Compositional analysis in the nano-regime:A SIMS perspective

A serious problem in secondary ion mass spectrometry (SIMS) analysis is its "matrix effect" that hinders the quantification of a certain species in a sample and consequently, appropriate corrective measures are taken to calibrate the secondary ion currents into respective concentrations for accurate compositional analysis. Use of "calibration standards" is necessary for this purpose. Detection of molecular MCsn+ ions (M-element to be analyzed, n=1, 2, 3,....) under Cs+ ion bombardment is a possible mean to minimize such matrix effect, enabling one to quantify without the need of calibration standards. Our recent studies on MCsn+ molecular ions aim towards the understanding of their formation mechanisms, which are important to know their effects on SIMS quantification.In-depth quantitative analysis is a major strength of SIMS for which 'depth resolution' is of significant relevance. The optimal choice of the impact parameters during SIMS analyses can play an effective role in obtaining data with ultra-high depth resolution. SIMS is possible at depth resolution in the nm or even sub-nm range, with quantifiable data obtained from the top monolayer onwards into the material. With optimized experimental conditions, like extremely low beam current (down to ～10 nA), and low bombarding energy (below 1 keV), ultra-high depth resolution SIMS has enabled interfacial composition analysis of ultra-thin films, quantum wells, heterostructures, etc. and complex low-dimensional structures with high precision and repeatability.     

Synthesis and X-ray Crystal Structures of Two Luminescent Imidazopyridinium Derivatives from the Corresponding N-(aryl)-Pyridine-2-aldimines

Syntheses and X-ray structural characterizations of two new luminescent imidazopyridinium derivatives, 2-(phenyl)-N(3)-(4(methyl)phenyl)-imidazo[1,5a] pyridinium perchlorate (1) and 2-(pyridyl)-N(3)-(4-(chloro)phenyl)-imidazo[1,5a] pyridinium perchlorate (2) are reported. The compounds are prepared in one step from N-(4-(methyl)phenyl) pyridine-2-aldimine and N-(4-(chloro)phenyl) pyridine-2-aldimine respectively in a transformation mediated by Mn(OAc)₂-KMnO₄ mixture. It is found that the molecular structures of the two compounds are similar. In the solid state, 1 forms a three-dimensional network through a series of hydrogen bonds between the cations and anions in the lattice while 2 forms a similar but less extensively linked network. The substitution of hydrogen at the 2-position of the imidazopyridinium ring by phenyl or 2-(pyridyl) affects the nature of their first excited states as detected by changes in their emission and absorption spectra.     

Sol-gel synthesis of cubic titanium dioxide nanoparticle using poly(ethylene glycol) as a capping agent: voltammetric simultaneous determination of uric acid and guanine

Titanium dioxide nanoparticles (NPs) were synthesized by a sol-gel method from hexafluorotitanic acid using poly(ethylene glycol) as a capping agent. The crystal structure and morphology of the NPs were characterized by X-ray diffraction, FESEM, and TEM. The NPs were used to modify a graphite paste electrode for simultaneous determination of uric acid (UA) and guanine (GU). The effect of calcination temperature on crystal structure and electrocatalytic activity was investigated. The electrochemical responses to UA and GU at bare GP, TiO₂–350/GP, and TiO₂–600/GP electrodes were compared. The DPV oxidation peaks of UA and GU were found to be strongest at around 304 and 673 mV, respectively, against Ag/AgCl reference electrode, and this are well separated for effective simultaneous determination. UA and GU can be simultaneously determined by this method. Response is linear within the range 0.1–500 μM and 0.1–40 μM for UA and GU, respectively. The detection limits are 70 nM for UA and 50 nM for GU (at an S/N? ratio of?3). The TiO₂–600/GP electrode showed excellent analytical performance when analyzing spiked urine and serum samples.

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Graphical abstract A graphical representation of cubic TiO₂ nanoparticle formation during hydrolysis through sol-gel process.

