CHEMICAL-SHIFTS

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Theoretical calculations of chemical shifts of meta
l chelates of 1, 2 
naphthoquinone dioxime

Theoretical calculations of chemical shifts of meta l chelates of 1, 2 naphthoquinone dioxime

It is observed that silver chelate is made up of seven atom ring and the valence of silver is two. The chelates of cadmium, lead, zinc and mercury with 1-2 naphthoquinone dioxime are formed with six member ring and deprotonation is not taking place which is confirmed the chemical shifts calculated and experimental values. The predicted chemical shifts of nitrogen, oxygen and metal atoms are good in aggriment. These values are in reported range. The assignments were confirmed with the help of animation process which is available in Gaussian 09 computer code. The results suggest that it shows the formation of chelates with five member ring.
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Substituent effects on Ni 61 NMR chemical shifts

Substituent effects on Ni 61 NMR chemical shifts

Quantitatively, this huge difference in δ( 61 Ni) values is far too large to be ascribed solely to such benzene-like ring currents, because the latter are independent of the probe nucleus, and would be the same in ppm for the metal as for any other lighter nucleus such as 1 H. 8 Typical effects for protons located in the shielding cones of aromatic compounds amount to but a few ppm, 7b and the largest upfield shift due to ring currents, δ( 3 He) of endohedral He complexes of "superaromatic" fullerene anions do not exceed -50 ppm. 9 Qualitatively, however, the use of 61 Ni chemical shifts as a probe into the electronic structure of Ni complexes is of interest, taking advantage of the broad chemical shift range and sensitivity towards substituent effects that is typical for transition-metal NMR. 10 In the heyday of nickel chemistry, 61 Ni NMR has been employed as means of spectroscopic characterisation for a number of complexes, 11,12 but the problems associated with the large
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The effects of extraframework species on the structure based prediction of 31P isotropic chemical shifts of aluminophosphates

The effects of extraframework species on the structure based prediction of 31P isotropic chemical shifts of aluminophosphates

changes in the local geometry, it was often not possible to use the experimental crystal structures to predict meaningful chemical shifts (for our approach or any similar method that relies on accurate knowledge of the structure). This phenomenon is well known within the field of solid-state NMR spectroscopy, with many researchers now routinely optimizing crystal structures computationally prior to the calculation of NMR parameters. While the aim of our structure-spectrum relationship is to predict NMR parameters where these cannot be calculated by a higher level of theory (thus precluding the use of such computational pre- optimization of the structure), there remains the inescapable fact that, in order to provide a meaningful prediction, the structure itself must be a meaningful representation of the material. In cases where such structures were available, we demonstrated that the structure-spectrum relationship does have genuine predictive power. Although not demonstrated here, it would also be possible to predict 31 P chemical shifts
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A study of Fe3O4@ Si18O27 catalyst through Statistical-Nucleus Independent Chemical Shifts(S-NICS) method

A study of Fe3O4@ Si18O27 catalyst through Statistical-Nucleus Independent Chemical Shifts(S-NICS) method

On the other hand, the nearby protons will experience three fields: the applied field, the shielding field of the valence electrons and the field due to the p systems. So field lines opposed to the applied field cause a reduced field in this area equivalent to shielding, anisotropic induced magnetic field lines due to the induced circulation of the p electron in the ring area of benzene, naphthalene and borazine.S-NICS has been investigated by the Monte Carlo model by computation of nucleus-independent chemical shifts in many points of shielding areas around the rings of borazine, benzene and naphthalene, by choosing specified and suitable distances (Scheme 3). The statistical simulation by the Monte Carlo method is the generation of pseudo-random numbers that are distributed in a Gaussian distribution, and the algorithm is based on a pseudorandom number generator that produces numbers x that are uniformly distributed in the interval [0, 1).
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OXIDO- AND DIOXIDOVANADIUM(V) COMPLEXES WITH O-VANILLIN SEMICARBAZONE: SYNTHESIS AND CRYSTAL STRUCTURE

OXIDO- AND DIOXIDOVANADIUM(V) COMPLEXES WITH O-VANILLIN SEMICARBAZONE: SYNTHESIS AND CRYSTAL STRUCTURE

H/ 15 N HMBC spectrum of complex 2, two cross-peaks are present for the imine proton at δ 8.30 ppm: with nitrogen nuclei at δ 238 ppm and δ 311 ppm. Both experimental values of chemical shifts for these particular semicarbazone nitrogen nuclei exclude the involvement of pure keto- form of the ligand in the coordination to metal, being an obvious indication on the afore- mentioned extended π-delocalization along the semicarbazone chain also occurring in DMSO-d 6

