The role of sulphates and organic vapours in growth of newly formed particles in a eucalypt forest

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photooxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.

Fast and effective focused retrieval

Building an efficient and an effective search engine is a very challenging task. In this paper, we present the efficiency and effectiveness of our search engine at the INEX 2009 Efficiency and Ad Hoc Tracks. We have developed a simple and effective pruning method for fast query evaluation, and used a two-step process for Ad Hoc retrieval. The overall results from both tracks show that our search engine performs very competitively in terms of both efficiency and effectiveness.

Analysis of stream cipher based authenticated encryption schemes

Authenticated Encryption (AE) is the cryptographic process of providing simultaneous confidentiality and integrity protection to messages. This approach is more efficient than applying a two-step process of providing confidentiality for a message by encrypting the message, and in a separate pass providing integrity protection by generating a Message Authentication Code (MAC). AE using symmetric ciphers can be provided by either stream ciphers with built in authentication mechanisms or block ciphers using appropriate modes of operation. However, stream ciphers have the potential for higher performance and smaller footprint in hardware and/or software than block ciphers. This property makes stream ciphers suitable for resource constrained environments, where storage and computational power are limited. There have been several recent stream cipher proposals that claim to provide AE. These ciphers can be analysed using existing techniques that consider confidentiality or integrity separately; however currently there is no existing framework for the analysis of AE stream ciphers that analyses these two properties simultaneously. This thesis introduces a novel framework for the analysis of AE using stream cipher algorithms. This thesis analyzes the mechanisms for providing confidentiality and for providing integrity in AE algorithms using stream ciphers. There is a greater emphasis on the analysis of the integrity mechanisms, as there is little in the public literature on this, in the context of authenticated encryption. The thesis has four main contributions as follows. The first contribution is the design of a framework that can be used to classify AE stream ciphers based on three characteristics. The first classification applies Bellare and Namprempre's work on the the order in which encryption and authentication processes take place. The second classification is based on the method used for accumulating the input message (either directly or indirectly) into the into the internal states of the cipher to generate a MAC. The third classification is based on whether the sequence that is used to provide encryption and authentication is generated using a single key and initial vector, or two keys and two initial vectors. The second contribution is the application of an existing algebraic method to analyse the confidentiality algorithms of two AE stream ciphers; namely SSS and ZUC. The algebraic method is based on considering the nonlinear filter (NLF) of these ciphers as a combiner with memory. This method enables us to construct equations for the NLF that relate the (inputs, outputs and memory of the combiner) to the output keystream. We show that both of these ciphers are secure from this type of algebraic attack. We conclude that using a keydependent SBox in the NLF twice, and using two different SBoxes in the NLF of ZUC, prevents this type of algebraic attack. The third contribution is a new general matrix based model for MAC generation where the input message is injected directly into the internal state. This model describes the accumulation process when the input message is injected directly into the internal state of a nonlinear filter generator. We show that three recently proposed AE stream ciphers can be considered as instances of this model; namely SSS, NLSv2 and SOBER-128. Our model is more general than a previous investigations into direct injection. Possible forgery attacks against this model are investigated. It is shown that using a nonlinear filter in the accumulation process of the input message when either the input message or the initial states of the register is unknown prevents forgery attacks based on collisions. The last contribution is a new general matrix based model for MAC generation where the input message is injected indirectly into the internal state. This model uses the input message as a controller to accumulate a keystream sequence into an accumulation register. We show that three current AE stream ciphers can be considered as instances of this model; namely ZUC, Grain-128a and Sfinks. We establish the conditions under which the model is susceptible to forgery and side-channel attacks.

High-throughput vectors for efficient gene silencing in plants

A major challenge in the post-genome era of plant biology is to determine the functions of all genes in the plant genome. A straightforward approach to this problem is to reduce or knockout expression of a gene with the hope of seeing a phenotype that is suggestive of its function. Insertional mutagenesis is a useful tool for this type of study but is limited by gene redundancy, lethal knockouts, non-tagged mutants, and the inability to target the inserted element to a specific gene. The efficacy of gene silencing in plants using inverted-repeat transgene constructs that encode a hairpin RNA (hpRNA) has been demonstrated by a number of groups, and has several advantages over insertional mutagenesis. In this paper we describe two improved pHellsgate vectors that facilitate rapid generation of hpRNA-encoding constructs, pHellsgate 4 allows the production of an hpRNA construct in a single step from a single polymerase chain reaction product, while pHellsgate 8 requires a two-step process via an intermediate vector. We show that these vectors are effective at silencing three endogenous genes in Arabidopsis, FLOWERING LOCUS C, PHYTOENE DESATURASE and ETHYLENE INSENSITIVE 2. We also show that a construct of sequences from two genes silences both genes.

ortho-Bromo(propa-1,2-dien-1-yl)arenes : substrates for domino reactions

o-Bromo(propa-1,2-dien-1-yl)arenes exhibit novel and orthogonal reactivity under Pd catalysis in the presence of secondary amines to form enamines (concerted Pd insertion, intramolecular carbopalladation, and terminative Buchwald–Hartwig coupling) and of amides to form indoles (addition, Buchwald–Hartwig cyclization, and loss of the acetyl group). The substrates for these reactions can be accessed in a reliable and highly selective two-step process from 2-bromoaryl bromides.

