Semiempirical and ab initio conformational analysis of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane with application of GIAO-SCF methods to NMR spectrum interpretation

The GIAO-SCF method for calculating isotropic nuclear magnetic shielding values has been utilized to explain certain features in the ¹H-NMR spectrum of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane. Population distributions of the low-energy conformers based on their ab initio energies were used to produce weighting factors for the individual calculated shielding values to calculate the weighted average of the shielding values for a complete set of conformers. The differences in ¹H chemical shifts between the hydrogens of the two methyl groups and between the axial and equatorial hydrogens in 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane were shown to be due to energy differences between the chair and boat orientations of the six-membered ring and contribution from a twist-boat conformation. Results suggest a hypothesis that intramolecular differences in chemical shift might be calculated to a greater degree of accuracy than chemical shifts calculated relative to a standard.     

Calculation of NMR spectra of substituted benzenes using a microcomputer

A BASIC microcomputer program for the systematic analysis of ¹H and ¹³C chemical shifts of substituted benzenes using published substituent chemical shifts has been written. The program will calculate spectra for permutations of three or four substituents and determine the root-mean-square difference between the calculated and observed shifts.     

Computation of through-space NMR shielding effects in aromatic ring pi-stacked complexes

Aromatic compounds can form dimeric complexes in solution. Substituted aromatics tend to form parallel-stacked complexes, either aligned or offset. The HF-GIAO method in Gaussian 03 was employed to calculate the NMR isotropic shielding values of the proximal hydrogen of diatomic hydrogen probes above and below the center of the ring and above and below an unsubstituted ring carbon of 1,3,5-trimethylbenzene in a face-to-face pi-stacked aligned complex with 1,3,5-trinitrobenzene. The calculated isotropic shielding values for the aromatic hydrogens of each of the substituted rings were subtracted from the isotropic shielding values calculated for the comparable positions in the complex. Complexation results in each aromatic ring shielding the other ring. Also, the calculated isotropic shielding values for the proximal hydrogen of a diatomic hydrogen probe over (or under) each of the individual substituted benzenes were subtracted from the isotropic shielding values calculated for the comparable positions in the complex. The difference is the shielding increment due to complexation. Complexation results in increased NMR shielding of a hydrogen probe molecule on both sides of the pi-stacked complex, with slightly more shielding due to complexation on the side nearest 1,3,5-trimethylbenzene. The results are interpreted in terms of polarization of the pi cloud of the substituted benzenes by complexation and its NMR consequences. Finally, NMR shielding calculations were done on the optimized structure of N-phenylpyrrole dimer. The data were compared to concentration-dependent NMR shift data to estimate the percent dimer present.     

Modeling through-space magnetic shielding over ethynyl,cyano, and nitro groups

In a strong magnetic field, covalently bonded hydrogen nuclei located over a pi bonded functional group experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the pi bond and various other intramolecular shielding effects. Gauge including atomic orbital (GIAO)-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net through-space proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over simple molecules that contain a carbon-carbon triple bond, a carbon-nitrogen triple bond, or a nitro group. These net shielding increments of the proximate proton of methane, plotted against their Cartesian coordinates, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over each group. The predictive capability of each equation has been validated by calculating shielding increments of protons over the functional group in known structures. These shielding increments are then used to adjust predicted chemical shifts for through-space shielding effects, and the adjusted values are compared to experimentally observed chemical shifts. The algorithms for predicting the shielding increment for a proton over these functional groups can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Their use can substantially improve the accuracy of the estimated chemical shift of a proton in the vicinity of these functional groups, and thus assist in spectral assignments and in correct structure determination.     