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Reactivity of 1-Isothiocyanato Six Membered Silatrane towards Lewis Acids

Reactivity of 1-Isothiocyanato Six Membered Silatrane towards Lewis Acids

All operations were carried out under dry nitrogen atmosphere. Solvents were freshly distilled under inert atmosphere from sodium (hexane), and phosphorus pentaoxide (dichloromethane) before use. Hydrous iron(III) chloride, nickel(II) chloride, cobalt(II) chloride, copper(II) chloride were converted to their anhydrous form using thionyl chloride. 1- Isothiocyanato six membered ring silatrane was synthesized according to procedure reported in literature [6]. IR spectra were obtained as thin films or nujol mulls on Perkin-Elmer RX-1 FTIR spectrophotometer. 1 H (300.4 MHz), 13 C (75.45 MHz), 29 Si NMR (59.60 MHz) spectra were obtained on JEOL AL 300 instrument. Chemical shifts were reported with respect to TMS as an external standard.
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The synthesis and characterization of new higher nuclearity arene ruthenium sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

The synthesis and characterization of new higher nuclearity arene ruthenium sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

Chemical shifts, Ru-N bondlengths and distances of cymene-Ru for two cationic complexes with nitrogen containing ligands Crystallographic data of the mono-ammonia complex Chemical shifts[r]

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Accelerated Imaging Techniques for Chemical Shift Magnetic Resonance Imaging

Accelerated Imaging Techniques for Chemical Shift Magnetic Resonance Imaging

affecting the quality of the water-fat separation. ..................................................................... 64   Figure 3.6 A prospectively undersampled dataset of entire abdominal cavity reconstructed with the proposed method. A sagittal reformat of the fat images is shown (a). Fat and water images are shown for slices 30, 60, and 90 (b). These three slices correspond to the three horizontal lines in (a). Net acceleration factor for this acquisition was 7.0. .......................... 65   Figure 3.7 Water and fat images of 32 coil, 3D abdominal data with (8 virtual coils) and without (32 coils) coil compression. Water and fat difference images (amplified by a factor of 10) show the accuracy of the coil compression. Images were acquired at a net acceleration factor of 3.1. ............................................................................................................................. 66   Figure 4.1 Digital phantom simulation of metabolite separation. Metabolite images with chemical shifts corresponding to pyruvate, pyruvate hydrate, lactate, alanine, and bicarbonate were reconstructed using the proposed reconstruction for cases of low and high B 0
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Insights into the acid base properties of PtIV diazidodiam(m)inedihyroxido complexes from multinuclear NMR spectroscopy

Insights into the acid base properties of PtIV diazidodiam(m)inedihyroxido complexes from multinuclear NMR spectroscopy

an ionizable group usually re- sults in shifts of the NMR peaks from nearby nuclei in a molecule. Such shifts occur when the rate of proton ex- change is fast on the NMR time scale and represents the weighted average of the chemical shifts of the protonated and deprotonated forms. pH titration curves are then ana- lyzed by curve-fitting approaches (e.g. Henderson–Hassel- balch equation-based algorithms), allowing pK a determina-

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Intelligent Neural Network For Bacteria Classification: An Innovation In Artificial Neural Network

Intelligent Neural Network For Bacteria Classification: An Innovation In Artificial Neural Network

In this section, we discussed some relevant research works which have been done by the application of Artificial Neural Network (ANN).Larsen et al. in 2015 [2] found and analysed some ecologically important microbial communities. . The authors focused on the prediction of microbial community structure by using Artificial Neural Network (ANN) and revealed a Microbial Assembled Prediction (MAP) model which could work on environmental parameters. In this study the ANN based model basically was used to determine bacterial community structure fluctuation with the changes of environment. Shen and Bax in 2015 [3] developed a neural network based robust TALOS-N computer program for protein structural study by NMR spectroscopy. Through this, study TALOS-N was found to be a useful tool to get torsion angles by analyzing chemical shifts of its backbone and also to calculate the NMR protein structure.The application of of neural network method in TALOS-N program it was possible to predict the side-chain χ1 torsion angles and if maximum outcome probability did not satisfy the cutoff value, then outcome was shown as not predicted otherwise predicted. Here cutoff value was a barrier for prediction.
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The synthesis and characterization of new higher nuclearity arene ruthenium sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

The synthesis and characterization of new higher nuclearity arene ruthenium sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