Au-Pd alloy nanoparticle catalyzed selective oxidation of benzyl alcohol and tandem synthesis of imines at ambient conditions

Alloy nanoparticles (NPs) of gold and palladium on ZrO2 support (Au–Pd@ZrO2) were found to be highly active in oxidation of benzyl alcohols and can be used for the tandem synthesis of imines from benzyl alcohols and amines via a one-pot, two-step process at mild reaction conditions. The first step of the process is oxidation of benzyl alcohol to benzaldehyde, excellent yields were achieved after 7 h reaction at 40 °C without addition of any base. In the second step, aniline was introduced into the reaction system to produced N-benzylideneaniline. The benzaldehyde obtained in the first step was completely consumed within 1 h. A range of benzyl alcohols and amines were investigated for the general applicability of the Au–Pd alloy catalysts. It is found that the performance of the catalysts depends on the Au–Pd metal contents and composition. The optimal catalyst is 3.0 wt% Au–Pd@ZrO2 with a Au:Pd molar ratio 1:1. The alloy NP catalyst exhibited superior catalytic properties to pure AuNP or PdNP because the surface of alloy NPs has higher charge heterogeneity than that of pure metal NPs according to simulation of density function theory (DFT)

Synthesis of novel beta-aryl-beta-(methylthio)acroleins via Vilsmeier-Haack protocol as potential 1,3-dielectrophilic three-carbon building blocks

A new general route for the synthesis of novel beta-aryl-beta-(methylthio)acroleins, a class of stable potential 1,3-dielectrophilic synthons, has been reported. The overall protocol involves treatment of either beta-chloroacroleins or their precursor iminium salts (generated in situ from the corresponding active methylene ketones under Vilsmeier-Haack reaction conditions) with S,S-dimethyldithiocarbonates (DDC)/aqueous KOH in either a one-pot or two-step process. The dimethyldithiocarbonate (DDC)/30% aqueous KOH has been shown to be an excellent source of methylthiolate anion. (C) 2014 Elsevier Ltd. All rights reserved.

Combining data sets of satellite-retrieved products for basin-scale water balance study: 2. Evaluation on the Mississippi Basin and closure correction model

In this study, we applied the integration methodology developed in the companion paper by Aires (2014) by using real satellite observations over the Mississippi Basin. The methodology provides basin-scale estimates of the four water budget components (precipitation P, evapotranspiration E, water storage change Delta S, and runoff R) in a two-step process: the Simple Weighting (SW) integration and a Postprocessing Filtering (PF) that imposes the water budget closure. A comparison with in situ observations of P and E demonstrated that PF improved the estimation of both components. A Closure Correction Model (CCM) has been derived from the integrated product (SW+PF) that allows to correct each observation data set independently, unlike the SW+PF method which requires simultaneous estimates of the four components. The CCM allows to standardize the various data sets for each component and highly decrease the budget residual (P - E - Delta S - R). As a direct application, the CCM was combined with the water budget equation to reconstruct missing values in any component. Results of a Monte Carlo experiment with synthetic gaps demonstrated the good performances of the method, except for the runoff data that has a variability of the same order of magnitude as the budget residual. Similarly, we proposed a reconstruction of Delta S between 1990 and 2002 where no Gravity Recovery and Climate Experiment data are available. Unlike most of the studies dealing with the water budget closure at the basin scale, only satellite observations and in situ runoff measurements are used. Consequently, the integrated data sets are model independent and can be used for model calibration or validation.

Metal-insulator transition characteristics of vanadium dioxide thin films synthesized by ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture

We report the synthesis of high quality vanadium dioxide (VO2) thin films by a novel spray pyrolysis technique, namely ultrasonic nebulized spray pyrolysis of aqueous combustion mixture (UNSPACM). This simple and cost effective two step process involves synthesis of a V2O5 film on an LaAlO3 substrate followed by a controlled reduction to form single phase VO2. The formation of M1 phase (p21/c) is confirmed by Raman spectroscopic studies. A thermally activated metal-insulator transition (MIT) was observed at 61 degrees C, where the resistivity changes by four orders of magnitude. Activation energies for the low conduction phase and the high conduction phase were obtained from temperature variable resistance measurements. The infrared spectra also show a dramatic change in reflectance from 13% to over 90% in the wavelength range of 7-15 mu m. This indicates the suitability of the films for optical switching applications at infrared frequencies.