An NMR shielding model for protons above the plane of a carbonyl group

Covalently bonded hydrogen nuclei located over the plane of a carbonyl group in a strong magnetic field experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the carbon-oxygen double bond and various other intramolecular shielding effects. GIAO-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over formaldehyde. The net shielding increments of the proximate proton of methane, plotted against its Cartesian coordinates relative to the center of the carbon-oxygen double bond, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over the plane of a carbonyl group. The predictive capability of this equation has been validated by calculating the shielding increments of protons over the plane of a carbonyl group in known structures, using this as a correction to the chemical shift estimated by subtituent effects and comparing the result to experimentally observed chemical shifts. Shielding is predicted by this equation for protons located in the region from over the center of the carbon-oxygen double bond to beyond the carbon atom; deshielding is predicted for protons located above and beyond the oxygen atom. This prediction differs from those made by the long-held "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the shielding increment for a proton over a carbonyl group can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Its use can improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-oxygen double bond, and thus assist in spectral assignments and in correct structure determination.     

DFT studies on armchair (5, 5) SWCNT functionalization. Modification of selected structural and spectroscopic parameters upon two-atom molecule attachment

Density functional theory (DFT) studies on adsorption of several gaseous homo- and hetero-diatomic molecules (AB) including H₂, O₂, N₂, NO and CO on external surface of H-capped pristine armchair (5, 5) single-walled carbon nanotube (SWCNT) were conducted. Structures of C₇₀H₁₀ and the corresponding C₇₀H₁₀–AB adducts were fully optimized at the B3LYP/6-311G* level of theory. Calculated HOMO/LUMO energy gaps (E_g), ¹³C NMR chemical shifts and IR/Raman parameters were analyzed and critically compared with available experimental data. Significant changes of carbon NMR atom chemical shifts (up to −100 ppm) and shielding anisotropies (up to −180 ppm) at sites of addition were observed. Functionalized SWCNTs produced IR and Raman spectra different from the pristine nanotube model. The selective changes in vibrational spectra will help in assigning the topology of functionalization at the nanotube wall.     

Identifying regions of interest in reading an image

The aim of this study is to develop an effective method to analyze regions of interest (ROIs). Two experiments were conducted at different times using different groups of observers with different images on different displays. Observers’ eye-movement data were collected. Fixation maps showing CIELAB L¹ values were created. The ΔL¹ values between the two maps were used to quantify differences in visual fields, counting methods, observer variability and repeatability between the two experiments.The results showed that fixation maps can be used to effectively analyze the distribution of eye movements between images. The ΔL¹ value calculated for two fixation maps is easy to understand and computes differences based only on ROIs more effectively than differences based on the entire image. The results from the two experiments were consistent, indicating that eye-tracking data are robust for evaluating image quality.     

An algorithm for predicting proton nuclear magnetic resonance deshielding over a carbon-carbon double bond

Hydrogen nuclei located over a carbon-carbon double bond in a strong magnetic field experience NMR shielding effects that result from the magnetic anisotropy of the nearby double bond and various other intramolecular shielding effects. We have used GIAO, a subroutine in Gaussian 98, to calculate isotropic shielding values and to predict the proton NMR shielding increment for a simple model system: methane held in various orientations, positions, and distances over ethene. The average proton NMR shielding increments of several orientations of methane have been plotted versus the Cartesian coordinates of the methane protons relative to the center of ethene. A single empirical equation for predicting the NMR shielding experienced by protons over a carbon-carbon double bond has been developed from these data. The predictive capability of this equation has been validated by comparing the shielding increments for several alkenes calculated using our equation to the experimentally observed shielding increments. This equation predicts the NMR shielding effects more accurately than previous models that were based on fewer geometries of methane over ethene. In fact, deshielding is predicted by this equation for protons over the center and within about 3 A of a carbon-carbon double bond. This result is in sharp contrast to predictions made by the long-held McConnell "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the (de)shielding increment for a proton over an alkene can be used in a spreadsheet on a PC or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. In either application its use can substantially improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-carbon double bond, and thus assist in spectral assignments and in correct structure determination.     

