysates exhibited a higher glucose consumption and greater potential growth for surfactant (in comparison with non-scCO<inf>2</inf> treated stover) axnd ethanol production (a 40% increase in overall ethanol production after scCO<inf>2</inf> pre-treatment). This work represents an important development in the extraction of high value components from low value wastes and demonstrates the benefits of using scCO<inf>2</inf> extraction as a first-step in biomass processing, including enhancing downstream processing of the biomass for the production of 2nd generation biofuels as part of an integrated holistic biorefinery.
The concept of a metal-free and all-organic electroluminescent device is appealing from both sustainability and cost perspectives. Herein, we report the design and fabrication of such a light-emitting electrochemical cell (LEC), comprising a blend of an emissive semiconducting polymer and an ionic liquid as the active material sandwiched between two poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) conducting-polymer electrodes. In the off-state, this all-organic LEC is highly transparent, and in the on-state, it delivers uniform and fast to turn-on bright surface emission. It is notable that all three device layers were fabricated by material- and cost-efficient spray-coating under ambient air. For the electrodes, we systematically investigated and developed a large number of PEDOT:PSS formulations. We call particular attention to one such p-type doped PEDOT:PSS formulation that was demonstrated to function as the negative cathode, as well as future attempts towards all-organic LECs to carefully consider the effects of electrochemical doping of the electrode in order to achieve optimum device performance.
Three amorphous forms of Ar hydrate were produced using the crystalline clathrate hydrate Ar·6.5H2O (structure II, Fdm, a ≈ 17.1 Å) as a precursor and structurally characterized by a combination of isotope substitution (36Ar) neutron diffraction and molecular dynamics (MD) simulations. The first form followed from the pressure-induced amorphization of the precursor at 1.5 GPa at 95 K and the second from isobaric annealing at 2 GPa and subsequent cooling back to 95 K. In analogy to amorphous ice, these amorphs are termed high-density amorphous (HDA) and very-high-density amorphous (VHDA), respectively. The third amorph (recovered amorphous, RA) was obtained when recovering VHDA to ambient pressure (at 95 K). The three amorphs have distinctly different structures. In HDA the distinction of the original two crystallographically different Ar guests is maintained as differently dense Ar–water hydration structures, which expresses itself in a split first diffraction peak in the neutron structure factor function. Relaxation of the local water structure during annealing produces a homogeneous hydration environment around Ar, which is accompanied with a densification by about 3%. Upon pressure release the homogeneous amorphous structure undergoes expansion by about 21%. Both VHDA and RA can be considered frozen solutions of immiscible Ar and water in which in average 15 and 11 water molecules, respectively, coordinate Ar out to 4 Å. The local water structures of HDA and VHDA Ar hydrates show some analogy to those of the corresponding amorphous ices, featuring H2O molecules in 5- and 6-fold coordination with neighboring molecules. However, they are considerably less dense. Most similarity is seen between RA and low density amorphous ice (LDA), which both feature strictly 4-coordinated H2O networks. It is inferred that, depending on the kind of clathrate structure and occupancy of cages, amorphous states produced from clathrate hydrates display variable local water structures.
A promising fabrication method of electron transporting interlayers for solution-processed optoelectronic devices by electrophoretic deposition (EPD) of colloidal zinc oxide (ZnO) nanocrystals was demonstrated. A low voltage of 3-5 V and a short deposition time of 40 s at room temperature were found to be sufficient to generate dense and uniform ZnO thin films. The EPD ZnO nanocrystal films were applied as ETLs for inverted organic solar cell and polymer light emitting diodes (PLEDs). By optimizing the EPD processing of ZnO nanocrystal electron transporting layers (ETLs), inverted organic solar cells based on [3,4-b]-thiophene/benzodithiophene (PTB7): [6-6]-phenyl-C71-butyric acid methyl ester (PC71BM) and poly(3-hexylthiophene) (P3HT): [6-6]-phenyl-C-61-butyric acid methyl ester (PC61BM) with an average PCE of 8.4% and 4.0% were fabricated. In combination with the PLEDs and flexible devices results, we conclude that the EPD processed ZnOnanocrystal thin films can serve as high quality ETLs for solution-processed optoelectronic devices.
