Diels-alder adducts of 3,6-dibromophencyclone with symmetrical 1,4-disubstituted-cis-2-butenes: comparisons with the adduct of phencyclone and N-benzylmaleimide, and one-dimensional and two-dimensional nuclear magnetic resonance studies and ab initio structure calculations

Hindered Diels-Alder adducts have been prepared from 3,6-dibromophencyclone, 2, with cis-1,4-diacetoxy-2-butene, 3; cis-2-butene-1,4-diol, 4; and N-benzylmaleimide, 5. The adduct from the parent phencyclone, 1, with N-benzylmaleimide was prepared for comparison. One- and two-dimensional (1D and 2D) proton and carbon-13 NMR studies (at 7.05 tesla, ambient temperatures), including high-resolution COSY45 and HETCOR (XHCORR) chemical shift correlation spectra, were performed, allowing extensive rigorous assignments for protons and protonated carbons. Substantial anisotropic shielding was seen for the ortho protons of the N-benzyl group in the adducts of 5 with 1 or 2, with these aryl protons resonating at 6.25 ppm (CDCl3) for each adduct. The unsubstituted bridgehead phenyls of all four adducts showed slow exchange limit (SEL) 1H and 13C spectra. Greater shift dispersions for the bridge-head phenyl protons in the adducts from 5 relative to those from 3 or 4 suggested the role of the imide carbonyls for anisotropic contributions or for influences on adduct geometry. Ab initio geometry optimizations were performed at the Hartree-Fock level with the 6-31G* basis set (or the LACVP* basis set for the bromine-containing compounds) for each of the adducts. For the two adducts from benzylmaleimide, separate minima were located corresponding to conformers in which the benzyl group was directed into the adduct cavity (syn) or out of the adduct cavity (anti). Calculated energies and geometric parameters for the adducts are presented, and these suggested a significantly different structure for the dibromo diacetate adduct, in terms of general symmetry and bridgehead phenyl geometries, compared to the other adducts.     

1H and 13C nuclear magnetic resonance studies of the hindered phencyclone adducts of some smaller branched N-alkyl maleimides: rigorous aryl proton assignments with high-resolution two-dimensional (COSY45) spectroscopy, and anisotropic shielding effects and ab initio geometry optimizations

Phencyclone, 1, a potent Diels-Alder diene, reacts with a series of N-alkylmaleimides, 2, to form hindered adducts, 3. The 300 MHz 1H and 75 MHz 13C NMR studies of these adducts at ambient temperatures have demonstrated slow rotations on the nuclear magnetic resonance (NMR) timescales for the unsubstituted bridgehead phenyl groups, and have revealed substantial magnetic anisotropic shielding effects in the 1H spectra of the N-alkyl groups of the adducts. The selected N-alkyl groups for the target compounds emphasized smaller branched alkyls, including C3 (isopropyl, a); C4 (isobutyl, b; and t-butyl, c); C5 (n-pentyl, d; isopentyl [isoamyl], e; 1-ethylpropyl, f; t-amyl, g;) and a related C8 isomer (1,1,3,3-tetramethylbutyl ["t-octyl"], h). The straight-chain n-pentyl analog was included as a reference. This present work on the branched N-alkylmaleimide adducts appreciably extends our earlier compilation on the N-n-alkylmaleimide adducts. Key methods for proton assignments included "high-resolution" 1H-1H chemical shift correlation spectroscopy, COSY45. 13C NMR of the adducts, 3, verified the expected number of aryl carbons for slow exchange limit (SEL) spectra of the bridgehead phenyl groups. The synthetic routes involved reaction of the corresponding amines, 4, with maleic anhydride to give the N-alkylmaleamic acids, 5, which underwent cyclodehydration to form the maleimides, 2. Magnetic anisotropic shielding magnitudes for alkyl group protons in the adducts were calculated relative to corresponding proton chemical shifts in the maleimides. Geometry optimizations for the above adducts (and for the N-n-butylmaleimide adduct) were performed at the Hartree-Fock level with the 6-31G* basis set. The existence of different contributing conformers for the adducts is discussed with respect to their calculated energies and implications regarding experimentally observed anisotropic shielding magnitudes.     

