Coverage-dependent structural phase transformations in the adsorption of pentacene on an aperiodically modulated Cu film.

Surface ordering of pentacene molecules adsorbed on an aperiodic Cu surface has been studied with density functional theory (DFT) and scanning tunnelling microscopy as a function of coverage. Below 0.73 ML (5.3 × 1013 molecules cm-2), the adsorbate structure is row-like with the molecular axes aligned with the rows in the Cu structure. Between this coverage and 1 ML (7.3 × 1013 molecules cm-2), a structural phase with a checkerboard structure is seen. At this coverage region, the molecules are very close to each other which leads to unusual bending. At higher coverages, a further phase transition to a high-density row structure is seen for most of the film. DFT with van der Waals functionals is employed to study how the molecule-molecule and molecule-surface interactions evolve as a function of coverage.

Influence of leaching on surface composition, microstructure, and valence band of single grain icosahedral Al-Cu-Fe quasicrystal.

The use of quasicrystals as precursors to catalysts for the steam reforming of methanol is potentially one of the most important applications of these new materials. To develop application as a technology requires a detailed understanding of the microscopic behavior of the catalyst. Here, we report the effect of leaching treatments on the surface microstructure, chemical composition, and valence band of the icosahedral (i-) Al-Cu-Fe quasicrystal in an attempt to prepare a model catalyst. The high symmetry fivefold surface of a single grain i-Al-Cu-Fe quasicrystal was leached with NaOH solution for varying times, and the resulting surface was characterized by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The leaching treatments preferentially remove Al producing a capping layer consisting of Fe and Cu oxides. The subsurface layer contains elemental Fe and Cu in addition to the oxides. The quasicrystalline bulk structure beneath remains unchanged. The subsurface gradually becomes Fe3O4 rich with increasing leaching time. The surface after leaching exhibits micron sized dodecahedral cavities due to preferential leaching along the fivefold axis. Nanoparticles of the transition metals and their oxides are precipitated on the surface after leaching. The size of the nanoparticles is estimated by high resolution transmission microscopy to be 5-20 nm, which is in agreement with the AFM results. Selected area electron diffraction (SAED) confirms the crystalline nature of the nanoparticles. SAED further reveals the formation of an interface between the high atomic density lattice planes of nanoparticles and the quasicrystal. These results provide an important insight into the preparation of model catalysts of nanoparticles for steam reforming of methanol.

Templated quasicrystalline molecular ordering.

Quasicrystals are materials with long-range ordering but no periodicity. We report scanning tunneling microscopy (STM) observations of quasicrystalline molecular layers on 5-fold quasicrystal surfaces. The molecules adopt positions and orientations on the surface consistent with the quasicrystalline ordering of the substrate. Carbon-60 adsorbs atop sufficiently separated Fe atoms on icosahedral Al-Cu-Fe to form a unique quasicrystalline lattice, whereas further C60 molecules decorate remaining surface Fe atoms in a quasi-degenerate fashion. Pentacene (Pn) adsorbs at 10-fold symmetric points around surface-bisected rhombic triacontahedral clusters in icosahedral Ag-In-Yb. These systems constitute the first demonstrations of quasicrystalline molecular ordering on a template.

Crystalline and quasicrystalline allotropes of Pb formed on the fivefold surface of icosahedral Ag-In-Yb.

Crystalline and quasicrystalline allotropes of Pb are formed by evaporation on the fivefold surface of the icosahedral (i) Ag-In-Yb quasicrystal under ultra-high vacuum. Lead grows in three dimensional quasicrystalline order and subsequently forms fivefold-twinned islands with the fcc(111) surface orientation atop of the quasicrystalline Pb. The islands exhibit specific heights (magic heights), possibly due to the confinement of electrons in the islands. We also study the adsorption behavior of C60 on the two allotropes of Pb. Scanning tunneling microcopy reveals that a high corrugation of the quasicrystalline Pb limits the diffusion of the C60 molecules and thus produces a disordered film, similar to adsorption behavior of the same molecules on the clean substrate surface. However, the sticking coefficient of C60 molecules atop the Pb islands approaches zero, regardless of the overall C60 coverage.

Seasonal trends in organochlorine pesticide residues in raw bovine milk from rural areas of Haryana, India.

Seasonal trends in organochlorine pesticides residues namely, 1,2,3,4,5,6-hexachlorocyclohexane (HCH) isomers, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane (DDT) and its metabolites and endosulfan stereo isomers were investigated in raw bovine milk samples from rural areas of Ambala, Gurgaon and Hisar districts of the state of Haryana for winter, summer, and post-monsoon seasons. Highest concentration of HCH and DDT was found in 43 % and 53 % milk samples, respectively in post-monsoon season whereas highest values of endosulfan was reported in 36 % samples during winter season. During the study period only 2 % milk samples exceeded the maximum residue limit recommended by WHO for ΣHCH, 1 % samples each for α-HCH and γ-HCH, 9 % samples for ß-HCH as recommended by PFAA and 30 % samples for ΣDDT as prescribed by FAO. No statistical difference in the mean concentration of ∑HCH and ∑Endosulfan could be observed in any of the three districts. However, ∑DDT concentration showed marked difference [F(2, 25) = 12.42, p = 0.00018)] among the three districts.