We investigate optically induced ultrafast magnetization dynamics in [Co(0.5 nm)/Pd(1 nm)](5)/NiFe(t) exchange-spring samples with tilted perpendicular magnetic anisotropy using a time-resolved magneto-optical Kerr effect magnetometer. The competition between the out-of-plane anisotropy of the hard layer, the in-plane anisotropy of the soft layer and the applied bias field reorganizes the spins in the soft layer, which are modified further with the variation in t. The spin-wave spectrum, the ultrafast demagnetization time, and the extracted damping coefficients - all depend on the spin distribution in the soft layer, while the latter two also depend on the spin-orbit coupling between the Co and Pd layers. The spin-wave spectra change from multimode to single-mode as t decreases. At the maximum field reached in this study, H = 2.5 kOe, the damping shows a nonmonotonic dependence on t with a minimum at t = 7.5 nm. For t < 7.5 nm, intrinsic effects dominate, whereas for t > 7.5 nm, extrinsic effects govern the damping mechanisms.
We report a microfluidic sample preparation platform called "Slipdisc" based on slipchip technology. Slipdisc is a rotational slipchip that uses a unique hand-wound clockwork mechanism for precise movement of specially fabricated polycarbonate discs. In operation, the microchannels and microchambers carved on the closely aligned microfluidic discs convert from continuous filled paths to defined compartments using the slip movement. The clockwork mechanism introduced here is characterised by a food dye experiment and a conventional HRP TMB reaction before measuring lactate dehydrogenase (LDH) enzyme levels, which is a crucial biomarker for neonatal diagnostics. The colorimetry based detection of LDH was performed with an unmodified camera and an image analysis procedure based on normalising images and observing changes in red channel intensity. The analysis showed a close to unity coefficient of determination (R2 = 0.96) in detecting the LDH concentration when compared with a standard Chemical Analyser, demonstrating the excellent performance of the slipdisc platform with colorimetric detection. The versatile point of care sample preparation platform should ideally be suited for a multitude of applications at resource-limited settings.
Here we present the synthesis and characterization of a new 2'-N-Guanidino, 4'-C-ethylene bridged thymidine (GENA-T) modified oligonucleotide possessing North-locked sugar conformation. Incorporation of GENA-T nucleotide though did not change the thermal stability of the oligonucleotides toward the complementary RNA; it significantly increased the stability of the parallel triplex at pH 7. The melting temperature of the triplex was increased by +9.5 degrees C as compared to that of the isosequential unmodified sequence. Moreover this modification imparted exceptional nuclease stability to the oligonucleotides for over 33 h. This study clearly demonstrates that GENA-T modified oligonucleotides could improve triplex formation with phenomenal enzymatic stability and could be used for various biomedical applications.
In the present study, versatile multifunctional unreported triazolo[1,5-a]quinoline derivatives were prepared. Compounds 1-19 were synthesized by adopting appropriate synthetic routes and were pharmacologically evaluated for their in vitro anticancer activity against human cancer cell lines: hepatocellular liver carcinoma (HEPG2) and Caucasian breast adenocarcinoma (MCF-7), in addition to their antibacterial and antifungal activities. Compound 4 demonstrated strong inhibitory effects against breast cancer (MCF-7), whereas compounds 8 and 19 exhibited moderate activity against breast carcinoma cell line MCF-7. Compounds 16 and 19 gave moderate activity against liver carcinoma cell line HEPG2. The antimicrobial activity of the prepared compounds was tested against bacteria and fungi. Among them, the results of antimicrobial activity indicated that compounds 4, 9, 11, 13, 15, 17, 18 and 19 were the most active compounds. Compound 4 exhibited strong activity against Fusarium sp., whereas compounds 9, 11, 15, 17, 18 and 19 showed high activity against Escherichia coli. More specifically, compound 17 displayed a high inhibitory effect against Bacillus cereus, Escherichia coli and Rhizoctonia sp.
