Second harmonic generation in some donor-acceptor ethylenes—I

We report the absorption spectra, oscillator strengths, ground state and excited state dipole moments, and molecular second order polarizability coefficients (βCT) due to donor—acceptor charge transfer in four trisubstituted ethylenes, namely 1,1-bisdimethylamino-2-nitroethylene, 1,1-bispyrolidino-2-nitroethylene, 1,1-bispiperidino-2-nitroethylene and 1,1-bismorpholino-2-nitroethylene. The results are compared with that of trans-N,N-dimethylamino-nitroethylene, which has a large βCT. The powder second harmonic generation (SHG) intensity of all these molecules is also measured and only 1,1-bispiperidino-2-nitroethylene is found to possess an efficiency of 20% of that of urea under the same conditions. The SHG efficiency of this compound and deficiency in the other molecules in the powdered state is discussed in terms of their arrangements in the unit cell. The crystal structure of the active molecule is also presented and the structure—property relationship is critically examined in all these molecules.

Formation and preservation of pedogenic carbonates in South India, links with paleo-monsoon and pedological conditions: Clues from Sr isotopes, U-Th series and REEs

The influence of the pedogenic and climatic contexts on the formation and preservation of pedogenic carbonates in a climosequence in the Western Ghats (Karnataka Plateau, South West India) has been studied. Along the climosequence, the current mean annual rainfall (MAR) varies within a 80 km transect from 6000 mm at the edge of the Plateau to 500 mm inland. Pedogenic carbonates occur in the MAR range of 500-1200 mm. In the semi-arid zone (MAR: 500-900 mm), carbonates occur (i) as rhick hardpan calcretes on pediment slopes and (ii) as nodular horizons in polygenic black soils (i.e. vertisols). In the sub-humid zone (MAR: 900-1500 mm), pedogenic carbonates are disseminated in the black soil matrices either as loose, irregular and friable nodules of millimetric size or as indurated botryoidal nodules of centimetric to pluricentimetric size. They also occur at the top layers of the saprolite either as disseminated pluricentimetric indurated nodules or carbonate-cemented lumps of centimetric to decimetric size. Chemical and isotopic (Sr-87/Sr-86) compositions of the carbonate fraction were determined after leaching with 0.25 N HCl. The corresponding residual fractions containing both primary minerals and authigenic clays were digested separately and analyzed. The trend defined by the Sr-87/Sr-86 signatures of both labile carbonate fractions and corresponding residual fractions indicates that a part of the labile carbonate fraction is genetically linked to the local soil composition. Considering the residual fraction of each sample as the most likely lithogenic source of Ca in carbonates, it is estimated that from 24% to 82% (55% on average) of Ca is derived from local bedrock weathering, leading to a consumption of an equivalent proportion of atmospheric CO2. These values indicate that climatic conditions were humid enough to allow silicate weathering: MAR at the time of carbonate formation likely ranged from 400 to 700 mm, which is 2- to 3-fold less than the current MAR at these locations. The Sr, U and Mg contents and the (U-234/U-238) activity ratio in the labile carbonate fraction help to understand the conditions of carbonate formation. The relatively high concentrations of Sr, U and Mg in black soil carbonates may indicate fast growth and accumulation compared to carbonates in saprolite, possibly due to a better confinement of the pore waters which is supported by their high (U-234/U-238) signatures, and/or to higher content of dissolved carbonates in the pore waters. The occurrence of Ce, Mn and Fe oxides in the cracks of carbonate reflects the existence of relatively humid periods after carbonate formation. The carbonate ages determined by the U-Th method range from 1.33 +/- 0.84 kyr to 7.5 +/- 2.7 kyr and to a cluster of five ages around 20 kyr, i.e. the Last Glacial Maximum period. The young occurrences are only located in the black soils, which therefore constitute sensitive environments for trapping and retaining atmospheric CO2 even on short time scales. The maximum age of carbonates depends on their location in the climatic gradient: from about 20 kyr for centimetric nodules at Mule Hole (MAR = 1100 mm/yr) to 200 kyr for the calcrete at Gundlupet (MAR = 700 mm/yr, Durand et al., 2007). The intensity of rainfall during wet periods would indeed control the lifetime of pedogenic carbonates and thus the duration of inorganic carbon storage in soils. (C) 2010 Elsevier Ltd. All rights reserved.

