A parameterized model of heat storage by lake sediments

A model of seasonal heat storage by lake sediments is proposed oriented at applications in climate modeling and at lake parameterization in numerical weather prediction. The computational efficiency is achieved by reformulating of the heat transfer problem as a set of ordinary differential equations for evolution of the temperature wave inside the upper sediment layer. Arising temperature and depth scales completely replace the conductivity of the sediment in the heat transfer equation and can be easily achieved from the lake water temperature observations without any data on the sediment thermal properties. The method is proposed for the scales estimation from the inverse solution of the model equations in special case of the constant water-sediment heat flux in ice-covered lakes. The method is tested on data from sediments of Lake Krasnoye, North-Western Russia. The long-term (1961–2002) modeling of temperature in German lakes Müggelsee and Heiligensee with a coupled one-dimensional model of lake water column and sediments has demonstrated an appreciable effect of the sediment heat storage on near-bottom temperatures in both lakes. Thus, incorporation of the sediment layer into lake temperature models can essentially improve, at low computational costs, the model performance, especially for shallow lakes. In addition, a better forecast of near-bottom temperature evolution on climatic scales can provide a better understanding of the response of lake benthic communities to global warming.     

A Novel Photoswitchable Azobenzene-Containing Local Anesthetic Ethercaine with Light-Controlled Biological Activity In Vivo

Pain is a common symptom that impairs the quality of life for people around the world. Local anesthetics widely used for pain relief have a number of side effects, which makes the development of both new drugs and new ways to control their activity particularly important. Photopharmacology makes it possible to reduce the side effects of an anesthetic and control its biological activity in the body. The purpose of this work was to create a new light-controlled local anesthetic and study its biological activity in animals. A compound with a simple scheme of synthesis was chosen to shift the UV-Vis absorption band towards the visible range of the spectrum and was synthesized for the first time. Some computer calculations were performed to make sure that the aforementioned changes would not lead to loss of biological activity. The micellar form of the new compound was prepared, and in vivo biological studies were carried out in rabbits. The existence of a local anesthetic effect, which disappeared almost completely on irradiation with light (λ = 395 nm), was shown using the surface anesthesia model. Moreover, the possibility of multiple reversible changes in the biological activity of ethercaine under the action of light was demonstrated. The latter compound manifests no local irritating effect, either. The data obtained indicate the prospects for the development of new compounds based on azobenzene for light-controlled local anesthesia.     

Transport and recombination in solar cells: New perspectives

The functioning of the solar cells relies on the photo-generation of carriers in p–n junctions and their subsequent recombination in the quasi-neutral regions. A number of basic issues concerning the physics of the operation of solar cells still remain obscure. This paper reports on some unsolved basic problems, namely: a model of the recombination processes that does not contradict Maxwell's equations; the role played by space charges in the transport phenomena, and the formation of quasi-neutral regions under the presence of non-equilibrium photo-generated carriers. In this work, a new formulation of the theory that explains the underlying physical phenomena involved in the generation of a photo-e.m.f. is presented.     

Thermal instability in freshwater lakes under ice: Effect of salt gradients or solar radiation?

The phenomenon of “temperature dichotomy”, or anomalous heating of surface water under the ice up to temperatures exceeding 4 °C is known to take place occasionally in solar-heated ice-covered freshwater lakes and has usually been explained by the stabilizing effect of the weak vertical salinity gradient created by the melt water flux from the ice and supporting the unstable temperature distribution. Here, we report an observation of the local temperature maximum in the upper part of the water column of ice-covered Lake Vendyurskoe (northwestern Russia). The observation was accompanied by vertically resolved measurements of the conductivity allowing estimation of the dissolved salts effect on the vertical density distribution. The results demonstrate insufficiency of the salt gradient to support the vertical stability of water column. Therefore, we suggest the vertically inhomogeneous radiation absorption to be the probable stabilizing mechanism here, similarly to radiatively heated boundary layers in the ocean, the atmosphere and star interiors. An analytical solution of the heat transfer equation is derived describing the temperature profile evolution in ice-covered lakes subject to solar radiation heating above the maximum density temperature. Observed daytime temperature profiles agree well with the analytical model that suggests the absence of convective mixing. According to the model, the temperature maximum is formed within a day that supports the hypothesis about the stabilizing effect of the solar radiation absorption. We conclude that in temperate lakes the warm layer should have diurnal character and should be destroyed during the nighttime by convection. In polar lakes, in turn, the warm layer can exist during essentially longer periods that is supported by application of the model to the previously published data from Lake Peters, Alaska. In this case, the ice melting rate can be significantly affected by the increased temperature gradient beneath the ice. Apart from potential effects on the ice melting rate and the spring plankton development in lakes, the regime represents a rare geophysical example of instability driven solely by radiative heating with many useful analogies in planetary and stellar physics.     

