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111.
Vehkamäki H Määttänen A Lauri A Kulmala M Winkler P Vrtala A Wagner PE 《The Journal of chemical physics》2007,126(17):174707
In this paper we present a new form of the nucleation theorems applicable to heterogeneous nucleation. These heterogeneous nucleation theorems allow, for the first time, direct determination of properties of nanoclusters formed on pre-existing particles from measured heterogeneous nucleation probabilities. The theorems can be used to analyze the size (first theorem) and the energetics (second theorem) of heterogeneous clusters independent of any specific nucleation model. We apply the first theorem to the study of small water and n-propanol clusters formed at the surface of 8 nm silver particles. According to the experiments the size of the two-component critical clusters is found to be below 90 molecules, and only less than 20 molecules for pure water, less than 300 molecules for pure n-propanol. These values are drastically smaller than the ones predicted by the classical nucleation theory, which clearly indicates that the nucleating clusters are too small to be quantitatively described using a macroscopic theory. 相似文献
112.
We study the conformational reorganization of formic acid (FA) in solid neon and report the higher-energy cis-FA monomer and one form of the trans-cis FA dimers. They were prepared by selective vibrational excitation of the trans-FA monomer and trans-trans dimer. The proton tunneling decay of cis-FA monomer is surprisingly very fast in solid neon, two orders of magnitude faster than in solid argon. It was also found that the stability of the trans-cis dimer against proton tunneling is enormously enhanced in solid neon compared to the monomer (by a factor of approximately 300). These results are discussed in terms of matrix solvation and hydrogen bonding. 相似文献
113.
We have postulated a mechanism for the reaction of sulfuric acid with stabilized Criegee intermediates (sCIs). We have computed Gibbs free energies for the reaction of sulfuric acid with two biogenic sCIs and three smaller model species. We have also calculated Gibbs free energies for two competing sink reactions. Due to the large size of the biogenic sCIs, the computations have been performed at the relatively modest B3LYP/6-31G(d,p) and B3LYP/6-311+G(2d,p) levels. However, single-point RI-CC2/def2-QZVPP calculations for the (CH3)(2)COO model species are in good agreement with the B3LYP results. The reaction is found to be strongly exothermic for all studied species. Activation barrier calculations on the (CH3)(2)COO model species further indicate that the reaction with sulfuric acid may proceed significantly faster than the sink reaction with water. If the same applies to the biogenic sCIs, the proposed reactions could account for some part of the organically assisted new particle formation events observed in the atmosphere. 相似文献
114.
Adipic and malonic acid aqueous solutions: surface tensions and saturation vapor pressures 总被引:1,自引:0,他引:1
Riipinen I Koponen IK Frank GP Hyvärinen AP Vanhanen J Lihavainen H Lehtinen KE Bilde M Kulmala M 《The journal of physical chemistry. A》2007,111(50):12995-13002
The surface tension of adipic aqueous solutions was measured as a function of temperature (T=278-313 K) and adipic acid mole fraction (X=0.000-0.003) using the Wilhelmy plate method. A parametrization fitted to these data is presented. The evaporation rates of binary water-malonic and water-adipic acid droplets were measured with a TDMA technique at different temperatures (T=293-300 K) and relative humidities (58-80%), and the saturation vapor pressures of subcooled liquid malonic and adipic acids were derived from the data using a binary evaporation model. The temperature dependence of the vapor pressures was obtained as least-squares fits to the derived vapor pressures: ln(Psat,l) (Pa)=220.2389-22634.96/T (K)-26.66767 ln T (K) for malonic acid and ln(Psat,l) (Pa)=140.6704-18230.97/T (K)-15.48011 ln T (K) for adipic acid. 相似文献
115.
Natalia Tong-Ochoa Kari Kopra Markku Syrjänpää Nicolas Legrand Harri Härmä 《Analytica chimica acta》2015
Protein post-translational modifications (PTMs) are regulatory mechanisms carried out by different enzymes in a cell. Kinase catalyzed phosphorylation is one of the most important PTM affecting the protein activity and function. We have developed a single-label quenching resonance energy transfer (QRET) assay to monitor tyrosine phosphorylation in a homogeneous high throughput compatible format. Epidermal growth factor receptor (EGFR) induced phosphorylation was monitored using Eu3+-chelate labeled peptide and label-free phosphotyrosine specific antibody in presence of a soluble quencher molecule. In the QRET kinase assay, antibody binding to phosphorylated Eu3+-peptide protects the Eu3+-chelate from luminescence quenching, monitoring high time-resolved luminescence (TRL) signals. In the presence of specific kinase inhibitor, antibody recognition and Eu3+-chelate protection is prevented, allowing an efficient luminescence quenching. The assay functionality was demonstrated with a panel of EGFR inhibitors (AG-1478, compound 56, erlotinib, PD174265, and staurosporine). The monitored IC50 values ranged from 0.08 to 155.3 nM and were comparable to those found in the literature. EGFR activity and inhibition assays were performed using low nanomolar enzyme and antibody concentration in a 384-well plate format, demonstrating its compatibility for high throughput screening (HTS). 相似文献
116.
