Lewis base mediated autoionization of GeCl2 and SnCl2

Cationic and anionic species of heavier low-valent group 14 elements are intriguing targets in main group chemistry due to their synthetic potential and industrial applications. In the present study, we describe the synthesis of cationic (MCl(+)) and anionic (MCl(3)(-)) species of heavier low-valent group 14 elements of germanium(II) and tin(II) by using the substituted Schiff base 2,6-diacetylpyridinebis(2,6-diisopropylanil) as Lewis base (LB). Treatment of LB with 2 equiv of GeCl(2)·dioxane and SnCl(2) in toluene gives compounds [(LB)Ge(II)Cl](+)[Ge(II)Cl(3)](-) (1) and [(LB)Sn(II)Cl](+)[Sn(II)Cl(3)](-) (2), respectively, which possess each a low-valent cation and an anion. Compounds 1 and 2 are well characterized with various spectroscopic methods and single crystal X-ray structural analysis.     

On the structure and desorption dynamics of DNA bases adsorbed on gold: a temperature-programmed study

The structure and desorption dynamics of mono- and multilayer samples of adenine, cytosine, guanine, and thymine on polycrystalline gold thin films are studied using temperature-programmed desorption-infrared reflection absorption spectroscopy (TPD-IRAS) and temperature-programmed desorption-mass spectroscopy (TPD-MS). It is shown that the pyrimidines, adenine and guanine, adsorb to gold in a complex manner and that both adhesive (adenine) and cohesive (guanine) interactions contribute the apparent binding energies to the substrate surface. Adenine displays at least two adsorption sites, including a high-energy site (210 degrees C, approximately 136 kJ/mol), wherein the molecule coordinates to the gold substrate via the NH2 group in an sp3-like, strongly perturbed, nonplanar configuration. The purines, cytosine and thymine, display a less complicated adsorption/desorption behavior. The desorption energy for cytosine (160 degrees C, approximately 122 kJ/mol) is similar to those obtained for adenine and guanine, but desorption occurs from a single site of dispersed, nonaggregated cytosine. Thymine desorbs also from a single site but at a significantly lower energy (100 degrees C, approximately 104 kJ/mol). Infrared data reveal that the monolayer architectures discussed herein are structurally very different from those observed for the bases in the bulk crystalline state. It is also evident that both pyrimidines and purines adsorb on gold with the plane of the molecule in a nonparallel orientation with respect to the substrate surface. The results of this work are discussed in the context of improving the understanding of the design of capturing oligonucleotides or DNA strands for bioanalytical applications, in particular, for gold nanoparticle-based assays.     

Reply to da Rocha and Rodrigues' comments on the orientation congruent algebra and twisted forms in electrodynamics

The recent claim by da Rocha and Rodrigues that the nonassociative orientation congruent algebra (???? algebra) and native Clifford algebra are incompatible with the Clifford bundle approach is false. The new native Clifford bundle approach, in fact, subsumes the ordinary Clifford bundle one. Associativity is an unnecessarily too strong a requirement for physical applications. Consequently, we obtain a new principle of nonassociative irrelevance for physically meaningful formulas. In addition, the adoption of formalisms that respect the native representation of twisted (or odd) objects and physical quantities is required for the advancement of mathematics, physics, and engineering because they allow equations to be written in sign‐invariant form. This perspective simplifies the analysis of, resolves questions about, and ends needless controversies over the signs, orientations, and parities of physical quantities.     

Effects of enhanced UV-B on pigment-based phytoplankton biomass and composition of mesocosm-enclosed natural marine communities from three latitudes