An overview of geoengineering of climate using stratospheric sulphate aerosols

We provide an overview of geoengineering by stratospheric sulphate aerosols. The state of understanding about this topic as of early 2008 is reviewed, summarizing the past 30 years of work in the area, highlighting some very recent studies using climate models, and discussing methods used to deliver sulphur species to the stratosphere. The studies reviewed here suggest that sulphate aerosols can counteract the globally averaged temperature increase associated with increasing greenhouse gases, and reduce changes to some other components of the Earth system. There are likely to be remaining regional climate changes after geoengineering, with some regions experiencing significant changes in temperature or precipitation. The aerosols also serve as surfaces for heterogeneous chemistry resulting in increased ozone depletion. The delivery of sulphur species to the stratosphere in a way that will produce particles of the right size is shown to be a complex and potentially very difficult task. Two simple delivery scenarios are explored, but similar exercises will be needed for other suggested delivery mechanisms. While the introduction of the geoengineering source of sulphate aerosol will perturb the sulphur cycle of the stratosphere signicantly, it is a small perturbation to the total (stratosphere and troposphere) sulphur cycle. The geoengineering source would thus be a small contributor to the total global source of 'acid rain' that could be compensated for through improved pollution control of anthropogenic tropospheric sources. Some areas of research remain unexplored. Although ozone may be depleted, with a consequent increase to solar ultraviolet-B (UVB) energy reaching the surface and a potential impact on health and biological populations, the aerosols will also scatter and attenuate this part of the energy spectrum, and this may compensate the UVB enhancement associated with ozone depletion. The aerosol will also change the ratio of diffuse to direct energy reaching the surface, and this may influence ecosystems. The impact of geoengineering on these components of the Earth system has not yet been studied. Representations for the formation, evolution and removal of aerosol and distribution of particle size are still very crude, and more work will be needed to gain confidence in our understanding of the deliberate production of this class of aerosols and their role in the climate system.     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Luminescent-plasmonic core–shell microspheres,doped with Nd3+ and modified with gold nanoparticles,exhibiting whispering gallery modes and SERS activity

Multifunctional core/shell type,luminescent-plasmonic material composed of lanthanide doped microspheres(≈50 μm) and gold nanoparticles(Au NPs;≈10-20 nm) deposited onto their surface,were successfully prepared(Nd~(3+):YAS@Au).The material was synthesized to combine the luminescence properties of the Nd~(3+)-doped microspheres,i.e.whispering resonance with plasmonic activity of the surface Au NPs,i.e.surface enhanced Raman scattering(SERS) effect,within a single,micro-sized material.The luminescent-plasmonic microspheres were used as the active SERS substrate for detection of the organic probe,and for generation of Whispering Gallery Modes(WGM),which red-shift together with increasing laser power(temperature elevation).The products obtained were analysed with optical,scanning and transmission electron microscopy(SEM and TEM),as well as by Raman,absorption and photoluminescence spectroscopies.     

Decamethylosmocene-catalyzed efficient oxidation of saturated and aromatic hydrocarbons and alcohols with hydrogen peroxide in the presence of pyridine

Decamethylosmocene, (Me₅C₅)₂Os (1), is a pre-catalyst in a very efficient oxidation of alkanes with hydrogen peroxide in acetonitrile at 20–60 °C. The reaction proceeds with a substantial lag period that can be reduced by the addition of pyridine in a small concentration. The lag period can be removed if 1 is incubated with pyridine and/or H₂O₂ in MeCN prior to the alkane oxidation. Alkanes, RH, are oxidized primarily to the corresponding alkyl hydroperoxides, ROOH. Turnover numbers attain 51,000 in the case of cyclohexane (maximum turnover frequency was 6000 h^?1) and 3600 in the case of ethane. The oxidation of benzene and styrene also occurs with a lag period to afford phenol and benzaldehyde, respectively. A kinetic study of cyclohexane oxidation and selectivity parameters (measured in the oxidation of n-heptane, methylcyclohexane, isooctane, cis- and trans-dimethylcyclohexanes) indicates that the oxidation of saturated, olefinic, and aromatic hydrocarbons proceeds with the participation of hydroxyl radicals. The 1/H₂O₂/py/MeCN system also oxidizes 1-phenylethanol to acetophenone.     

Magnetic pulse controlled microstructure development in Co49Ni21Ga30 single crystals

A pulsed magnetic field (MF) up to 0.6?T leads to the generation of fine microstructure through the change in the dynamics of the interaction process between the MF and the magnetic- and microstructure in Co₄₉Ni₂₁Ga₃₀ magnetic shape memory alloy single crystals. This paper addresses the impact of pulsed and permanent MF on the transformation behaviour in Co₄₉Ni₂₁Ga₃₀. A pulsed MF can result in different microstructural accommodation processes in stress-induced martensite, as compared to an application of a mechanical stress or permanent MF. In a pulsed MF, the development of new nano-twin systems in the martensitic structure of the CoNiGa alloy and the formation of fine magnetic domains at the microscale are observed.