Evaluation of Collections 4 and 5 of the MODIS Gross Primary Productivity product and algorithm improvement at a tropical savanna site in northern Australia

In this study, we assessed the accuracy of the MODIS (Moderate Resolution Imaging Spectroradiometer) GPP (gross primary productivity) Collections 4.5, 4.8 and 5 along with Leaf Area Index (LAI), fraction of absorbed Photosynthetically Active Radiation (fPAR), light use efficiency (LUE) and meteorological variables that are used to estimate GPP for a northern Australian savanna site. Results of this study indicated that the MODIS products captured the seasonal variation in GPP, LAI and fPAR well. Using the index of agreement (IOA), it was found that Collections 4.5 and 4.8 (IOA 0.89 respectively) agreed reasonably well with flux tower measurements between 2001 and 2006. It was also found that MODIS Collection 4.5 predicted the dry season GPP well (Relative Predictive Error (RPE) 4.17%, IOA 0.72 and Root Mean Square Error (RMSE) of 1.05 g C m^− 2 day^− 1), whilst Collection 4.8 performed better in capturing wet season dynamics (RPE 1.11%, IOA 0.80 and RMSE of 0.91 g C m^− 2 day^− 1). Although the wet season magnitude of GPP was predicted well by Collection 4.8, an examination of the inputs to the GPP algorithm revealed that MODIS fPAR was too high, but this was compensated by PAR and LUE that was too low. Although LAI and fPAR estimated by Collection 5 were more accurate, GPP for this Collection resulted in a much lower value (RPE 25%) due to errors in other factors. Recalculation of MODIS GPP using site specific input parameters indicated that MODIS fPAR was the main reason for the differences between MODIS and tower derived GPP followed by LUE and meteorological inputs. GPP calculated using all site specific values agreed very well with tower data on an annual basis (IOA 0.94, RPE 6.06% and RMSE 0.83 g C m^− 2 day^− 1) but the early initiation of the growing season calculated by the MODIS algorithm was improved when the vapor pressure deficit (VPD) function was replaced with a soil water deficit function. The results of this study however, reinforce previous findings in water limited regions, like Australia, and incorporation of soil moisture in a LUE model is needed to accurately estimate the productivity.     

Molecular dynamics simulation of salt rejection through silicon carbide nanotubes as a nanostructure membrane

Salt rejection phenomenon was investigated using armchair silicon carbide (SiC) nanotubes under applied electric fields. The systems included the (7,7) and (8,8) SiC nanotubes surrounded by silicon nitride membrane immersed in a 0.4 mol/L aqueous solution of sodium chloride. Results of molecular dynamics (MD) simulations for selective separation of Na⁺ and Cl⁻ ions showed that the (7,7) SiC nanotube is suitable for separation of cations and the (8,8) SiC nanotube can be used for separating anions. The water desalination by SiC nanotubes was demonstrated by potential of mean force for Na⁺ and Cl⁻ ions in each SiC nanotube. Furthermore, the ionic current, ion residence time, and the radial distribution functions of species were measured to evaluate the properties of the system. Based on the results of this research, the studied SiC nanotubes can be recommended as a nanostructure model for water desalination.     

An algorithm for predicting the NMR shielding of protons over substituted benzene rings

In a strong magnetic field, hydrogen nuclei located over an aromatic ring experience a reduced magnetic field as a result of the induced magnetic field associated with circulating pi electrons. We used GIAO-SCF, an ab initio subroutine in Gaussian 94 to calculate isotropic shielding values and to determine the proton nuclear magnetic resonance (NMR) shielding increment for a simple model system: methane held at various positions over a substituted benzene ring. The NMR shielding increments experienced by the proximal protons of methane have been mapped as a function of their position X, Y, and Z relative to the center of aniline and, separately, nitrobenzene. A mathematical function of the same form has been fit to the three-dimensional shielding increment surface at each of five distances from the face of each aromatic ring. In addition, a single mathematical equation has been developed for predicting the shielding caused by either substituted aromatic ring. The chemical shifts predicted by using the results of this equation in conjunction with additive substituent increments are compared to observed values.     

