Growth Kinetics of ZnO Nanocrystals in the Presence of a Base: Effect of the Size of the Alkali Cation

Following an earlier study (J. Am. Chem Soc. 2007, 129, 4470) describing a very unusual growth kinetics of ZnO nanoparticles, we critically evaluate here the proposed mechanism involving a crucial role of the alkali base ion in controlling the growth of ZnO nanoparticles using other alkali bases, namely, LiOH and KOH. While confirming the earlier conclusion of the growth of ZnO nanoparticles being hindered by an effective passivating layer of cations present in the reaction mixture and thereby generalizing this phenomenon, present experimental data reveal an intriguing nonmonotonic dependence of the passivation efficacy on the ionic size of the alkali base ion. This unexpected behavior is rationalized on the basis of two opposing factors: (a) solvated cationic radii and (b) dissociation constant of the base.

An unusual axial co-ordination of phenolate oxygen to copper(II): crystal structure of chloro(2-[bis(2-pyridylmethyl)aminomethyl]-4-nitrophenolato)copper(II)

A tripod ligand possessing two pyridine moieties and a phenolato group as pendants forms a mononuclear complex with an axial copper(II)–phenolate co-ordination in a square-pyramidal environment.

Electron energy loss spectroscopic study of Cr(CO)6, Mo(CO)6 and W(CO)6 in the vapour phase

Electron energy loss spectra (EELS) of Cr, Mo and W hexacarbonyls in the vapour phase are reported. Most of the bands observed are similar to those in optical spectra, but the two high energy transitions in the 9·8–11·2 eV region are reported here for the first time. Based on the orbital energies from the ultraviolet photoelectron spectra and the electronic transition energies from EELS and earlier optical studies, the molecular energy level schemes of these molecules are constructed.

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Indian Ocean Dipole: Processes and impacts

Equatorial Indian Ocean is warmer in the east, has a deeper thermocline and mixed layer, and supports a more convective atmosphere than in the west. During certain years, the eastern Indian Ocean becomes unusually cold, anomalous winds blow from east to west along the equator and southeastward off the coast of Sumatra, thermocline and mixed layer lift up and the atmospheric convection gets suppressed. At the same time, western Indian Ocean becomes warmer and enhances atmospheric convection. This coupled ocean-atmospheric phenomenon in which convection, winds, sea surface temperature (SST) and thermocline take part actively is known as the Indian Ocean Dipole (IOD). Propagation of baroclinic Kelvin and Rossby waves excited by anomalous winds, play an important role in the development of SST anomalies associated with the IOD. Since mean thermocline in the Indian Ocean is deep compared to the Pacific, it was believed for a long time that the Indian Ocean is passive and merely responds to the atmospheric forcing. Discovery of the IOD and studies that followed demonstrate that the Indian Ocean can sustain its own intrinsic coupled ocean-atmosphere processes. About 50% percent of the IOD events in the past 100 years have co-occurred with El Nino Southern Oscillation (ENSO) and the other half independently. Coupled models have been able to reproduce IOD events and process experiments by such models – switching ENSO on and off – support the hypothesis based on observations that IOD events develop either in the presence or absence of ENSO. There is a general consensus among different coupled models as well as analysis of data that IOD events co-occurring during the ENSO are forced by a zonal shift in the descending branch of Walker cell over to the eastern Indian Ocean. Processes that initiate the IOD in the absence of ENSO are not clear, although several studies suggest that anomalies of Hadley circulation are the most probable forcing function. Impact of the IOD is felt in the vicinity of Indian Ocean as well as in remote regions. During IOD events, biological productivity of the eastern Indian Ocean increases and this in turn leads to death of corals over a large area.Moreover, the IOD affects rainfall over the maritime continent, Indian subcontinent, Australia and eastern Africa. The maritime continent and Australia suffer from deficit rainfall whereas India and east Africa receive excess. Despite the successful hindcast of the 2006 IOD by a coupled model, forecasting IOD events and their implications to rainfall variability remains a major challenge as understanding reasons behind an increase in frequency of IOD events in recent decades.