Chemical shifts, Ru-N bondlengths and distances of cymene-Ru for two cationic complexes with nitrogen containing ligands Crystallographic data of the mono-ammonia complex Chemical shifts[r]

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Cryptococcus neoformans Chemotyping by Quantitative Analysis of 1H Nuclear Magnetic Resonance Spectra of Glucuronoxylomannans  with a Computer-Simulated Artificial Neural Network

Cryptococcus neoformans Chemotyping by Quantitative Analysis of 1H Nuclear Magnetic Resonance Spectra of Glucuronoxylomannans with a Computer-Simulated Artificial Neural Network

Quantitation of SRGs: PeakFit. The original proton NMR data for the SRG region were analyzed by using PeakFit as described in Materials and Methods. The PeakFit analysis using the FELIX ASCII file generated from the primary pro- ton NMR data for the SRG region recorded for the GXM from C. neoformans isolate 150 is given in Fig. 5. The area for each identifiable resonance appearing in the proton NMR spectrum (Fig. 4) was assigned to a particular SRG based on its characteristic proton chemical shifts, identified as described above (Table 2). The area data depicted in Fig. 5 were used to calculate the percent occurrence of the SRGs present in the GXM from C. neoformans isolate 150 (Table 3). The analysis was repeated for all the GXMs available, and the results were tabulated (Table 3). The PeakFit data were normalized to 100%.
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Probing intermolecular interactions and three dimensional packing of organic molecules by solid state NMR

Probing intermolecular interactions and three dimensional packing of organic molecules by solid state NMR

In the context of this thesis, solid-state NMR has much potential to play a significant role in the complete structural determination of crystalline powders, primarily in collaboration with first-principles calculations methods of NMR chemical shifts. Specifically, the GIPAW (Gauge Including Projector Augmented Waves) [77, 78] computational approach, developed over the last decade, is based on Density Functional Theory (DFT) and uses planewave pseudopotentials to provide an accuracte description of electronic charge den- sity, and hence NMR chemical shifts, for periodic solid-state materials. GI- PAW has made it possible for NMR parameters to be calculated with surprising accuracy, using existing crystallographic structures such as those determined by single-crystal diffraction, hence, establishing a definitive link between the two complementary characterisation techniques. Experimental and GIPAW- based computational studies have been applied with ever increasing success to a wide range of molecular and materials systems [2, 3, 65, 79–87].
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Two dimensional NMR lineshape analysis

Two dimensional NMR lineshape analysis

also effective to use larger ROIs and fit the overlapping peaks directly. The fitting process itself is best conducted as an iterative process, due to the large number of free parameters (each spin has two chemical shifts and linewidths associated with each state, plus global model parameters). For example, it is often effective to fit chemical shifts and linewidths for the first spectrum alone, then hold these parameters constant for the remainder of the session. If additional constraints are known, for example K d values from other biophysical methods, these can also be held
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Lanthanide Shift Reagents and Their Applications in Nuclear Magnetic Resonance Spectroscopy-A Perespective

Lanthanide Shift Reagents and Their Applications in Nuclear Magnetic Resonance Spectroscopy-A Perespective

Hinkley used to find the paramagnetic shift in case of chlorestrol. The results obtained were landmark and form the basis of paramagnetic NMR spectroscopy. In his experiments, the NMR spectrum of cholesterol without any paramagnetic lanthanide complex (lanthanide shift reagent) show overlapped peaks or resonances and it was difficult to interpret the NMR spectrum. In another case he added little amount of paramagnetic lanthanide complex to the cholesterol solution, the huge chemical shifts were noticed and this form the basis of paramagnetic nuclear magnetic spectroscopy based on induced shift reagents.
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Structure determination, vibrational bands and chemical shift assignments of 3-(4-(3-(2,5-dimethylphenyl)-3-methylcyclobutyl)thiazol-2-yl)-2-(o-tolyl)thiazolidin-4-one: A combined experimental and quantum chemical density-functional theory studies

Structure determination, vibrational bands and chemical shift assignments of 3-(4-(3-(2,5-dimethylphenyl)-3-methylcyclobutyl)thiazol-2-yl)-2-(o-tolyl)thiazolidin-4-one: A combined experimental and quantum chemical density-functional theory studies