The prime requirements for the spin transfer torque based ferromagnetic (FM)/nonmagnetic (NM) bilayer spin devices are (i) the absence of two-magnon scattering (TMS) noise, (ii) minimum energy dissipation and (iii) fast switching. To realize these objectives we have studied the thickness, Py (permalloy) thicknesses (t(Py)) and beta-Ta thicknesses (t(Ta)), dependent magnetization dynamics behaviour of the epitaxial Py (t(Py) = 3-20 nm)/beta-Ta (t(Ta) = 1.5-15 nm) system. The t(Py) dependence of TMS in epitaxial Py nanolayers (t(Py) = 3-20 nm) grown on a Si(400)/TiN(200) (8 nm) substrate is explored in terms of uniform and non-uniform magnetization precession regimes by employing ferromagnetic resonance field (H-r), linewidth (Delta H), and Gilbert damping constant (alpha) behaviour. It is found that in Py, t(Py) < 10 nm, layers TMS is dominating due to non-uniform precession of the magnetization. However in Py, t(Py) >= 10 nm, layers the uniform magnetization precession dominates, therefore Py layers, t(Py) >= 10 nm, are almost free from TMS. Furthermore, a nearly TMS free 12 nm epitaxial Py(200) layer is capped with beta-Ta (t(Ta) = 1.5-15 nm) layers to explore the t(Ta) dependent magnetization precession of epitaxial Py (12 nm) in terms of change in effective Gilbert damping constant (alpha(eff)). An anomalous decrease in alpha(eff) from 0.0087 at t(Ta) = 0 to a minimum value of 0.0077 at t(Ta) = 6 nm, and its subsequent increase for t(Ta) > 6 nm are observed in the epitaxial Py (12 nm)/beta-Ta(t(Ta)) system. Therefore the Si(400)/TiN(200) (8 nm)/Py(200) (12 nm)/beta-Ta(200) (6 nm) epitaxial system with nearly uniform magnetic precession and minimum effective Gilbert damping is suitable for low energy loss and ultrafast switching applications in spin transfer torque devices.
In this work, three types of polymers based on epsilon-caprolactone have been synthesized: poly(epsilon-caprolactone), polystyrene-poly(epsilon-caprolactone), and polystyrene-poly(epsilon-caprolactone-r-trimethylene carbonate) (SCT), where the polystyrene block was introduced to improve the electrochemical and mechanical performance of the material. Solid polymer electrolytes (SPEs) were produced by blending the polymers with 10-40 wt% lithium bis(trifluoromethane) sulfonimide (LiTFSI). Battery devices were thereafter constructed to evaluate the cycling performance. The best performing battery half-cell utilized an SPE consisting of SCT and 17 wt% LiTFSI as both binder and electrolyte; a Li vertical bar SPE vertical bar LiFePO4 cell that cycled at 40 degrees C gave a discharge capacity of about 140 mA h g(-1) at C/5 for 100 cycles, which was superior to the other investigated electrolytes. Dynamic mechanical analysis (DMA) showed that the storage modulus E' was about 5 MPa for this electrolyte.
In this work, three-dimensional (3D) aerogels and hydrogels based on lignin-containing arabinoxylan (AX) and cellulose nanofibers (CNF) were prepared. The effects of the CNF and the crosslinking with citric acid (CA) of various contents (1, 3, 5 wt%) were evaluated. All the aerogels possessed highly porous (above 98%) and lightweight structures. The AX-CNF hydrogel with a CA content of 1 wt% revealed a favorable network structure with respect to the swelling ratio; nanofiber addition resulted in a five-fold increase in the degree of swelling (68 g of water per g). The compressive properties were improved when the higher CA content (5 wt%) was used; when combined with CNF, there was a seven-fold enhancement in the compressive strength. The AX-CNF hydrogels were prepared using a green and straightforward method that utilizes sustainable resources efficiently. Therefore, such natural hydrogels could find application potential, for example in the field of soft tissue engineering.
A water-soluble rhodium complex formed from commercially available [Rh(COD)(CH3CN)(2)]BF4 and 1,3,5-triaza-7-phosphaadamantane (PTA) catalyzes the isomerization of both codeine and morphine into hydrocodone and hydromorphone with very high efficiency. The reaction is performed in water, allowing isolation of the final products by simple filtration, which results in very high isolated yields. The reactions can be easily scaled up to 100 g.