Computation of through-space NMR shielding effects by aromatic ring-cation complexes: substantial synergistic effect of complexation

The HF-GIAO method in Gaussian 03 was employed to calculate the NMR isotropic shielding values of a diatomic hydrogen probe and to predict the through-space proton NMR shielding increment surfaces above benzene complexed with ammonium, lithium, sodium, potassium, magnesium or calcium ion. The sum of the calculated isotropic shielding values for the proximal hydrogen of a diatomic hydrogen probe over benzene and those calculated at appropriate positions relative to cations were subtracted from the isotropic shielding values calculated for the complexes. The result is a shielding increment for complexation. Complexation results in a synergistic effect on NMR shielding. Enhanced shielding was observed over the π electron cloud of benzene upon complexation with the cations, more than the sum of the separate effects of the aromatic ring and the charge. The results are interpreted in terms of polarization of the π cloud of benzene by the cation and its consequences.     

Evaluation of satellite based primary production modelling in the semi-arid Sahel

The MODIS (Moderate Resolution Imaging Spectroradiometer) primary productivity products are evaluated against observed Above-ground Net Primary Production (AGNPP) in the semi-arid Senegal 2001. MODIS net primary productivity (NPP) modelling is a light use efficiency (LUE) based approach incorporating constraints on vegetation productivity arising from simulated radiation, water demand and temperature data from NASA's Data Assimilation Office (DAO). Annually integrated MODIS PSN (MOD17A2 net photosynthesis, Collection 4) explains more of the observed biomass variation (r² = 0.77) than MODIS fAPAR (fraction Absorbed Photosynthetically Active Radiation, Collection 4) (r² = 0.72), indicating the effect of including the canopy stress scalar (ε_s) based on DAO data combined with modelled maintenance respiration costs (of leaf and fine roots). Annual MODIS NPP (MOD17A3, Collection 4 (C4) and Collection 4.5 (C4.5)) including growth respiration and live wood maintenance respiration costs and modified DAO input (C4.5) however increases the residual unexplained observed AGNPP variance (C4 NPP; r² = 0.49) (C4.5 NPP; r² = 0.37). The overall quality of the annual NPP MODIS C4 and C4.5 products are moderate for the semi-arid Senegal because of the annual respiration cost modelling and a change in C4.5 biome-specific parameters stored in a Biome Properties Look-Up Table (BPLUT) is the main contributor to the observed discrepancy between C4 and C4.5 NPP. The dynamic range of the values of all MOD17 products was too low when compared to observed AGNPP. An estimate of canopy water stress (SIWSI; Shortwave Infrared Water Stress Index) derived from MODIS channels 2 and 6 and photosynthetically active radiation (PAR) irradiance derived from geostationary METEOSAT data were tested for primary production modelling using a stepwise linear regression analysis. PAR irradiance was combined with MODIS fAPAR into APAR (Absorbed Photosynthetically Active Radiation) explaining 79% of the observed AGNPP variation. Introducing SIWSI significantly increased the explained variance of observed AGNPP (r² = 0.89). MODIS-derived percentage tree cover was tested as a predictor based on the hypothesis that tree cover provides information on differences in respiratory costs between trees and grasses thereby accounting for variations in the LUE conversion efficiency ε. No significant reduction in residual unexplained AGNPP variance was found. Earth observation based derivation of PAR and canopy water stress from SIWSI suggest potential improvements to primary production models in semi-arid biomes that can be implemented in general NPP modelling LUE methodology.     