Itsevalikoituminen verkkokyselytutkimuksen haasteena

Internet-yhteyksien käyttö yleistyi Suomessa vuoden 1993 jälkeen, mistä lähtien Internetiä on alettu käyttämään yhä enemmän tiedonkeruun apuvälineenä. Apuvälineenä Internetiä käytetään sekä yhteydenotossa vastaajiin että vastauksien keruussa. Internetin avulla tehtyihin kyselytutkimuksiin liittyy edelleen paljon avoimia metodologisia kysymyksiä. Useimmiten perinteistä, satunnaistettua otoksen keruuta ei voida suorittaa, koska kehikkoperusjoukkoa ei pystytä määrittelemään. Tällöin joudutaan turvautumaan itsevalikoituneeseen verkkotiedonkeruuseen, jossa kyselyä mainostetaan avoimesti tutkimuksen kohteena olevalle ryhmälle ja vastaajat itse päättävät osallistuvatko kyselyyn vai eivät. Samalla Internet-populaation alipeitto voi aiheuttaa harhaa tutkimustuloksiin, jos tavoiteperusjoukkona on jokin suuri populaatio, jossa kaikki eivät käytä Internetiä. Tutkielman tavoite on antaa kuva verkkotiedonkeruun ajanmukaisista menetelmistä sekä erityisesti selvittää itsevalikoituneen verkkotiedonkeruun tilastollista metodologiaa, mahdollisuuksia ja rajoituksia. Tarkoituksena on myös selvittää, kuinka hyvin valikoituneen verkkokyselytutkimuksen harhan korjaaminen onnistuu ajanmukaisilla painotusmenetelmillä. Kyselytutkimusten vastauskadosta sekä valikoituneisuudesta johtuvaa harhaa voidaan korjata painotusmenetelmillä, jos vastauskadon mekanismia tai valikoitumismekanismia pystytään selittämään. Harhaa voidaan korjata sopivien apumuuttujien avulla, jotka korreloivat tulosmuuttujan tai osallistumispäätöksen kanssa. Apumuuttujien tiedot täytyy olla tiedossa sekä kyselyyn osallistujilta että ei-osallistujilta. Perinteisen todennäköisyysotantaan perustuvan aineiston vastauskadosta johtuvaa harhaa korjataan useimmiten jälkiosituspainoilla. Itsevalikoituneen verkkokyselytutkimuksen valikoitumisharhan korjaamiseen on esitetty kaksivaiheista painotusmenetelmää, jonka tarkoituksena on korjata harhaa, joka johtuu Internetin käyttömahdollisuudesta sekä itse osallistumispäätöksestä. Internetin käyttömahdollisuus voidaan mallintaa propensiteettipistemäärän avulla, jonka käänteislukua voidaan käyttää painokertoimena harhan korjaamiseksi. Osallistumispäätöksestä johtuvaa harhaa voidaan korjata tasaamalla aineiston apumuuttujien reunajakaumat vastaamaan populaation reunajakaumia. Tutkimuksessa tarkastellaan kolmea aineistoa. Kelan tutkimusosasto keräsi vuoden 2010 syyskuussa pilotin itsevalikoituneesta verkkokyselytutkimuksesta. Kyselyllä pyrittiin kartoittamaan Suomen 16–80-vuotiaiden kansalaisten yksityisten terveys- ja hammashoitopalvelujen hintatietoja ja tarpeita. Sama kysely lähetettiin myös otosperusteisesti Kelan työntekijöille. Molemmissa kyselyissä vastaukset kerättiin sähköisellä Internet-kyselyllä. Lisäksi tutkielmassa tarkastellaan TNS Gallupin otosperusteisesti Suomen kansalaisilta keräämään suppeampaa puhelinhaastattelukyselyä, jota käytettiin myös itsevalikoituneen aineiston kalibrointiaineistona. Kyselytutkimusaineistojen vastauskatoa korjattiin erilaisilla painotusmenetelmillä, joiden avulla pystyttiin tarkastelemaan kuinka hyvin eri painotusmenetelmät pystyvät korjaamaan valikoitumisesta johtuvaa harhaa. Otosperusteisia verkkokyselytutkimuksia korjattiin jälkiosituspainoilla ja painotuksissa onnistuttiin hyvin, koska aineistossa ei ollut suurta valikoituneisuutta. Itsevalikoituneen verkkokyselytutkimuksen painotuksessa jouduttiin kohtaamaan paljon ongelmia, koska aineisto oli suuresti valikoitunut, ja siinä oli paljon vastauskatoa. Itsevalikoituneen aineiston valikoitumisen harhaa onnistuttiin kuitenkin osaksi korjaamaan, ja osa tulosmuuttujien jakaumatiedoista vastasi lähes otosperusteisen kyselytutkimuksen jakaumatietoja. Tutkimuksen keskeisin tulos oli, että vaikka verkkokyselyn tekeminen on halvempaa ja vähemmän työläämpää kuin otosperusteisen kyselytutkimuksen tekeminen, verkkokyselytutkimuksen suunnitteluun on panostettava entistä enemmän. Itsevalikoituneen verkkokyselytutkimuksen keruussa on suunniteltava tarkemmin kyselyn mainostaminen vastaajaehdokkaille, jotta valikoitumisesta johtuvaa harhaa voidaan paremmin hallita. Tutkimuksessa kävi myös ilmi, että sekä asennetta ja käyttäytymistä kuvaavia kysymyksiä on tärkeä olla kyselytutkimuksissa mukana, koska näiden avulla pystytään selittämään paremmin valikoitumisesta johtuvaa harhaa, kuin pelkästään sosiodemografisten muuttujien avulla.