The present DFT investigation supports a previous conclusion of Dean et al. that hydroxylation occurs without epoxide intermediate at room temperature due to a strong electrostatic interaction of peroxide ions with π electrons of CC bonds of chalcone, and 3-hydroxyflavone has been found to be the major product. The calculated activation energy difference (ΔG#) of initial enolization followed by hydroxylation or simultaneous cyclization and hydroxylation has been found to be negligible (∼4 kcal mol-1). On the other hand, epoxide formation requires significant activation energy, which is supposed to occur at high temperatures. In addition, if epoxide is formed, the ring opens by an attack of phenolic oxygen, occurring preferentially at α position via a five-member transition state due to a low activation barrier height (19.82 kcal mol-1 in the gas phase and 19.55 kcal mol-1 in ethanol) compared to that of a six-member transition state (44.41 kcal mol-1 at B3LYP in the gas phase and 38.55 kcal mol -1 in ethanol). It is also observed that the solvation study does not affect the main conclusion of the paper. These findings also support the previous observation of Dean et al. Predicted ΔG# in different DFT functionals are consistent, although the total energy is significantly different
Monoalkylation of primary amines using amine hydrobromides and alkyl bromides has been carried out. Under controlled reaction conditions the reactant primary amine was selectively deprotonated and made available for reaction, while the newly generated secondary amine remained protonated, and did not participate in alkylation further. Reaction was carried out under mild reaction conditions and was applicable to a wide range of primary amines and alkyl bromides.
Designing a facile and low-cost methodology to fabricate earth-abundant catalysts is very much needed for a wide range of applications. Herein, a simple and straightforward approach was developed to tune the electronic properties of cobalt oxide nanostructures by doping them with nickel and then using them to catalyze the oxygen evolution reaction (OER) in an aqueous solution of 1.0 M KOH. The addition of a nickel impurity improved the conductivity of the cobalt oxide, and further increased its activity towards the OER. Analytical techniques such as scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and powder X-ray diffraction (XRD) were used to investigate, respectively, the morphology, composition and crystalline structure of the materials used. The nickel-doped cobalt oxide material showed randomly oriented nanowires and a high density of nanoparticles, exhibited the cubic phase, and contained cobalt, nickel and oxygen as its main elements. The nickel-doped cobalt oxide also yielded a Tafel slope of 82 mV dec(-1) and required an overpotential of 300 mV to reach a current density of 10 mA cm(-2). As an OER catalyst, it was shown to be durable for 40 h. Electrochemical impedance spectroscopy (EIS) analysis showed a low charge-transfer resistance of 177.5 ohms for the nickel-doped cobalt oxide, which provided a further example of its excellent OER performance. These results taken together indicated that nickel doping of cobalt oxide can be accomplished via a facile approach and that the product of this doping can be used for energy and environmental applications.
A two-step deposition technique is used for preparing CH3NH3PbI3 perovskite solar cells. Using ZrO2 and TiO2 as a mesoporous layer, we obtain an efficiency of 10.8% and 9.5%, respectively, under 1000 W m(-2) illumination. The ZrO2 based solar cell shows higher photovoltage and longer electron lifetime than the TiO2 based solar cell.
The recalcitrance of plastics like nylon and other polyamides contributes to environmental problems (e.g. microplastics in oceans) and restricts possibilities for recycling. The fact that hitherto discovered amidases (EC 3.5.1. and 3.5.2.) only show no, or low, activity on polyamides currently obstructs biotechnological-assisted depolymerization of man-made materials. In this work, we capitalized on enzyme engineering to enhance the promiscuous amidase activity of polyesterases. Through enzyme design we created a reallocated water network adapted for hydrogen bond formation to synthetic amide backbones for enhanced transition state stabilization in the polyester-hydrolyzing biocatalysts Humicola insolens cutinase and Thermobifida cellulosilytica cutinase 1. This novel concept enabled increased catalytic efficiency towards amide-containing soluble substrates. The afforded enhanced hydrolysis of the amide bond-containing insoluble substrate 3PA 6,6 by designed variants was aligned with improved transition state stabilization identified by molecular dynamics (MD) simulations. Furthermore, the presence of a favorable water-molecule network that interacted with synthetic amides in the variants resulted in a reduced activity on polyethylene terephthalate (PET). Our data demonstrate the potential of using enzyme engineering to improve the amidase activity for polyesterases to act on synthetic amide-containing polymers.