Morphology of the poly(vinyl alcohol)–poly(vinyl acetate) copolymer in macrodefect-free composites: a 13C magic-angle-spinning nuclear magnetic resonance and 1H spin-diffusion study

A study was made of the macrodefect-free (MDF) composite based on aluminate cement and a poly(vinyl alcohol)–poly(vinyl acetate) (PVAc) copolymer by ¹³C cross-polarization magic-angle-spinning nuclear magnetic resonance. The spectra were run on both the copolymer and the MDF composite in order to observe the atomic environments of the carbon nuclei. An analysis of the intramolecular hydrogen bonds showed a stronger modification in the sample containing CaAl₂O₄ (CA) than in that containing Ca₃Al₂O₆ (C₃A). From the spectra, it was seen that deacetylation had occurred, and that there was interaction between acetate groups and the calcium and aluminium ions. Proton relaxation times both in the laboratory frame, T ₁(H), and in the rotating frame, T1ρ(H), were exploited for the study of the dimension of the polymer matrix in MDF composites. An extended interphase was identified in the composite containing CA. A comparison with the behaviour of the composite based on silicates Ca₃SiO₅–PVAc highlights the better mixing of the phases in the MDF composites containing CA. This revised version was published online in November 2006 with corrections to the Cover Date.     

Quantum Chemical ab initio Investigations of Non-Covalent Bonding Derivatives of Fullerene C60 and Li Atom or Cs2, C6H6 Molecules

Abstract

Quantum chemical ab initio investigations of the stability of the non-covalent fullerene complexes: C₆₀ molecule + Li atom, two C₆₀, two C₆₀ + CS₂, C₆₀ + CS₂, C₆₀ + C₆H₆ were performed using Hartree-Fock (HF) and Density Functional Theory (DFT) methods in various basis sets. The inclusion of electron correlation effect calculated by using DFT B3PW91 model during the optimization of Li atom position above hexagonal of C₆₀ gives the smaller distance from the centre of C₆₀ equal to 7.75 Å and large positive energy of formation equal to 4.452 kcal/mol in comparison with HF calculated distance 8.39 Å and energy of formation 1.810 kcal/mol. The positive energy of formation equal to 0.483 kcal/mol for optimized complex two C₆₀ + one CS₂ was found by HF. The presence of CS₂ molecule stabilises this complex with the energy equal to 0.281 kcal/mol. Complexes: C₆₀ + CS₂, C₆₀ + C₆H₆ do not possess the positive energy of formation.     

Contribution of 1H combined rotation and multipulse spectroscopy nuclear magnetic resonance to the study of tricalcium silicate hydration

Hydration products of tricalcium silicate (C₃S) are the calcium silicate hydrates (C–S–H) and portlandite. Silica fume, added to anhydrous cement in industrial formulations, reacts with portlandite and leads to C–S–H slightly different from the previous one (this reaction is called the pozzolanic reaction). C₃S hydration at 120 °C with and without silica fume has been studied by two ¹H nuclear magnetic resonance techniques: combined rotation and multi-pulse spectroscopy (CRAMPS) and magic angle spinning (MAS). The static spectra are broadened by the proton–proton dipolar interaction. The ¹H MAS technique does not allow us to remove the effects of this interaction completely and cannot be in this case a quantitative method. Therefore the CRAMPS technique, which can remove the broadening of the interaction because of the use of a multipulse sequence associated with the sample rotation, was used. It is shown that the CRAMPS NMR spectra allow us to describe the action of silica fume on the hydrates and to reveal the competition between portlandite formation around the C₃S grains and portlandite dissolution near the silica grains until the complete dissolution of portlandite. This revised version was published online in November 2006 with corrections to the Cover Date.     