A series of three outdoor mesocosm experiments was undertaken in Rimouski (Canada), Ubatuba (Brazil) and Ushuaia (southern Argentina) to examine the effects of lamp-enhanced UV-B (280-320 nm) on phytoplankton communities isolated from seawater at each site. Detailed pigment composition was used to identify these communities. Each experiment compared three replicated UV-B treatments, consisting of natural sunlight conditions (NUVB), low-level UV-B enhancement corresponding to local 30% ozone depletion (LUVB) and high-level enhancement corresponding to 60% ozone depletion (HUVB). Each mesocosm (ca 2 m deep) was mixed continuously (turnover time, ca 1.3 h) and samples were obtained daily over 7-10 days. In Rimouski a large diatom bloom occurred during the first week. Repeated-measures analysis of variance (RM-ANOVA), with time as the repeated factor, showed slight but statistically significant increases in the chlorophyll (Chl) a level with the HUVB treatment, which were especially obvious over the last 3 days of the experiment. A large decrease in grazers (ciliates) that was observed concurrently with this treatment is the most likely explanation for the increase in Chl a level. The lack of negative effect on algal biomass by enhanced UV-B is attributed to the mixing inside the mesocosms and to the relatively low UV-B penetration. In Ubatuba levels of most pigments decreased over time, particularly fucoxanthin, Chl c3 and alloxanthin. The RM-ANOVA showed no effect of the UV-B treatments, except for Chl c3, which had significantly lower concentrations under natural UVB conditions, indicating that enhanced UV-B directly or indirectly favored Chl c3 algae (likely prymnesiophytes). Although particulate organic carbon concentration was significantly larger during HUVB treatment than during the other treatments, Chl a was unaffected, suggesting that enhanced UV-B favored heterotrophs. Lack of algal growth during this experiment was attributed to low nutrient concentrations (which were the lowest of the three sites), high irradiances (which were the highest noon incident photosynthetically available radiation and UV of the three sites) and UV-B penetration down to the bottom of the mesocosms. In Ushuaia a small bloom took place over the first 5 days. The RM-ANOVA showed no overall effect of the UV-B treatments for any of the pigments examined but on the last 3 days of the experiment several green algae-type pigments, such as Chl b and siphonein, showed increased concentrations under the HUVB treatment. UV-B enhancement hence favored green algae, as seen from the stronger increase over time in the ratio of Chl b to Chl a associated with the HUVB treatment. UV-B enhancement also seemed to cause a slight decrease in physiological condition, because the relative concentration of chlorophyllide a and some pheophorbides that may be the product of dying algae increased during the HUVB treatments in Ubatuba and particularly in Ushuaia (where UV-B also penetrated to the bottom of mesocosms). For all three sites changes in phytoplankton biomass due to the UV-B treatments were minor, even though UV-B enhancement was important. This study indicates that effects of enhanced UV-B on the community structure of both phytoplankton and their grazers are potentially more important than effects on overall algal biomass.     

Modulating and scanning the mode-lock frequency of an 800-MHz femtosecond Ti:sapphire laser

An 800-MHz self-mode-locked femtosecond Ti:sapphire laser has been developed whose mode-lock frequency can be robustly scanned and modulated. The laser is based on the three-element design of Ramaswamy-Paye and Fujimoto [Opt. Lett. 19, 1756 (1994)]. By translation and modulation of the position of the prismatic output coupler, the mode-lock frequency can be reliably scanned more than 1% and modulated at 80 Hz with a deviation of 2.5 kHz without interrupting the mode lock, changing the pulse length, or inducing significant amplitude modulation. An application in tunable high-resolution terahertz spectroscopy is also demonstrated.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Core electrostatic fluctuations and particle transport in a reversed-field pinch

Potential and electron-density fluctuation profiles, phi(r) and ?(e)(r)/n(e), are measured for the first time in the core of a reversed-field pinch using a heavy ion beam probe. It is found that the fluctuations are broadband and correlated with the core resonant m/n=1/6 tearing mode. The electrostatic-fluctuation-induced particle transport in the core of standard RFP plasmas, estimated from measured , is small compared to the total particle flux. Measurements of fluctuations and estimates of fluctuation induced particle transport in improved confinement RFP discharges are also presented.     

Spatial resolution optimization of backscattered electron images using Monte Carlo simulation

The relation between probe size and spatial resolution of backscattered electron (BSE) images was studied. In addition, the effect of the accelerating voltage, the current intensity and the sample geometry and composition were analyzed. An image synthesis method was developed to generate the images from backscattered electron coefficients obtained from Monte Carlo simulations. Spatial resolutions of simulated images were determined with the SMART-J method, which is based on the Fourier transform of the image. The resolution can be improved by either increasing the signal or decreasing the noise of the backscattered electron image. The analyses demonstrate that using a probe size smaller than the size of the observed object (sample features) does not improve the spatial resolution. For a probe size larger than the feature size, the spatial resolution is proportional to the probe size.