Spatially and temporally controlled drug delivery is important for implant and tissue engineering applications, as the efficacy and bioavailability of the drug can be enhanced, and can also allow for drugging stem cells at different stages of development. Long-term drug delivery over weeks to months is however difficult to achieve, and coating of 3D surfaces or creating patterned surfaces is a challenge using coating techniques like spin- and dip-coating. In this study, mesoporous films consisting of SBA-15 particles grown onto silicon wafers using wet processing were evaluated as a scaffold for drug delivery. Films with various particle sizes (100-900 nm) and hence thicknesses were grown onto trichloro(octadecyl)silane-functionalized silicon wafers using a direct growth method. Precise patterning of the areas for film growth could be obtained by local removal of the OTS functionalization through laser ablation. The films were incubated with the drug model 3,3 -dioctadecyloxacarbocyanine perchlorate (DiO), and murine myoblast cells (C2C12 cells) were seeded onto films with different particle sizes. Confocal laser scanning microscopy (CLSM) was used to study the cell growth, and a vinculin-mediated adherence of C2C12 cells on all films was verified. The successful loading of DiO into the films was confirmed by UV-vis and CLSM. It was observed that the drugs did not desorb from the particles during 24 hours in cell culture. During adherent growth on the films for 4 h, small amounts of DiO and separate particles were observed inside single cells. After 24 h, a larger number of particles and a strong DiO signal were recorded in the cells, indicating a particle mediated drug uptake. The vast majority of the DiO-loaded particles remained attached to the substrate also after 24 h of incubation, making the films attractive as longer-term reservoirs for drugs on e.g. medical implants.
Fast (60 kHz) magic angle spinning solid-state NMR allows very sensitive proton detection in highly paramagnetic organometallic powders. We showcase this technique with the complete assignment of H-1 and C-13 resonances in a high-spin Fe(ii) polymerisation catalyst with less than 2 mg of sample at natural abundance.
The influence of temperature on adsorption and the adsorbed layer properties of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) were investigated on silica and hydrophobized silica surfaces immersed in aqueous polymer solution. To achieve a concise understanding a quartz crystal microbalance with dissipation, ellipsometry, and atomic force microscopy imaging were employed. These techniques provide complimentary information on the structure, mass and viscoelastic properties of the polymer layers. Adsorption was first allowed at 25 degrees C. Next, the temperature was increased step-wise up to 50 degrees C and then decreased again. This procedure highlights the temperature dependence of the adsorbed material, as well as the hysteresis in the adsorption due to temperature cycling. A change in temperature not only affects the adsorbed amount, but also the properties of the layer as illustrated by measurements of its water content, thickness and viscoelasticity.
Understanding the conformational preferences of free ligands in solution is often necessary to rationalize structure–activity relationships in drug discovery. Herein, we examine the conformational behavior of an epimeric pair of side-chain stapled peptides that inhibit the FAD dependent amine oxidase lysine specific demethylase 1 (LSD1). The peptides differ only at a single stereocenter, but display a major difference in binding affinity. Their Raman optical activity (ROA) spectra are most likely dominated by the C-terminus, obscuring the analysis of the epimeric macrocycle. By employing NMR spectroscopy, we show a difference in conformational behavior between the two compounds and that the LSD1 bound conformation of the most potent compound is present to a measurable extent in aqueous solution. In addition, we illustrate that Molecular Dynamics (MD) simulations produce ensembles that include the most important solution conformations, but that it remains problematic to identify relevant conformations with no a priori knowledge from the large conformational pool. Furthermore, this work highlights the importance of understanding the scope and limitations of the available techniques for conducting conformational analyses. It also emphasizes the importance of conformational selection of a flexible ligand in molecular recognition.