A note on the choice of interfacial friction angle

Estimates of interfacial friction angle (delta) are necessary for the design of retaining structures and deep foundations, Recommendations in the literature regarding delta values are often contradictory and are therefore not easy to apply in geotechnical design, A critical examination of past studies in terms of data generation techniques used and conclusions drawn indicates that two distinctly different test procedures/techniques have been evolved. The interfacial situation in practice can also be categorized into two broad types, These two types of interface problems in geotechnical engineering are (a) the structure is placed on the free surface of prepared fill (type A situation) and (b) the fill is placed against the material surface which functions as a confined boundary (type B situation), The friction angle delta depends on the surface roughness of the construction material, But in the type A situation, it is independent of density and its limiting maximum value (delta(lim)) is the critical state friction angle phi(cv). In the type B situation, it is dependent on density of the fill and its limiting maximum value is the peak angle of internal friction phi(p) of the fill.

Electrical and Optical Properties of Diketopyrrolopyrrole-Based Copolymer Interfaces in Thin Film Devices

Two donor acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) have been synthesized for their application in organic devices such as metal-insulator semiconductor (MIS) diodes and field-effect transistors (FETs). The semiconductor-dielectric interface was characterized by capacitance-voltage and conductance-voltage methods. These measurements yield an interface trap density of 4.2 x 10(12) eV(-1) cm(-2) in TDPP-BBT and 3.5 x 10(12) eV(-1) cm(-2) in PDPP-BBT at the flat-band voltage. The FETs based on these spincoated DPP copolymers display p-channel behavior with hole mobilities of the order 10(-3) cm(2)/(V s). Light scattering studies from PDPP-BBT FETs show almost no change in the Raman spectrum after the devices are allowed to operate at a gate voltage, indicating that the FETs suffer minimal damage due to the metal-polymer contact or the application of an electric field. As a comparison Raman intensity profile from the channel-Au contact layer in pentacene FETs are presented, which show a distinct change before and after biasing.

Punching shear strength of flat slab corner column connections .1. Reinforced concrete connections

This paper presents the details of an experimental study on punching shear strength and behaviour of reinforced concrete corner column connections in flat slabs; a quasi-empirical method is proposed for computing the punching shear strength. The method has also been extended for punching shear strength prediction at interior and edge column connections. The test results compare better with the strengths predicted by the proposed method than those by Ingvarson, Zaglool and Pollet available in the literature. Further, the experimental strengths of interior, edge and corner column connections have been compared with the strengths predicted by the proposed method and the two codes of practice, viz. ACI and BS code, to demonstrate the usefulness of the method.