Organochlorine pesticide residues in drinking water in the rural areas of Haryana, India.

Drinking water samples collected from rural areas of three districts of Haryana during pre-monsoon and post-monsoon periods were analysed for the presence of organochlorine pesticide residues. The main source of drinking water in rural areas, i.e. groundwater in Ambala and Gurgaon districts and surface water supply in Hisar district, was found to be contaminated with isomers of HCH and endosulfan and metabolites of DDT, whereas dieldrin remained below detection limits. During the study period, the mean values observed for total HCH, DDT and endosulfan were 87.6, 848.2, and 27.4 ng/L and 99.8, 275.3 and 164.2 ng/L, respectively, for Ambala and Gurgaon districts. In the case of Hisar district, the values were 78.5, 115.9, and 53.0 ng/L, respectively. During the study period, 37% of the samples exceeded the total pesticide level of 500 ng/L indicated in the EECD directive for drinking water. Seasonal variations of pesticide residues were also observed during the study period.

The surface science of quasicrystals.

The surfaces of quasicrystals have been extensively studied since about 1990. In this paper we review work on the structure and morphology of clean surfaces, and their electronic and phonon structure. We also describe progress in adsorption and epitaxy studies. The paper is illustrated throughout with examples from the literature. We offer some reflections on the wider impact of this body of work and anticipate areas for future development.

Pesticide pollution of River Ghaggar in Haryana, India.

Ghaggar, one of the major rivers of northern India originating in outer Himalayas and flowing through the state of Punjab, Haryana, and Rajasthan, is put to multiple uses. Along its course of 464 km, it receives discharge from various cities and runoff from agricultural lands. Punjab and Haryana are two predominantly agricultural states of India using substantial amounts of agrochemicals, yet there are no reports available in literature on the level of pesticides in the stretch of river Ghaggar through Punjab and Haryana. This is the first report on pesticide pollution of the river Ghaggar in Haryana. Water samples along the 230-km stretch of the river in Haryana were analyzed for the presence of organochlorine insecticide residues. While aldrin and dieldrin were below detection limits, both hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) were traceable in all the water samples. High concentration of beta-HCH among SigmaHCH indicates old pollution source whereas predominance of p,p'-DDT among SigmaDDT reflects its recent use in the catchment area of the river. The concentrations of HCH and DDT in all the samples were above the permissible limits prescribed by the European Commission Directive for drinking purposes.

Competition among Bradyrhizobium strains for nodulation of green gram (Vigna radiata): use of dark-nodule strain.

The competitiveness of dual-strain inoculum of Bradyrhizobium strains S24 and GR4 was demonstrated for nodulation of green gram (Vigna radiata). Strain S24 formed pink nodules, GR4 produced visually distinguishable dark-brown nodules. When a mixture of these Bradyrhizobium strains was applied as inoculum, nodules of both pink and dark-brown types were formed on the same root. The strain GR4, which was less competitive than strain S24, was mutagenized with N-methyl-N'-nitro-N-nitrosoguanidine to obtain pigment-diverse mutants and six selected mutants were screened for symbiotic parameters. One mutant produced pink nodules and appreciably increased plant dry mass. The competitive ability of this mutant lacking brown pigment was compared with that of strain S24 by using antibiotic resistance markers; it showed increased nodulation competitiveness than its parent strain GR4. The dark-brown nodule-phenotype could be useful in evaluating nodulation competitiveness of "cowpea miscellany" bradyrhizobia in soil where dark-brown nodule-forming strains are not indigenous.

Water quality index and suitability assessment of urban ground water of Hisar and Panipat in Haryana.

Ground water quality in two well-developed cities of Haryana, viz. Hisar and Panipat was assessed for drinking purpose based on water quality parameters like pH, EC, turbidity, TDS, alkalinity, total hardness, calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), chloride (Cl), nitrate (NO3), phosphate (PO4), sulphate (SO4) and fluoride (F) with respect to different land-use areas viz. residential, industrial, commercial and agricultural. Water quality index based on 9 parameters showed that at Panipat, underground water in all the land-use zones was fit for consumption (WQI < 50), whereas at Hisar, water in agricultural areas was good in quality, but that in other areas varied in magnitude of pollution (WQI > 50 to 100).

Groundwater quality assessment in different land-use areas of Faridabad and Rohtak cities of Haryana using deviation index.

Physico-chemical parameters were analysed to evaluate the groundwater quality of the two important cities of Haryana, Faridabad and Rohtak, and the pollution status of groundwater was compared using deviation index (DI). Groundwater of both the cities had high alkalinity, hardness, total dissolved solids (TDS) and electrical conductivity. The groundwater of Faridabad showed low fluoride concentration whereas in 74% of groundwater samples of Rohtak the fluoride levels were high. Land use and waste disposal practices were found to have an important effect on groundwater pollution.

Structure of the twofold surface of the icosahedral Ag-In-Yb quasicrystal.