The 3,4-dihydroquinazolinone (DHQ) moiety is a highly valued scaffold in medicinal chemistry due to the vast number of biologically-active compounds based on this core structure. Current synthetic methods to access these compounds are limited in terms of diversity and flexibility and often require the use of toxic reagents or expensive transition-metal catalysts. Herein, we describe the discovery and development of a novel cascade cyclization/Leuckart–Wallach type strategy to prepare substituted DHQs in a modular and efficient process using readily-available starting materials. Notably, the reaction requires only the addition of formic acid or acetic acid/formic acid and produces H2O, CO2 and methanol as the sole reaction byproducts. Overall, the reaction provides an attractive entry point into this important class of compounds and could even be extended to isotopic labelling via the site-selective incorporation of a deuterium atom.
Three different models of ethylene interaction with copper species, namely, the Cu(100) surface, odd-numbered copper clusters C2H4/Cu-n (where n = 3, 7, 11, 15, 17, 19, 21, 25 and 27) and atomic copper C2H4/Cu were studied theoretically. It was found that the ethylene molecule possesses three different types of bonding depending on the presence of the unpaired spin on the reacting copper atom. These bonding structures demonstrate different types of band gap (bulk) or SOMO-LUMO gaps (cluster/atom), where SOMO stands for the singly occupied and LUMO means the lowest unoccupied molecular orbitals of the copper species. The obtained results are in good agreement with the previous experimental and computational results on the structural, spectral and energetic properties of the studied species. The bulk copper and sub-nanosized clusters (n > 7) build up the mono-pi-bonded ground state complexes with ethylene where the latter species possesses the C-2v symmetry. The single-atom complex C2H4/Cu forms the CS-symmetrical ground state (X) over tilde (2)A' and the excited B-2(2) and B-4 state complexes of the C-2v and C-2 symmetry, respectively. The (X) over tilde (2)A' state complex is mono-sigma-bonded and involves the singlet ethylene moiety. The more tightly bound excited B-2(2) complex has the di-sigma-bonded structure and corresponds to the triplet ethylene. The adiabatic energy difference between the B-2(2) and (X) over tilde (2)A' states is equal to 10.8 kcal mol(-1) and can be ascribed to the singlet-triplet splitting of the ethylene moiety interacting with copper. The QTAIM analysis supports the coordination type of the Cu-C bonds in all the studied complexes. Formation of the C2H4/Cu(100), C2H4/Cu-n and C2H4/Cu species is in accord with the well-known Dewar-Chatt-Duncanson model, in such a way that the opposing sigma-donation step yields the ground state complex ((X) over tilde (2)A'), while the subsequent more expensive supporting pi*-back donation step provides the excited B-2(2) state complex. In the present paper we have developed a computational procedure to optimize the latter complex.
Three amorphous forms of Ar hydrate were produced using the crystalline clathrate hydrate Ar·6.5H2O (structure II, Fd3m, a ≈ 17.1 Å) as a precursor and structurally characterized by a combination of isotope substitution (36Ar) neutron diffraction and molecular dynamics (MD) simulations. The first form followed from the pressure-induced amorphization of the precursor at 1.5 GPa at 95 K and the second from isobaric annealing at 2 GPa and subsequent cooling back to 95 K. In analogy to amorphous ice, these amorphs are termed high-density amorphous (HDA) and very-high-density amorphous (VHDA), respectively. The third amorph (recovered amorphous, RA) was obtained when recovering VHDA to ambient pressure (at 95 K). The three amorphs have distinctly different structures. In HDA the distinction of the original two crystallographically different Ar guests is maintained as differently dense Ar–water hydration structures, which expresses itself in a split first diffraction peak in the neutron structure factor function. Relaxation of the local water structure during annealing produces a homogeneous hydration environment around Ar, which is accompanied with a densification by about 3%. Upon pressure release the homogeneous amorphous structure undergoes expansion by about 21%. Both VHDA and RA can be considered frozen solutions of immiscible Ar and water in which in average 15 and 11 water molecules, respectively, coordinate Ar out to 4 Å. The local water structures of HDA and VHDA Ar hydrates show some analogy to those of the corresponding amorphous ices, featuring H2O molecules in 5- and 6-fold coordination with neighboring molecules. However, they are considerably less dense. Most similarity is seen between RA and low density amorphous ice (LDA), which both feature strictly 4-coordinated H2O networks. It is inferred that, depending on the kind of clathrate structure and occupancy of cages, amorphous states produced from clathrate hydrates display variable local water structures.