Aperiodic Variability in the Cane-Zebiak Model: A Diagnostic Study

The finite predictability of the coupled ocean-atmosphere system is determined by its aperiodic variability. To gain insight regarding the predictability of such a system, a series of diagnostic studies has been carried out to investigate the role of convergence feedback in producing the aperiodic behavior of the standard version of the Cane-Zebiak model. In this model, an increase in sea surface temperature (SST) increases atmospheric heating by enhancing local evaporation (SST anomaly feedback) and low-level convergence (convergence feedback). The convergence feedback is a nonlinear function of the background mean convergence field. For the set of standard parameters used in the model, it is shown that the convergence feedback contributes importantly to the aperiodic behaviour of the model. As the strength of the convergence feedback is increased from zero to its standard value, the model variability goes from a periodic regime to an aperiodic regime through a broadening of the frequency spectrum around the basic periodicity of about 4 years. Examination of the forcing associated with the convergence feedback reveals that it is intermittent, with relatively large amplitude only during 2 or 3 months in the early part of the calendar year. This seasonality in the efficiency of the convergence feedback is related to the strong seasonality of the mean convergence over the eastern Pacific. It is shown that if the mean convergence field is fixed at its March value, aperiodic behavior is produced even in the absence of annual cycles in the other mean fields. On the, other hand, if the mean convergence field is fixed at its September value, the coupled model evolution remains close to periodic, even in the presence of the annual cycle in the other fields. The role of convergence feedback on the aperiodic variability of the model for other parameter regimes is also examined. It is shown that a range exists in the strength of the SST anomaly feedback for which the model variability is aperiodic even without the convergence feedback. It appears that in the absence of convergence feedback, enhancement of the strength of the air-sea coupling in the model through other physical processes also results in aperiodicity in the model.

Crystal structures, spectral and magnetic properties of (µ-hydroxo)(µ-acetato)dicopper(II) complexes containing chelating amines

The reaction of [Cu2(O2CMe)4(H2O)2] with N, N, N′, N′-tetramethylethane- 1,2-diamine (tmen) in ethanol yielded the dicopper(II) complex [Cu2(OH)(O2CMe)(tmen)2][ClO4]21. A similar reaction with N, N- dimethylethane- 1,2-diamine (dmen) afforded a crystalline product 2 in which two dicopper(II) complexes, [Cu2(OH)(O2CMe)(dmen)2][ClO4]22a and [Cu2(OH)(O2CMe)(H2O)2(dmen)2][ClO4]22b, are cocrystallized in a 1 : 1 molar ratio along with 2NaClO4. The crystal structures of 1 and 2 have been determined. The complexes have an asymmetrically dibridged [Cu2(µ-OH)(µ-O2CMe)]2+ core. The co-ordination geometry of the metal is square planar (CuO2N2). The copper atoms in 2b have a square-pyramidal CuO3N2 co-ordination sphere. The Cu Cu distances and Cu–O–Cu angles in 1, 2a and 2b are 3.339(2), 3.368(3), 3.395(7)Å, 120.1(2), 116.4(1) and 123.6(2)°, respectively. Complex 1 exhibits an axial ESR spectrum in a methanol glass giving g∥= 2.26 (A∥= 164 × 10–4 cm–1) and g⊥= 2.04. The ESR spectra obtained from the bulk material of the dmen product are indicative of the presence of two dimers, viz. complex 2a(g∥= 2.25, A∥= 165 × 10–4 cm–1; g⊥= 2.03) and 2b(g∥= 2.19, A∥= 184 × 10–4 cm–1; g⊥= 2.0). Variable-temperature magnetic susceptibility measurements on these complexes show an intramolecular antiferromagnetic coupling in the dimeric core. The fitting parameters are J=–27.8 cm–1, g= 2.1 for complex 1 and J=–10.1 cm–1, g= 2.0 for 2. The magnetostructural properties of the complexes are discussed. There is a linear correlation of the –2J values with the Cu Cu distances among dibridged complexes having square-planar copper(II) centres.

Nonaxisymmetric unsteady motion over a rotating disk in the presence of free convection and magnetic field

The nonaxisymmetric unsteady motion produced by a buoyancy-induced cross-flow of an electrically conducting fluid over an infinite rotating disk in a vertical plane and in the presence of an applied magnetic field normal to the disk has been studied. Both constant wall and constant heat flux conditions have been considered. It has been found that if the angular velocity of the disk and the applied magnetic field squared vary inversely as a linear function of time (i.e. as (1??t*)?1, the governing Navier-Stokes equation and the energy equation admit a locally self-similar solution. The resulting set of ordinary differential equations has been solved using a shooting method with a generalized Newton's correction procedure for guessed boundary conditions. It is observed that in a certain region near the disk the buoyancy induced cross-flow dominates the primary von Karman flow. The shear stresses induced by the cross-flow are found to be more than these of the primary flow and they increase with magnetic parameter or the parameter ? characterizing the unsteadiness. The velocity profiles in the x- and y-directions for the primary flow at any two values of the unsteady parameter ? cross each other towards the edge of the boundary layer. The heat transfer increases with the Prandtl number but reduces with the magnetic parameter.