1H nuclear magnetic resonance characterization of Portland cement: molecular diffusion of water studied by spin relaxation and relaxation time-weighted imaging

Water molecular dynamics in a hardened Portland cement were characterized by proton Fourier transform nuclear magnetic resonance (NMR) at 400 MHz. Three different types of water molecule (physically bound, chemically bound and porous trapped) were observed. When the hardened cement sample was heated at 105 °C, the physically bound water diffused out of the sample as a function of the heating time while the chemically bound water remained in a stable form. A trace amount of the porously trapped water was also detected to remain in the cavities of the hardened cement even after heating for up to 20 h at this temperature. The loss of the physically bound water proved to be a diffusion-controlled process as evidenced from the NMR data and from a gravimetric technique. A Pake doublet was observed in the NMR spectra. This is a result of the oscillation of the water molecules with hindered molecular motions due to their entrapment in the cement pores. Soaking the dried samples in water resulted in the diffusion of water back into the hardened cement as physically bound water. Nuclear spin–spin relaxation time, T2-weighted imaging showed that the distribution of the physically bound water inside the cylindrical sample formed a doughnut shape after overnight soaking. The residual air in the cement pores may have slowed down the diffusion rate of the water molecules back into the dried cement. © 1998 Kluwer Academic Publishers     

Solid state spatially resolved 1H and 19F nuclear magnetic resonance spectroscopy of dental materials by stray-field imaging

As part of a program to evaluate the use of stray-field magnetic resonance microimaging (STRAFI) in dental materials research spatially resolved nuclear magnetic resonance (NMR) for solid dental cements has been investigated. By applying a quadrature echo pulse sequence to a specimen positioned in the stray-field of a NMR spectrometer superconducting magnet the magnetic resonance within a thin slice was obtained. The specimen was stepped through the field in 500 m increments to record ¹ and ¹⁹F profiles and T₂ values at each point. The specimens were fully cured cylinders made from four types of restorative material (glass ionomer, resin modified glass ionomer, compomer, composite). The values for F¹⁹T₂ varied with material type and reflected the nature of the matrix structure. For all materials containing ¹⁹F in the glass two values were calculated for ¹⁹F T₂, one short and one long. These were relatively invariant. Solid state magic angle spinning (MAS)-NMR showed that they came from the glass. This suggests that a proportion of the element is relatively mobile (in a glass phase) and the remainder is more tightly bound (in a compound dispersed in the glass). This demonstration, that NMR microimaging of both ¹H and ¹⁹F in solid dental cements is possible, opens up exciting new possibilities for investigating the distribution of these elements (in particular fluorine) in solid dental materials. ©©1999©Kluwer Academic Publishers     

Local structures of mesoporous bioactive glasses and their surface alterations in vitro: inferences from solid-state nuclear magnetic resonance

We review the benefits of using (29)Si and (1)H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy for probing the local structures of both bulk and surface portions of mesoporous bioactive glasses (MBGs) of the CaO-SiO(2)-(P(2)O(5)) system. These mesoporous materials exhibit an ordered pore arrangement, and are promising candidates for improved bone and tooth implants. We discuss experimental MAS NMR results from three MBGs displaying different Ca, Si and P contents: the (29)Si NMR spectra were recorded either directly by employing radio-frequency pulses to (29)Si, or by magnetization transfers from neighbouring protons using cross polarization, thereby providing quantitative information about the silicate speciation present in the pore wall and at the MBG surface, respectively. The surface modifications were monitored for the three MBGs during their immersion in a simulated body fluid (SBF) for intervals between 30 min and one week. The results were formulated as a reaction sequence describing the interconversions between the distinct silicate species. We generally observed a depletion of Ca(2+) ions at the MBG surface, and a minor condensation of the silicate-surface network over one week of SBF soaking.     