Aerobic capacity of urban women homemakers in Bombay

Twenty-six healthy women homemakers residing in the metropolitan city of Bombay were studied on a treadmill and a cycle ergometer to determine their aerobic capacity ([Vdot]O₂ max) with a view to evaluating their cardio-respiratory fitness and ascertaining the job-demand-fitness-compatibility in household activities. The [Vdot]O₂ max was found to be significantly higher in treadmill experiments, i.e. 15% in absolute value and 18% in relative value, as compared with that obtained by cycle ergometry (p < 0·001). A much higher difference was observed in values derived from the two methods on the same subjects (i.e. 28% in absolute value and 31% in relative value). Thus, the [Vdot]O₂max obtained from treadmill experiments may be regarded as the maximal aerobic power or the highest oxygen uptake that an individual can attain during exercise, which in the sample of the present study was recorded as 1·901 min ^?1 (33·9 ml kg ^?1 min ^?1). The findings also revealed that age and body weight have a direct influence on [Vdot]O₂max, which was found to be significantly correlated, positively with the latter and negatively with the former (p<0·01 in both cases). The physiological job-demand of household activities seems to be compatible in relation to the [Vdot]O₂max of the homemakers.     

Bounds on the Diameter of One-Dimensional Pec Networks

The diameter of a packed exponential connections (PEC) network on N nodes is shown to be Θ([formula] × [formula]).⁴ A routing algorithm which can route between any two nodes in O([formula] × [formula]) steps is shown. A methodology to find a set of links to be used by a shortest path from node 1 to node N − 1 is derived. We also show that semigroup operations can be performed in O([formula] × [formula]) parallel steps.     

Enclosing Solutions of Singular Interval Systems Iteratively

Richardson splitting applied to a consistent system of linear equations Cx = b with a singular matrix C yields to an iterative method x^k+1 = Ax^k + b where A has the eigenvalue one. It is known that each sequence of iterates is convergent to a vector x^* = x^* (x⁰) if and only if A is semi-convergent. In order to enclose such vectors we consider the corresponding interval iteration with (|[A]|) = 1 where |[A]| denotes the absolute value of the interval matrix [A]. If |[A]| is irreducible we derive a necessary and sufficient criterion for the existence of a limit of each sequence of interval iterates. We describe the shape of and give a connection between the convergence of ( ) and the convergence of the powers of [A].Dedicated to Professor G. Mae on the occasion of his 65^th birthday     

A theoretical study on the characteristics of the intermolecular interactions in the active site of human androsterone sulphotransferase: DFT calculations of NQR and NMR parameters and QTAIM analysis

A theoretical study at the level of density functional theory (DFT) was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond interactions, in the active site of enzyme human androsterone sulphotransferase (SULT2A1/ADT). Geometry optimization, interaction energy, ²H, ¹⁴N, and ¹⁷O electric field gradient (EFG) tensors, ¹H, ¹³C, ¹⁷O, and ¹⁵N chemical shielding (CS) tensors, Natural Bonding Orbital (NBO) analysis, and quantum theory of atoms in molecules (QTAIM) analysis of this active site were investigated. It was found that androsterone (ADT) is able to form hydrogen bonds with residues Ser80, Ile82, and His99 of the active site. The interaction energy calculations and NBO analysis revealed that the ADT molecule forms the strongest hydrogen bond with Ser80. Results revealed that ADT interacts with the other residues through electrostatic and Van der Waals interactions. Results showed that these hydrogen bonds influence on the calculated ²H, ¹⁴N, and ¹⁷O quadrupole coupling constants (QCCs), as well as ¹H, ¹³C, ¹⁷O, and ¹⁵N CS tensors. The magnitude of the QCC and CS changes at each nucleus depends directly on its amount of contribution to the hydrogen bond interaction.     

Comparison of two hyperspectral imaging and two laser-induced fluorescence instruments for the detection of zinc stress and chlorophyll concentration in bahia grass (Paspalum notatum Flugge.)