Punching shear strength of flat slab corner column connections .2. Fibre-reinforced concrete connections

This paper gives the details of the studies undertaken to examine the strength and behaviour of fibre-reinforced concrete corner column connections in flat slabs. Tests have been conducted on 16 specimens with varying reinforcement ratio, moment/shear ratio (load eccentricity) and volume fraction of fibres. A quasi-empirical method has been proposed for computing the punching shear strength. The method has also been extended to fibre-reinforced concrete interior column connections, tests on which are available in the literature. The test results have been compared with the strength predicted by the proposed method for corner column as well as interior column connections and a satisfactory agreement noticed.

The log delta log t method for the determination of the coefficient of consolidation

The behaviour of saturated soils undergoing consolidation is very complex, It may not follow Terzaghi's theory over the entire consolidation process, Different soils may behave in such a way as to fit into Terzaghi's theory over some specific stages of the consolidation process (percentage of consolidation), This may be one of the reasons for the difficulties faced by the existing curve-fitting procedures in obtaining the coefficient of consolidation, c(v). It has been shown that the slope of the initial linear portion of the theoretical log U-log T curve is constant over a wider range of degree of consolidation, U, when compared with the other methods in use, This initial well-defined straight line in the log U-log T plot intersects the U = 100% line at T = pi/4, which corresponds to U = 88.3%, The proposed log delta-log t method is based on this observation, which gives the value of c(v) through simple graphical construction, In the proposed method, which is more versatile, identification of the characteristic straight lines is very clear; the intersection of these lines is more precise and the method does not depend upon the initial compression for the determination of c(v).

Secondary compression factor

When the variation of secondary compression, with log(10) t is non-linear, the quantification of secondary settlement through the coefficient of secondary compression, C-alpha epsilon, becomes difficult which frequently leads to an underestimate of the settlement, Log(10) delta - log(10) t representation of such true-compression data has the distinct advantage of exhibiting linear secondary compression behaviour over an appreciably larger time span. The slope of the secondary compression portion of the log(10) e - log(10) t curve expressed as Delta(log e)/(log t) and called the 'secondary compression factor', m, proves to be a better alternative to C-alpha epsilon and the prediction of secondary settlement is improved.

Collapse behaviour of a residual soil

Residually derived red soils occur in Bangalore District of Karnataka State, India. The porous and unsaturated nature of the red soils makes them susceptible to collapse on wetting under load. The present study analyses the collapse behaviour of an unsaturated bonded (undisturbed) red soil from Bangalore referenced to tests on samples in an unbonded (remoulded) state. A filter paper method was used to determine the matric suction of the bonded and unbonded specimens, and mercury intrusion porosimetry (MIP) was used to determine their soil structure. Analysis of the experimental results shows that bonding plays an important role in the collapse behaviour of the unsaturated residual soil. The results of the study also provide insight into the volume change behaviour of unsaturated bonded soils on wetting within and beyond the yield locus.

Seismic bearing capacity factors for spread foundations

The effect of horizontal earthquake body forces on the bearing capacity of foundations has been examined computationally in a rigorous manner by employing the method of stress characteristics. The bearing capacity factors N-c, N-q and N-y, due to the components of soil cohesion, ground surcharge pressure and soil unit weight respectively, have been plotted as a function of earthquake acceleration coefficient (a(h)) for different values of soil friction angle (phi). The inclusion of earthquake body forces causes a considerable reduction in the bearing capacity factors. The bearing capacity factors N-c and N-q are seen to be approximately of the same magnitude as those reported in the literature on the basis of different solution methods. However, the obtained values of N-y are found to be significantly smaller than the available results. The nature of the pressure distribution along the footing base and the geometry of the observed failure patterns vary with the consideration of earthquake body forces.