The structure of the twofold surface of the icosahedral (i-)Ag-In-Yb quasicrystal has been investigated using low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The LEED confirms that the surface exhibits quasicrystalline long range order with the twofold rotational symmetry expected from the bulk. STM images reveal a step-terrace structure with terrace size comparable to that of the other high symmetry surfaces of the same quasicrystal. The distribution of step heights and high resolution STM images of terraces suggest that the surface terminates at bulk planes that intersect the center of rhombic triacontahedral clusters, the building blocks of the system, as in the case of the threefold and fivefold surfaces of the system. These planes are rich in Yb and In. No facets are observed on the surface, suggesting that the twofold surface is as stable as the other high symmetry surfaces.

Scanning tunneling microscopy of a polygrain Al­Pd­Re quasicrystal: study of the relative surface stability.

Scanning tunneling microscopy and x-ray photoemission spectroscopy on a polygrain icosahedral (i-) Al­Pd­Re quasicrystal (QC) show the formation of the twofold surfaces with symmetry and composition expected from the bulk. The predominant occurrence of the twofold surface on the polygrain i-QC having random grain orientation, as well as preferential formation of terrace edges, kinks and voids along the twofold axes, consistently indicates that the twofold surface, which has the highest atomic density, is the most stable among all the crystallographic planes.

Templated three-dimensional growth of quasicrystalline lead.

Quasicrystals, materials with aperiodic long-range order, have been found in intermetallics, soft materials such as colloids and supermolecules, and also in two-dimensional monolayer films. Here we present the first example of three-dimensional growth of a single-element quasicrystalline film. Using a hitherto unexplored template, the icosahedral Ag-In-Yb quasicrystal, and various experimental techniques combined with theoretical calculations of adsorption energies, we find that lead atoms deposited on the surface occupy the positions of atoms in the rhombic triacontahedral cluster, the building block of the substrate, and thus grow in layers with different heights and adsorption energies. We show that the adlayer-adlayer interaction is crucial for stabilizing this epitaxial quasicrystalline structure. The finding opens an avenue for further investigation of the impact of the aperiodic atomic order over periodic order on the physical and chemical properties of materials.

The memory of surfaces: epitaxial growth on quasi-crystals.

If crystal structures can be viewed as repositories of information, then crystal surfaces offer a pathway by which this information can be used to grow new structures through the process of epitaxy. The information transfer process is one of self-organization, and the kinetic and energetic factors influencing this are complex. They include the relative strengths of the adsorbate-adsorbate and adsorbate-substrate interactions, the flux of incoming species and the temperature of the system. In this brief review, we explore how the interplay of these factors influences the degree to which the epitaxial structures retain the 'memory' of the template, illustrating the discussion with examples from epitaxy on quasi-crystal surfaces.

Epitaxial Bi allotropes on quasicrystal surfaces as templates for adsorption of pentacene and fullerene.

The growth of Bi on surfaces of Al-based quasicrystals yields a quasicrystalline monolayer which is followed by the formation of crystalline islands of various forms depending on coverage, deposition flux and substrate temperature. We have used the Bi thin films consisting of both crystalline and quasicrystalline allotropes as substrates to study the deposition of C(60) and pentacene molecules. Scanning tunneling microscopy (STM) reveals substrate-dependent differences in molecular adsorption.

The atomic structure of the threefold surface of the icosahedral Ag-In-Yb quasicrystal.

We report a study of the atomic structure of the threefold icosahedral (i-)Ag-In-Yb quasicrystal surface using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). The LEED confirms that the surface exhibits quasicrystalline long-range order with the threefold symmetry expected from the bulk. The STM reveals large atomically flat terraces separated by steps of different heights. A comparison of atomically resolved STM images for the terraces and the step-height distribution with the bulk structure of isostructural i-Cd-Yb shows that the terraces are formed at bulk planes intersecting the centers of the rhombic triacontahedral clusters that make up the bulk structure of the system. However, the stability of particular terraces may be influenced by the density of atoms in the interstices (glue atoms that bind the clusters) in the terraces and also by the chemical environment in the underlying atomic plane. The surface exhibits screw dislocations, which is explained in terms of a continuous atomic density along the threefold axis.

Structure and reactivity of Bi allotropes on the fivefold icosahedral Al-Pd-Mn quasicrystal surface.

The growth of Bi on a pseudomorphic Bi monolayer on the fivefold surface of the icosahedral Al-Pd-Mn quasicrystal has been investigated using low energy electron diffraction and scanning tunnelling microscopy. Initially randomly oriented pseudocubic islands are formed with a preference for an even number of layers. Subsequently a morphological transformation takes place to hexagonal Bi islands, which align along high symmetry directions of the substrate. The Bi flux is found to have a strong effect on which island structure is preferred. When C(60) is adsorbed on the three different allotropes of Bi present in this system, hexagonal C(60) islands are formed in each case. On the pseudocubic and hexagonal islands, the C(60) islands are aligned with the substrate. We discuss the energetic, kinetic and geometrical factors which influence the morphological transformation referred to above.