For modelling, X-ray coordinates were used as initial geometry, taken with the Babel operation on the Model tab in the WingGX software [34]. To obtain the electronic structure of compound, opti- mization calculations were performed at the DFT level by using the GAUSSIAN03 program package [36], wherein B3LYP function was chosen [30, 31], which combines Becke's three-parameter hy- brid exchange function. To understand the effects of sets based on structural and spectral characteristics, 6-31G(d,p) [a polarized basis set] and 6-31G+(d,p) [a diffuse basis set] were used in calculations. The structural parameters (bond distances, bond angles and torsion angles) and spectral assignments (vibra- tion frequencies and chemical shifts) from the theo- retical molecular structures [DFT/B3LYP/6- 31G(d,p) and DFT/B3LYP/6-31G+(d,p)] were compared with their experimental (X-ray diffrac- tion, FT-IR and NMR) data.
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An NMR study of molecular dynamics in organic crystalline compounds

An NMR study of molecular dynamics in organic crystalline compounds

Chemistry involves a great deal more than the study of molecules in the solution state. Many of the most exciting advances in modem chemistry involve the chemical and physical properties of solids. It would seem appropriate, therefore, to make NMR studies of such substances in the solid-state. With ordered crystalline solids a study of structure and dynamics is usually undertaken by X-ray diffraction methods but, important materials like polymers, silicates, resins, celluloses, coals and surface- immobilised reagents all containing amorphous structures are very difficult to study by diffraction methods. Solid-state NMR enables the chemist to probe the environment of the atoms in the solid matrix. Instead of being surrounded by a sheath of solvent molecules, the individual molecules of a solid lie side by side in the solid matrix with the orientation of their dipoles fixed in a random pattern. The resultant effect of this can be seen in the chemical shifts and splitting patterns. There are two main interactions:
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Integrating calculation and experiment : developing processes and tools for NMR crystallography of organic solids

Integrating calculation and experiment : developing processes and tools for NMR crystallography of organic solids

Chapter 4 is a publication entitled “Visualising packing interactions in solid- state NMR: Concepts and applications”. Ab initio calculations have a proven ability to predict and assign experimental solid-state NMR spectra. However, such calcu- lations also have the potential to provide deeper information, such as why nuclei have specific NMR parameters and what this tells us about their local environ- ment. In this paper we introduce a theoretical framework to address these aims. We show how the magnetic shielding can be divided into short-range terms arising from current close to the nucleus in question, and to a long range contribution. An analysis of 71 molecular crystals shows us that the majority of change in the chemi- cal shift for protons comes from the long-range term, however for heavier atoms the short-range terms dominate. This is why protons are the most sensitive nuclei for NMR crystallography investigations of intermolecular interactions associated with different solid-state forms. In addition to a GIPAW calculation on the full unit cell, the NMR magnetic shieldings are calculated for a single molecule in a box, and the differences in magnetic shielding are analysed. A framework for calculating the Nuclear Independent Chemical Shift (NICS) is demonstrated, where a calcula- tion is performed on a unit cell containing neighbouring molecules but excludes the molecule of interest. We also introduced a quantity known as the Magnetic Shield- ing Contribution Field (MSCF). Plots of the MSCF highlight the regions of space responsible for the shielding of a particular atom. We show how the combination of these tools can be used to identify the contribution of ring currents due to aromatic motifs and hydrogen bonds on NMR chemical shifts. We apply this formalism to ex- amine the intermolecular interactions in a host-guest compound, a pharmaceutical polymorph and a co-crystal.
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Solution structure of a Plasmodium falciparum AMA 1/MSP 1 chimeric protein vaccine candidate (PfCP 2 9) for malaria

Solution structure of a Plasmodium falciparum AMA 1/MSP 1 chimeric protein vaccine candidate (PfCP 2 9) for malaria

C/ 15 N-labeled PfCP-2.9 were expressed in P. pastoris for NMR structure analysis. The backbone chemical shift assignments can be obtained for a reasonable por- tion of the residues in PfCP-2.9. By comparing with the previously reported studies of the two domains alone, high similarity of chemical shifts was observed. Relatively larger differences were observed for only a small number of residues, which may be due to differ- ent experimental conditions (e.g., buffer pH and tem- perature). In fact, almost all the residues that showed significant chemical shift changes in PfAMA-1(III) were charged residues, with the exception of Cys63, which is near charged residues according to the NMR structure of PfAMA-1 (III). In addition, PfCP-2.9 was modified in the following ways: three glycosylation sites were removed by changing Asn to Gln, a hinge consisting of 28 residues was inserted between the two domains [21], and a 6×His-tag was added to its C-ter- minus. These modifications can also influence the che- mical shift of nearby residues.
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