Synthesis of Hollow Nanotubes of Zn2SiO4 or SiO2: Mechanistic Understanding and Uranium Adsorption Behavior

We report a facile synthesis of Zn2SiO4 nanotubes using a two-step process consisting of a wet-chemical synthesis of core-shell ZnO@SiO2 nanorods followed by thermal annealing. While annealing in air leads to the formation of hollow Zn2SiO4, annealing under reducing atmosphere leads to the formation of SiO2 nanotubes. We rationalize the formation of the silicate phase at temperatures much lower than the temperatures reported in the literature based on the porous nature of the silica shell on the ZnO nanorods. We present results from in situ transmission electron microscopy experiments to clearly show void nucleation at the interface between ZnO and the silica shell and the growth of the silicate phase by the Kirkendall effect. The porous nature of the silica shell is also responsible for the etching of the ZnO leading to the formation of silica nanotubes under reducing conditions. Both the hollow silica and silicate nanotubes exhibit good uranium sorption at different ranges of pH making them possible candidates for nuclear waste management.

Hidden role of anion exchange reactions in nucleation of colloidal nanocrystals

We investigate the processes involved in the nucleation of colloidal lead selenide nanoparticles. Our studies show that an unusual pathway - an anion exchange reaction, causes the nucleation of lead selenide nanocrystals. In this process, one quantum dot is transformed into another due to a substitution of its constituent anions. The existence of this pathway was never anticipated perhaps due to its unusually rapid kinetics. The nucleation and growth kinetics of colloidal lead selenide quantum dots are found to fit well to a two-step process. The rate constant associated with the anion exchange process is found to be four orders of magnitude greater than that of the nanocrystal growth. The complete consumption of the initial oxide nanoparticle thus provides a sharp, temporally well-defined nucleation event.

Optimization of nonvolatile holographic recording by application of an external electric field

The dependences of the recording properties of LiNbO3:Fe:Mn crystals on an external electric field (applied in the recording or fixing phase of the nonvolatile holographic recording process) are numerically investigated and the optimal conditions for applying an external electric field in this two-step process of nonvolatile holographic recording are discussed in detail. Significant improvement of the photorefractive performance has been found and experimental verifications using a small external electric field are described. Moreover, direct measures relating to the dominant photovoltaic mechanism in the doubly doped LiNbO3 crystals and the unconventional grating-enhanced fixing are revealed by applying an external electric field in the recording and the fixing phases, respectively.

Gas-phase production of gold-decorated silica nanoparticles.

Gold-decorated silica nanoparticles were synthesized in a two-step process in which silica nanoparticles were produced by chemical vapor synthesis using tetraethylorthosilicate (TEOS) and subsequently decorated using two different gas-phase evaporative techniques. Both evaporative processes resulted in gold decoration of the silica particles. This study compares the mechanisms of particle decoration for a production method in which the gas and particles remain cool to a method in which the entire aerosol is heated. Results of transmission electron microscopy and visible spectroscopy studies indicate that both methods produce particles with similar morphologies and nearly identical absorption spectra, with peak absorption at 500-550 nm. A study of the thermal stability of the particles using heated-TEM indicates that the gold decoration on the particle surface remains stable at temperatures below 900 °C, above which the gold decoration begins to both evaporate and coalesce.

Nucleation, growth, and control of ferroelectric-ferroelastic domains in thin polycrystalline films

The unique response of ferroic materials to external excitations facilitates them for diverse technologies, such as nonvolatile memory devices. The primary driving force behind this response is encoded in domain switching. In bulk ferroics, domains switch in a two-step process: nucleation and growth. For ferroelectrics, this can be explained by the Kolmogorov-Avrami-Ishibashi (KAI) model. Nevertheless, it is unclear whether domains remain correlated in finite geometries, as required by the KAI model. Moreover, although ferroelastic domains exist in many ferroelectrics, experimental limitations have hindered the study of their switching mechanisms. This uncertainty limits our understanding of domain switching and controllability, preventing thin-film and polycrystalline ferroelectrics from reaching their full technological potential. Here we used piezoresponse force microscopy to study the switching mechanisms of ferroelectric-ferroelastic domains in thin polycrystalline Pb 0.7Zr0.3TiO3 films at the nanometer scale. We have found that switched biferroic domains can nucleate at multiple sites with a coherence length that may span several grains, and that nucleators merge to form mesoscale domains, in a manner consistent with that expected from the KAI model. © 2012 American Physical Society.

Post-growth and in situ annealing on GaInNAs(Sb) and their application in 1.55 mu m lasers

Rapid thermal annealing (RTA) has been demonstrated as an important way to improve the crystal quality of GaInNAs(Sb)/GaAs quantum wells. However little investigation has been made into their application in laser growth, especially at a wavelength of 1.55 mu m. When a GaAs-based laser is grown, AlGaAs is usually used for cladding layers. The growth of the p-cladding layer usually takes 30-45 min at a growth temperature higher than that of the GaInNAs(Sb) active region, which affects the material quality. To investigate this effect, various post-growth annealing processes were performed to simulate this process. Great enhancement of the PL intensity was obtained by a two-step process which consisted of annealing first at 700 degrees C for 60 s and then at 600 degrees C for 45 min. We transferred this post-growth annealing to in situ annealing. Finally, a GaInNAsSb laser was grown with a 700 degrees C in situ annealing process. Continuous operation at room temperature of a GaAs-based dilute nitride laser with a wavelength beyond 1.55 mu m was realized for the first time.