Reversed-phase high-performance liquid chromatography combined with on-line UV diode array, FT infrared, and 1H nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry: application to a mixture of nonsteroidal antiinflammatory drugs

A prototype multiply hyphenated system has been applied to the analysis of a mixture of nonsteroidal antiinflammatory drugs separated by reversed-phase HPLC. Characterization of the model NSAIDs was achieved via a combination of diode array UV, 1H NMR, FT-IR spectroscopy, and time-of-flight mass spectrometry. This combination of spectrometers allowed the collection of UV, 1H NMR, IR, and mass spectra together with atomic composition data enabling almost complete structural characterization to be performed.     

1H MAS NMR (magic-angle spinning nuclear magnetic resonance) techniques for the quantitative determination of hydrogen types in solid catalysts and supports

Distinct hydrogen species are present in important inorganic solids such as zeolites, silicoaluminophosphates (SAPOs), mesoporous materials, amorphous silicas, and aluminas. These H species include hydrogens associated with acidic sites such as Al(OH)Si, non-framework aluminum sites, silanols, and surface functionalities. Direct and quantitative methodology to identify, measure, and monitor these hydrogen species are key to monitoring catalyst activity, optimizing synthesis conditions, tracking post-synthesis structural modifications, and in the preparation of novel catalytic materials. Many workers have developed several techniques to address these issues, including 1H MAS NMR (magic-angle spinning nuclear magnetic resonance). 1H MAS NMR offers many potential advantages over other techniques, but care is needed in recognizing experimental limitations and developing sample handling and NMR methodology to obtain quantitatively reliable data. A simplified approach is described that permits vacuum dehydration of multiple samples simultaneously and directly in the MAS rotor without the need for epoxy, flame sealing, or extensive glovebox use. We have found that careful optimization of important NMR conditions, such as magnetic field homogeneity and magic angle setting are necessary to acquire quantitative, high-resolution spectra that accurately measure the concentrations of the different hydrogen species present. Details of this 1H MAS NMR methodology with representative applications to zeolites, SAPOs, M41S, and silicas as a function of synthesis conditions and post-synthesis treatments (i.e., steaming, thermal dehydroxylation, and functionalization) are presented.     

Microphase structure and calculations of the interphase in poly (styrene-b-methylphenylsiloxane) diblock copolymers: a comparative study from small-angle X-ray scattering,electron spectroscopic imaging and solid-state nuclear magnetic resonance

The microphase structure of a series of poly (styrene-b-methylphenylsiloxane) (PS-b-PMPS)-diblock copolymers with various compositions and molecular weights has been studied by small-angle X-ray scattering, electron spectroscopic imaging and solid-state nuclear magnetic resonance spectroscopy. This diblock copolymer system is miscible within a distinct range of temperature and molecular weight exhibiting an upper critical solution temperature. The three chosen methods which complement each other can be applied to the chemically unmodified model system. The results of the various measurements correlate to describe the microphase structure, the domain size and the interphase.     

Demonstration of nuclear magnetic resonance imaging for void detection in carbon-fibre reinforced polymer composites,and comparison with ultrasound methods

Nuclear magnetic resonance imaging has been used as a method of void detection in carbonfibre reinforced polymer composites. This is accomplished by observation of signal from water molecules which have ingressed into surface-connected defect regions within the polymer composite. Problems associated with the conductivity of these samples are discussed, along with methods of overcoming those difficulties.     

A solid state 13C nuclear magnetic resonance investigation of the thermal degradation of a poly(ethylene glycol) and poly(vinyl alcohol) binder in an alumina ceramic

Cross polarization and magic angle spinning ¹³C nuclear magnetic resonance spectroscopy (CP-MAS ¹³C NMR) has been used to investigate the thermal degradation of poly(ethylene glycol) (PEG)-alumina, poly(vinyl alcohol) (PVA)-alumina, and a mixture of 6% PEG and 0.5% PVA in alumina. Samples were prepared by thermally treating each polymer at 450°C to remove pre-specified weight losses. The results showed that the polymer chains of both PEG and PVA thermally degraded as postulated in previously published mechanistic studies based on volatile degradation product analyses. The CP-MAS ¹³C NMR spectra of PEG and PVA in alumina showed that the two polymers thermally decomposed independently of each other. This revised version was published online in November 2006 with corrections to the Cover Date.     

Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses

Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.     

Structural,thermal, spectroscopic and magnetic studies of the (C2N2H10)0.5[FexV1−x(HPO3)2] (x = 0.26, 0.52, 0.74) solid solution

The (C₂N₂H₁₀)_0.5[Fe_xV_1−x(HPO₃)₂] (x = 0.26, 0.52 0.74) compounds have been obtained by mild solvothermal conditions in the form of micro-crystalline powder with brown color. The crystal structures were refined by X-ray powder diffraction data using the Rietveld method. The compounds crystallize in the monoclinic system, space group P2/c with the unit-cell parameters, a = 9.262(5) Å, b = 8.823(5) Å, c = 9.714(6) Å, β = 120.84(3)°; a = 9.245(1) Å, b = 8.823(1) Å, c = 9.698(1)Å, β = 120.80(1)° and, a = 9.254(4)Å, b = 8.822(4)Å, c = 9.702(4)Å, β = 120.73(3)° for (C₂N₂H₁₀)_0.5[Fe_0.26V_0.74 (HPO₃)₂] (1), (C₂N₂H₁₀)_0.5[Fe_0.52V_0.48(HPO₃)₂] (2), and (C₂N₂H₁₀)_0.5[Fe_0.74V_0.26(HPO₃)₂] (3). The compounds show an open crystalline structure with three-dimensional character, whose formula for the anionic inorganic skeleton is [M(HPO₃)₂]²⁻. The inorganic framework is formed by [MO₆] octahedra inter-connected by phosphite groups. The structure of the compounds exhibits channels extended along the [1 0 0] and [0 0 1] directions and the ethylendiammonium cations are located inside these channels, linked through hydrogen bonds and ionic interactions. The infrared spectra show the bands corresponding to the stretching (P–H) vibration of the phosphite group and the band corresponding to the deformation mode of the ethylendiammonium cation, δ(NH₃⁺). The thermal and thermodiffractometric behavior show that the compounds are stable up to approximately 300 °C, at higher temperatures the decomposition of the crystal structure by calcination of the organic cation starts. The diffuse reflectance spectra show bands of the V³⁺ ion (d²), and a band of the Fe³⁺ ion (d⁵), in a slightly distorted octahedral symmetry. The values of the Dq and Racah parameters (B and C) have been calculated for the V(III) cation. Magnetic measurements were performed on a powdered sample from 5 to 300 K at magnetic fields 1000, 500 and 100 G, in the ZFC and FC modes. At the magnetic field of 1000 G antiferromagnetic interactions were observed, but at 100 G have been detected higher values of the χ_m in the FC mode than those observed in the ZFC one, indicating the existence of a dominant ferromagnetic component at low temperature. The magnetization measurements show hystheresis loops at 5 K, with values of the remanent magnetization and coercive field of 1.91 emu/mol and 23 Gauss for (1), 25 emu/mol and 300 Gauss for (2), and 3 emu/mol and 50 Gauss for the compound (3).     

Role of high resolution in magnetic resonance (MR) imaging: Applications to MR angiography,intracranial T1-weighted imaging,and image interpolation

The role of high-resolution imaging has generally been limited because of the associated loss of signal-to-noise ratio (SNR) as voxel size decreases and imaging time increases. Despite these truths, we show that high-resolution imaging methods can be used to perform better magnetic resonance angiography (MRA), enhance visibility of small structures, and allow better image interpolation. Specifically, we show that very small vessels can be seen with conventional MRA methods, and small lesions on the order of a few cubic millimeters can be seen with a single dose of gadolinium diethyltriaminepentaacetic acid, and structures such as the hippocampal formation are best depicted when a high-resolution three-dimensional (3D) imaging method is used. We also show that image interpolation for the 3D visualization of structures with complicated geometry is best accomplished with a fractional voxel evaluation using the Fourier transform shift theorem on high-resolution images. We demonstrate that the expression for visibility, CNR √p, can be used to establish the optimal resolution to see a given structure. CNR refers to the contrast-to-noise ratio and p is the number of voxels occupied by the object in the image. The optimal resolution is determined from theoretical curves of visibility as a function of voxel size relative to object size. We also demonstrate the enhancement of small vessel visibility on individual images and maximum-intensity projection images with voxel sizes as small as 0.29 mm using 1024 sampled points in the readout direction. Using 3D visibility arguments, it is predicted that under the right conditions, objects of interest much smaller than the voxel size can be seen on conventional MR images. © 1997 John Wiley & Sons, Inc. Int J Imaging Syst Technol, 8, 529–543, 1997     