Ebben CJ Shrestha M Martinez IS Corrigan AL Frossard AA Song WW Worton DR Petäjä T Williams J Russell LM Kulmala M Goldstein AH Artaxo P Martin ST Thomson RJ Geiger FM 《The journal of physical chemistry. A》2012,116(32):8271-8290
This article summarizes and compares the analysis of the surfaces of natural aerosol particles from three different forest environments by vibrational sum frequency generation. The experiments were carried out directly on filter and impactor substrates, without the need for sample preconcentration, manipulation, or destruction. We discuss the important first steps leading to secondary organic aerosol (SOA) particle nucleation and growth from terpene oxidation by showing that, as viewed by coherent vibrational spectroscopy, the chemical composition of the surface region of aerosol particles having sizes of 1 μm and lower appears to be close to size-invariant. We also discuss the concept of molecular chirality as a chemical marker that could be useful for quantifying how chemical constituents in the SOA gas phase and the SOA particle phase are related in time. Finally, we describe how the combination of multiple disciplines, such as aerosol science, advanced vibrational spectroscopy, meteorology, and chemistry can be highly informative when studying particles collected during atmospheric chemistry field campaigns, such as those carried out during HUMPPA-COPEC-2010, AMAZE-08, or BEARPEX-2009, and when they are compared to results from synthetic model systems such as particles from the Harvard Environmental Chamber (HEC). Discussions regarding the future of SOA chemical analysis approaches are given in the context of providing a path toward detailed spectroscopic assignments of SOA particle precursors and constituents and to fast-forward, in terms of mechanistic studies, through the SOA particle formation process. 相似文献
117.
Vehkamäki H McGrath MJ Kurtén T Julin J Lehtinen KE Kulmala M 《The Journal of chemical physics》2012,136(9):094107
The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster. 相似文献
118.
Chernichenko K Nieger M Leskelä M Repo T 《Dalton transactions (Cambridge, England : 2003)》2012,41(30):9029-9032
Two 2-[bis(pentafluorophenyl)boryl]-N,N-dialkylanilines reported here exemplify a new class of intramolecular frustrated B/N Lewis pairs. A structure closely related to this class structure was synthesized in 2003 by Piers et al. but was unable to activate H(2). The new aminoboranes can activate hydrogen at near ambient conditions; besides, one of them can hydrogenate imines and enamines in a catalytic fashion demonstrating the validity of the original Piers' approach to hydrogen activation with ansa-aminoboranes. 相似文献
119.
Cascade linear phase recursive half-band filters implement the most efficient digital down converter
fred harris Elettra Venosa Xiaofei Chen Markku Renfors 《Analog Integrated Circuits and Signal Processing》2012,73(2):531-543
The digital down converter (DDC) is a fundamental component in modern DSP based receivers. The basic architecture is the DSP implementation of the Edwin Armstrong heterodyne circuit. It is formed by three processes, a quadrature heterodyne, a pair of low-pass filters, and an M-to-1 down sampler. The index M is the ratio of input to output bandwidth of the filtering process. When M is large, the filtering is often performed in two sub-filters: a cascade integrator comb (CIC) filter that performs most of the down sampling followed by a pair of half-band filters that perform spectral correction, some final bandwidth reduction, and the remainder of the down-sampling. The attraction of the CIC filter is that it performs the filtering without multiplies. In this paper we present two alternate filter structures that offer significant computational advantages over the conventional CIC based DDC. These architectures offer the minimum power implementation of a DDC and likely will find great value in battery operated radio receivers. 相似文献
120.
Winkler PM Vrtala A Steiner G Wimmer D Vehkamäki H Lehtinen KE Reischl GP Kulmala M Wagner PE 《Physical review letters》2012,108(8):085701
First order phase transitions involve nucleation, formation of nanoscale regions of a new phase within a metastable parent phase. Using the heterogeneous nucleation theorem we show how clusters formed by nucleation on single molecules evolve from the gas phase and determine the critical size beyond which condensation starts to form aerosol particles. Our experiments reveal the activation of molecules into droplets to happen via formation of critical clusters substantially larger than the seed molecule. The nanosized critical clusters were found to be well predicted by the Kelvin-Thomson relation pointing directly to the key step in the phase transition. 相似文献