Swelling pressure of sodium montmorillonites

Determination of the swelling pressure of montmorillonitic clays is required in many situations concerned with stability problems of foundations, retaining walls, slope stability of embankments and excavations in expansive soils. Recently expansive soils such as bentonite have been used as a mixture backfill material, for example as backfill material for nuclear waste disposal systems, for which a knowledge of the swelling pressure is desirable. This is the pressure required to keep the clay-water system at the required void ratio when it is allowed to absorb water or electrolyte. If the pressure is less than the swelling pressure, volume expansion occurs; if the pressure is more than the swelling pressure, volume compression occurs. Because of isomorphous substitutions in the crystal lattice, in general the clay particles carry negative charges at the surfaces of the platelets. Exchangeable cations in the clay media are attracted to these negative charges, but this attraction is opposed by the tendency of ions to be distributed. As a result, an electric diffuse double layer is formed (Gouy, 1910).

VIP blockade leads to microcephaly in mice via disruption of Mcph1-Chk1 signaling

Autosomal recessive primary microcephaly (MCPH) is a genetic disorder that causes a reduction of cortical outgrowth without severe interference with cortical patterning. It is associated with mutations in a number of genes encoding protein involved in mitotic spindle formation and centrosomal activities or cell cycle control. We have shown previously that blocking vasoactive intestinal peptide (VIP) during gestation in mice by using a VIP antagonist (VA) results in microcephaly. Here, we have shown that the cortical abnormalities caused by prenatal VA administration mimic the phenotype described in MCPH patients and that VIP blockade during neurogenesis specifically disrupts Mcph1 signaling. VA administration reduced neuroepithelial progenitor proliferation by increasing cell cycle length and promoting cell cycle exit and premature neuronal differentiation. Quantitative RT-PCR and Western blot showed that VA downregulated Mcph1. Inhibition of Mcph1 expression led to downregulation of Chk1 and reduction of Chk1 kinase activity. The inhibition of Mcph1 and Chk1 affected the expression of a specific subset of cell cycle-controlling genes and turned off neural stem cell proliferation in neurospheres. Furthermore, in vitro silencing of either Mcph1 or Chk1 in neurospheres mimicked VA-induced inhibition of cell proliferation. These results demonstrate that VIP blockade induces microcephaly through Mcph1 signaling and suggest that VIP/Mcph1/Chk1 signaling is key for normal cortical development.

Dynamic properties of sand from dry to fully saturated states

By using bender and extender elements test, the velocities of the primary and shear waves, V(P) and V(s) respectively, were measured for a sandy material by gradually varying the degree of saturation, S(r), between the dry and fully saturated states. The effect on the results of varying the relative density and effective confining pressure was also studied. The measurements clearly reveal that for a certain optimum S(r), which is around 0.7-0.9% for the chosen sand, the value of the shear modulus G reaches a maximum value, whereas the corresponding Poisson's ratio nu attains a minimum value. The values of the shear modulus corresponding to S(r) approximate to 0% and S(r) = 100% tend towards the same value. For values of Skempton's B parameter greater than 0.99, the values of V(P) and nu rise very sharply to those of water. The predictions from Biot's theory with respect to the variation of V(P) with S(r) match well with the measured experimental data.

Seismic reliability assessment of internal stability of reinforced soil walls using the pseudo-dynamic method

The study focuses on probabilistic assessment of the internal seismic stability of reinforced soil structures (RSS) subjected to earthquake loading in the framework of the pseudo-dynamic method. In the literature, the pseudo-static approach has been used to compute reliability indices against the tension and pullout failure modes, and the real dynamic nature of earthquake accelerations cannot be considered. The work presented in this paper makes use of the horizontal and vertical sinusoidal accelerations, amplification of vibrations, shear wave and primary wave velocities and time period. This approach is applied to quantify the influence of the backfill properties, geosynthetic reinforcement and characteristics of earthquake ground motions on reliability indices in relation to the tension and pullout failure modes. Seismic reliability indices at different levels of geosynthetic layers are determined for different magnitudes of seismic acceleration, soil amplification, shear wave and primary wave velocities. The results are compared with the pseudo-static method, and the significance of the present methodology for designing reinforced soil structures is discussed.