Bahia grass (Paspalum notatum Flugge.) plants were grown in silica sand and irrigated daily with one of five levels of Zn (0, 0.5, 25, 50, or 100 mg l⁻¹) to determine the effects of the heavy metal on the growth and development of plant canopies. Healthy and stressed plants were measured with two hyperspectral imagers, laser-induced fluorescence spectroscopy (LIFS), and laser-induced fluorescence imaging (LIFI) systems in order to determine if the four handheld remote sensing instruments were equally capable of detecting plant stress and measuring canopy chlorophyll levels in bahia grass. Symptoms of bahia grass plants grown at deficient (0 mg l⁻¹) or toxic (25, 50, or 100 mg l⁻¹) concentrations of Zn were dominated by leaf chlorosis and plant stunting. Leaf fresh weight, leaf dry weight, CO₂ assimilation, total chlorophyll, and leaf thickness followed (+) quadratic models in which control plants (0.5 mg l⁻¹ Zn) exhibited higher responses than plants grown at either deficient or toxic levels of Zn. Normalized difference vegetation index [NDVI=(NIR−Red)/(NIR+Red)] and ratio vegetation index [RVI=R₇₅₀/R₇₀₀, in which R denotes reflectance] values were calculated for calibrated digital images from both hyperspectral imagers. The NDVI and RVI values from both hyperspectral imagers were fit best by (+) quadratic models when treatments were constrained between 0 and 100 mg l⁻¹ Zn, but were fit best by linear regression models with (−) slopes when treatments were constrained between 0.5 and 100 mg l⁻¹ Zn. Furthermore, both NDVI and RVI algorithms were effective in predicting the concentrations of chlorophyll in canopies of bahia grass grown at the various levels of Zn. In contrast, red/far-red (R/FR) fluorescence ratios estimated from leaf fluorescence values measured with the LIFS and LIFI instruments were fit best by (−) quadratic models when treatments were constrained between 0 and 100 mg l⁻¹ Zn, but were fit best by linear regression models with (+) slopes when treatments were constrained between 0.5 and 100 mg l⁻¹ Zn. A series of regression analyses were conducted among plant biometric, biochemical, and leaf anatomical parameters (treated as independent variables) and the remote sensing algorithms, NDVI, RVI, blue/green (BL/GR), and R/FR (treated as dependant variables). In general, residuals were significantly higher for NDVI and RVI models compared to the BL/GR and R/FR models indicating that the NDVI and RVI algorithms were able to measure total chlorophyll and plant biomass more accurately than the BL/GR and R/FR algorithms. However, unique capabilities of LIFS and LIFI instruments continue to argue for the development of laser-induced fluorescence remote sensing technologies.     

Nonlinear mathematical modeling of seed spacing uniformity of a pneumatic planter using genetic programming and image processing

The purpose of this research was to represent the new laboratory test procedure that could be applicable in the field condition. Therefore, the performance of a pneumatic planter was investigated under laboratory conditions for maize, castor, fababean, sorghum, sugar beet, watermelon and cucumber seeds. The effect of operational speed [(1) 2.5–4 km/h and (2) 6–8.5 km/h] and vacuum pressure was evaluated by examining the quality of feed index, precision in spacing (coefficient of variation), miss index and multiple index. The most perfect operating parameter values for maize, castor, sorghum and sugar beet seeds were obtained at the first level of operating speed and 4.0 kPa pressure; for watermelon seed: second level of speed and 4.5 kPa pressure; and for cucumber seed: first level of speed and 4.5 kPa pressure. Furthermore, in order to determine the relationship between most important operating parameters affecting the performance of the pneumatic metering device and seed physical properties, regression models were developed using genetic programming (GP) algorithm. According to the results, the developed model using GP encompasses all physical properties of seeds as well as operational parameters. The model strongly describes the effect of investigated factors on seed spacing uniformity with values of the coefficient of determination R ² of 0.938, RMSE of 3.01 and MAE of 3.362087. Furthermore, the associated P value of 2.9851e−17 represents that the model is statistically significant. Model obtained from GP approach not only has a higher value of the coefficient of determination compared to regression model but is able to present the relationship between two operating parameters affecting the performance of row crop pneumatic metering device and seed physical properties, as well.