(C2N2H10)[FexV1−x(HPO3)F3] (x = 0.44, 0.72): Two new organically templated phosphites: Solvothermal synthesis and structural,thermal, spectroscopic and magnetic studies

(C₂N₂H₁₀)[Fe_xV_1−x(HPO₃)F₃] (x = 0.44, 0.72) have been synthesized using mild solvothermal conditions under autogenous pressure and the ethylenediamine molecule as templating agent. The crystal structures have been determined from X-ray single-crystal diffraction data. The compounds crystallize in the orthorhombic P2₁2₁2₁ space group with Z = 4 and unit-cell parameters a = 12.8494(9), b = 9.5430(6), c = 6.4372(5) Å, and a = 12.8578(1), b = 9.5342(1), c = 6.4370(7) Å for (C₂N₂H₁₀)[Fe_0.44V_0.56(HPO₃)F₃] and (C₂N₂H₁₀)[Fe_0.72V_0.28(HPO₃)F₃], (1) and (2), respectively. These isostructural compounds exhibit a monodimensional crystal structure formed by pillared double anionic chains with the formula [M(HPO₃)F₃]²⁻, extended along the [0 0 1] direction. These doubled ionic chains are the result of the linking of two simple chains in which there are alternating octahedral [MO₃F₃] and tetrahedral groups [HPO₃]. The ethylendiammonium cations are placed in the space delimited by three different chains. The metallic ions are interconnected by the pseudo-pyramidal (HPO₃)²⁻ phosphite oxoanions, adopting a slightly distorted octahedral geometry. The IR spectra show bands corresponding to the phosphite oxoanion and the ethylendiamonium cation at 2400 and 1600 cm⁻¹, respectively. The thermogravimetric analyses show that these phases are stable up to ca. 280 °C, at higher temperatures, the decomposition of the crystal structure begins by calcination of the organic cation and the elimination of the fluoride anions. The diffuse reflectance spectra show bands of the V³⁺ ion (d²) in octahedral symmetry. The values of the Dq (1540, 1540 cm⁻¹), and Racah parameters, B (560, 535 cm⁻¹) and C (3055, 3140 cm⁻¹) for (1) and (2), respectively, correspond with those usually found for octahedrically coordinated V(III) compounds. Magnetic measurements, performed on a powered sample from 5.0 to 300 K at 1000 G, in the ZFC and FC modes, indicate the existence of antiferromagnetic interactions.     

Hot Wear Behavior of Steels 28NCDV10/Z20C13: Influence of Pre-Oxidation and Comparison with Al2O3, Al2O3-TiO2 Coatings

The purpose of this work is to investigate the influence of the preexistent oxide film on friction process between the forming tool and the tube, during the piercing in hot metal forming. A wear behavior of a low alloy steel (28NCDV10) is studied on a cylinder-ring tribometer. Two different atmospheres, which are air and steam, are employed for oxidizing the rings at 85O°C. The experimental results of rings without pre-oxidation exhibit a severe oxidation wear and metal transfer from the cylinder to the ring. While the oxidation of the rings, notably in the case of steam, shows a decrease in the wear rate. For a comparison with metallic materials, we considered some ceramic materials: A1₂O₃, Al₂O₃-TiO₂ We find that the metallic materials pre-oxidized in steam have a better behavior than all the other materials tested.