Organometallic chemistry of diphosphazanes *1: VIII. Synthesis, spectroscopic studies and crystal structure of fac-[Mo(CO)3(MeCN)Ph2PN(iPr)P(Ph)(DMP)], and its reactions with tertiary phosphines

The reaction of fac-[Mo(CO)3(MeCN)3] with the unsymmetrical diphosphazane Ph2PN(iPr)P(Ph)(DMP) (L) gives the complex fac-[Mo(CO)3(MeCN)(L)] (2) in almost quantitative yield. The structure of the complex has been determined by an X-ray diffraction study. The compound reacts with PR3 (where R = Ph, OPh) to give fac-[Mo(CO)3(PR3)(L)] (3a, 4a), which undergoes an intramolecular isomerization to afford mer-[Mo(CO)3(PR3)(L)] (3b, 4b). Synthesis of cis-[Mo(CO)4(L)] (1) and fac-[MO(CO)3L] (2a) and their spectroscopic data are also reported.

Polarimetric Signatures in the Stratiform Region of a Mesoscale Convective System

Four polarimetric measurands were collected in the stratiform region of a mesoscale convective system. The four are the reflectivity factor, the differential reflectivity, the correlation coefficient between orthogonal copolar echoes, and the differential propagation constant. Most striking is a signature of large aggregates (about 10 mm in size) seen in the differential phase through the melting layer. Another significant feature is an abrupt notch in the correlation coefficient that occurs towards the bottom of the bright band. Aircraft observations and a one-dimensional cloud model are used to explain some polarimetric measurements and to infer the presence of aggregates, graupel, and supercooled cloud water in the stratiform region. These unique observations and model data provide inferences concerning the presence of graupel and the growth of large aggregates in the melting layer.

Stabilization of α-nickel hydoxide in the presence of organic additives: chemical route to bulk synthesis

Organic molecules such as glucose or lactose mediate the synthesis and stabilize alpha-nickel hydroxide in a simple precipitation reaction, while, in the absence of these additives, beta-nickel hydroxide is formed. The additives are not incorporated in the product phase.

Ion probing with Luminescent PbS Quantum dots in PVA

The PbS quantum dots synthesized in PVA are used to investigate their photoluminescence (PL) response to various ions such as Zn, Cd, Hg, Ag, Cu, Fe, Mn, Co, Cr and Ni ions. The enhancement in the photoluminescence intensity is observed with specific ions namely Zn, Cd, Hg and Ag. Among these four ions, the PL response to Hg and Ag even at sub-micro-molar concentrations is quite high, approximately an order of magnitude higher than Zn and Cd. It is interesting to observe that the change in Pb and S molar ratio has profound effect on the selectivity of these ions. The samples prepared under excess of S are quite effective compared to Pb. Indeed, the later one has hardly any effect on the photoluminescence response. These results also indicate that the sensitivity of these QDs could be fine-tuned by controlling the S concentration at the surface. Contrary to the above, Cu, Fe and Co quenches the photoluminescence. Another interesting property of PbS in PVA observed is photo-brightening mechanism due to the curing of the polymer with laser. However, the presence of excess ions at the surface changes its property to photo-darkening/brightening that depends on the direction of carrier transfer mechanism (from QDs to the surface adsorbed metal ions or vice-versa), which is an interesting feature for metal ion detectivity.

Studies on the 14α-hydroxylation of progesterone in mucor piriformis

Cell-free extracts with high 14?-hydroxylase activity were prepared from induced vegetative cell cultures of Mucor piriformis by grinding in potassium phosphate buffer (0.05 M, pH 8.0) containing glucose (0.25 M), KCl (1 mM), glutathione (1.0 mM) and glycerol (10%). Although the ideal pH for preparing the cell-free extract from vegetative cells was 8.0, the pH optimum of the hydroxylase was found to be 7.6. Microsomes (2.0 mg) prepared from the crude cell-free extract hydroxylated progesterone to 14?-hydroxyprogesterone in not, vert, similar60% yields in 30 min in the presence of NADPH and O2. Microsomes prepared from the uninduced cells did not contain any 14?-hydroxylase activity. The hydroxylase activity was inhibited to a significant extent by CO and p-chloromercuribenzoate whereas moderate inhibition was noticed in the presence of SKF-525A, metyrapone and N-methylmaleimideindicating the possible involvement of the cytochromeP-450 system in the reaction. The membrane bound hydroxylase was solubilized using Triton X-100 and the solubilized fraction contained nearly 35% of the original hydroxylase activity.