     

Design of a fused triazolyl 2-quinolinone unnatural nucleoside via tandem CuAAC-Ullmann coupling reaction and study of photophysical property

This report presents the design and synthesis of a novel fused triazolyl 2-quinolinone (FTQuon) nucleoside as a new generation of angularly widened unnatural nucleobase surrogate with two possible H-bonding faces-one H-bond acceptor and another donor. The synthesis via a tandem CuAAC-Ullmann coupling, the study of photophysical properties and theoretical calculation in the context of DNA are the main contents of this report. The newly designed nucleoside shows interesting photphysical property with slight blue shifted solvatochromicity. It also shows pH sensitive emission. All the theoretical DNA duplexes containing the FTQuon show right?handed B-form helicity as revealed from a molecular dynamics simulation using Schrodinger Macromodel. A theoretical (DFT) study indicates a good stabilizing property of FTQuon via pairing with natural pyrimidine bases. It also shows good interaction property with BSA protein signalled via a switch on fluorescence response.     

Evaluation of air permeability characteristics on the hybridization of carbon black with graphene nanoplatelets in bromobutyl rubber/epoxidized natural rubber composites for inner‐liner applications

Nanotechnology has been explored recently as a means of enhancing the properties of conventional elastomers for engineering applications. In the current study, the effect of nanofillers on air impermeability properties of Brominated isobutylene‐isoprene rubber (BIIR)/Epoxidized natural rubber (ENR) blend has analyzed for automotive applications. The ENR chosen is ENR 25 and ENR 50 (25 and 50% epoxidation) and prepared the blends in a ratio of 75:25 (BIIR:ENR), and from both blend based composites, a part of carbon black replaced with graphene nanoplatelets (GNP). The physical and thermal properties were compared for both binary blend nanocomposites to study the level of exfoliation and reinforcement behavior of GNP. Morphology studies were employed to reveal the level of interaction between GNP and carbon black in both blends. The influence of epoxidation in the formation of nanostructures in both blends have been evaluated, and the effect of nanostructures on air permeability properties was studied. The air impermeability of BIIR‐ENR 50 nanocomposites were improved with increasing platelet concentration, a 30% improvement in air permeability is obtained for BIIR‐ENR 50 composites over BIIR ‐ENR 25.     

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases [Co(L)?](ClO?)? (1-3), where L is 4'-phenyl-2,2':6',2'-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2'-terpyridine (an-tpy in 2) and 4'-(1- pyrenyl)-2,2':6',2'-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1?:?2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H?O (2?:?1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K(b) value of ～10? M?1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC?? values of 24.2 and 7.6 μM, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.     

A review of biphasic hydroformylation for long chain substrates

The regioselective hydroformylation reactions of long chain olefins catalyzed by different unmodified and modified Co-based, Rh-based catalysts are summarized. The mechanism of homogeneous hydroformylation reactions using Co-based/Rh-based catalysts (unmodified) showed inhibition of reaction rate due to higher partial pressure of CO and also caused difficulty in separating catalysts from the product mixture. Hydroformylation reactions in biphasic medium using water soluble catalysts (Rh, Co, Ru/TPPTS) with an effective surfactant, cetyltrimethylammonium bromide (CTAB), are discussed. The homogeneous biphasic systems are not applicable for long chain olefins due to their low solubility in aqueous phase.     

Behavior of the amphiphile CHAPS alone and in combination with the biopolymer inulin in water and isopropanol-water media

Self-aggregation of the zwitterionic surfactant 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) in water and isopropanol-water media, and interaction of the amphiphile with the biopolymer inulin in these media were investigated. The micellar properties of the zwitterionic surfactant and its associated interfacial and bulk properties along with the related energetic, and aggregation number were determined. The different stages of interaction of the CHAPS-inulin combines were identified and assessed. The complexes were formed and aggregated in solution at different stages of their molecular compositions. The aggregated sizes were determined by dynamic light scattering study and the morphology in the solvent removed states were examined using scanning electron microscope and transmission electron microscope techniques. The results witnessed formation of ensembles of varied and striking patterns.     

Near-complete absorption of intense, ultrashort laser light by sub-lambda gratings

We demonstrate near-100% light absorption and increased x-ray emission from dense plasmas created on solid surfaces with a periodic sub-lambda structure. The efficacy of the structure-induced surface plasmon resonance, responsible for enhanced absorption, is directly tested at the highest intensities to date (3 x 10{15} W cm{-2}) via systematic, correlated measurements of absorption and x-ray emission. An analytical grating model as well as 2D particle-in-cell simulations conclusively explain our observations. Our study offers a definite, quantitative way forward for optimizing and understanding the absorption process.