Biomedical subjects

Christian Fernandez

Publications and source records attributed to Christian Fernandez.

8 recordsLinked to original sources

PubMed2006

Structural and spatially resolved studies on the hardening of a commercial resin-modified glass-ionomer cement.

A commercial photopolymerizable resin-modified glass-ionomer (Fuji II LC) was studied using a variety of nuclear magnetic resonance (NMR) techniques. (1)H and (19)F stray-field imaging (STRAFI) enabled to follow the acid-base reaction kinetics in self-cured (SC) samples. Gelation and maturation processes with 25 min and 40 h average time constants, respectively, were distinguished. In self- & photo-cured (SPC) samples, two processes were also observed, which occurred with 2 s and 47 s average time constants. (1)H, (27)Al and (29)Si magic angle spinning (MAS) NMR, (13)C cross-polarization (CP)/MAS NMR and (27)Al multiple quanta (MQ)MAS NMR spectroscopy were used to obtain structural information on the glass and cements that were either SC or SPC. The presence of methacrylate groups was identified in the solid component. Unreacted hydroxyl ethylmethacrylate (HEMA) was detected in self-cured cement. (27)Al data showed that approximately 28% and 20% of Al is leached out from glass particles in SC and SPC samples, respectively. The upfield shift detected in (29)Si MAS NMR spectra of the cements is consistent with a decrease in the number of Al species in the second coordination sphere of the silicon structures. Scanning electron microscopy (SEM) showed existence of 3D shrinkage of the cement matrix in photo-cured cements.

Glass Ionomer Cements↗

PubMed2006

Characterization of microporous aluminophosphate IST-1 using (1)H Lee-Goldburg techniques.

The presence of two independent methylamine species in microporous aluminophosphate IST-1 (|(CH(3)NH(2))(4)(CH(3)NH(+)(3))(4)(OH(-))(4)|[Al(12)P(12)O(48)]) has been shown previously by synchrotron powder X-ray diffraction. One of these species, [N(1)-C(1)], links to a six-coordinated framework Al-atom [Al(1)], while the other methylamine [N(2)-C(2)] is protonated and hydrogen-bonded to three O-atoms [O(1), O(2) and O(12)]. We revisit the structure of IST-1 and report the complete assignment of the (1)H NMR spectra by combining X-ray data and high-resolution heteronuclear/homonuclear solid-state NMR techniques based on frequency-switched Lee-Goldburg homonuclear decoupling and (31)P-(31)P homonuclear recoupling. Careful analysis of the 2D (1)H-X homonuclear correlation (X=(1)H) and 2D heteronuclear correlation (X=(13)C, (31)P and (27)Al) spectra allowed the distinction of both methylamine species and the assignment of all (31)P and (13)C resonances. For the first time at a relatively high (9.4 T) magnetic field, symmetric doublet patterns have been observed in the (13)C spectra, caused by the influence of the (14)N second-order quadrupolar interaction.

Journal Article↗

PubMed2005

X-ray diffraction and solid-state NMR studies of a germanium binuclear complex.

A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).

Journal Article↗

PubMed2005

Multiplex MQMAS NMR of quadrupolar nuclei.

A multiplex phase cycling method (N. Ivchenko et al., J. Magn. Reson. 160 (2003) 52-58) has been used to record two-dimensional MQMAS spectra with a very short phase cycling. A straightforward procedure has been developed to easily process the data. Combining this Multiplex approach and the new Soft-Pulse-Adding-Mixing (SPAM) method considerably increases the signal-to-noise ratio of the conventional MQMAS experiment. The Multiplex acquisition procedure is much simpler than the echo/anti-echo method recently proposed, and has been applied with success to record (87)Rb spectra of RbNO(3) and (27)Al 3Q and 5Q MQMAS NMR of microporous aluminophosphate AlPO(4)-14.

Journal Article↗

PubMed2004

Stray-field imaging and multinuclear magnetic resonance spectroscopy studies on the setting of a commercial glass-ionomer cement.

A commercial glass-ionomer (Fuji II) was studied using different NMR techniques. 1H and 19F stray-field imaging (STRAFI) were used to monitor the curing kinetics of the cement and two processes were distinguished: the gelation and maturation phases. Characterization of the aluminium and silicon species present in the glass component and cement was performed by conventional 27Al and 29Si MAS and two-dimensional 27Al triple quantum MAS NMR (MQMAS) techniques. Quantification of the aluminium in the glass component and in the cement indicates the leaching of about 32% of the 4-coordinate aluminium, about 100% of the 5-coordinate aluminium and about 41% of the 6-coordinate aluminium, during the setting reaction. It is also shown that the 5-coordinate aluminium is only present in the surface layer created by the acid attack during the cement formation process. In the cement, silicon maintains species with four bridging oxygens after the leaching of tetrahedral (4-coordinate) aluminium. The silicon analysis correlates well with the aluminium determinations.

Aluminum↗

PubMed2003

I-STMAS, a new high-resolution solid-state NMR method for half-integer quadrupolar nuclei.

In complement to the previously proposed multiple-quantum magic-angle-spinning (MQMAS) and satellite transition MAS (STMAS) sequences, we describe a new two-dimensional high-resolution method, inverse-STMAS (I-STMAS) that allows second-order quadrupolar averaging. Like STMAS, I-STMAS correlates second-order quadrupole dephasing occurring on coherences related to the central transition (CT) and satellite transitions (STs), but does it in a reverse manner: CT evolves during the t(1) period while STs are detected during t(2). Although STMAS and I-STMAS are symmetric, there are some interesting and useful differences between the two methods. For example, we show that during the acquisition time t(2), it is possible to over-sample the data and then to process them to suppress the CT-CT correlation resonance.

Journal Article↗

PubMed2002

Triple-quantum magic angle spinning (27)Al NMR of aluminum hydroxides.

We show that (27)Al triple-quantum magic angle spinning (3Q-MAS) experiments alleviate the second-order quadrupolar broadening to reveal the structure-building units of nonequivalent aluminum octahedra in the most extensively studied aluminum hydroxides, namely, gibbsite, bayerite, and boehmite. Further, aided by ab initio calculations of the electric field gradient tensors, the 3Q-MAS/MAS results are shown to lead to the assignment of (27)Al isotropic resonances to the aluminum positions in their X-ray-determined structures. The present work paves the way for future studies on various structurally transformed materials derived from these basic aluminum hydroxides.

Journal Article↗

PubMed2002

Double-resonance decoupling for resolution enhancement of 31P solid-state MAS and 27Al --> 31P MQHETCOR NMR.

27Al decoupling has been used to remove residual J-coupling interactions between 31P and 27Al in microporous aluminophosphates AlPO4-14 and AlPO4-40. In combination with 1H high-power decoupling, 27Al adapted decoupling yields 31P spectra with optimal sensitivity and resolution. The importance of double-resonance decoupling is further demonstrated by incorporating this technique in the MQHETCOR sequence. Unambiguous assignment of all the AlPO4-14 nuclear magnetic resonances is achieved by combining multiple-quantum evolution in the 27Al dimension and double-resonance decoupling in the 31P acquisition domain.

Aluminum Compounds↗