Gaspard Huber

Gaspard Huber
Atomic Energy and Alternative Energies Commission | CEA · Institut rayonnement matière de Saclay (IRAMIS)

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62
Publications
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Introduction
Gaspard Huber currently works at the Institut rayonnement matière de Saclay (IRAMIS), Atomic Energy and Alternative Energies Commission. Gaspard does research in Spectroscopy. Their current project is 'gas binding in cage-molecules', and hyperpolarization of noble gases and from parahydrogen.

Publications

Publications (62)
Article
Full-text available
The study of the metabolome within tissues, organisms, cells or biofluids can be carried out by several bioanalytical techniques. Among them, nuclear magnetic resonance (NMR) is one of the principal spectroscopic methods. This is due to a sample rotation technique, high-resolution magic angle spinning (HR-MAS), which targets the analysis of heterog...
Article
Full-text available
Cucurbit[n]urils are rigid cage-molecules of pumpkin-like shape, made of n-glycoluril units, able to bind mainly neutral molecules and cations. In this work, we investigate the binding of three cucurbit[5]uril derivatives with dioxygen O2 and show that one of them, namely per-hydroxylated cucurbit[5]uril, (OH)10CB[5], is able to significantly bind...
Article
The analysis of complex mixtures of dissolved molecules is a major challenge, especially for systems that gradually evolve, e.g., in the course of a chemical reaction or in the case of chemical instability. 1D NMR is a fast and non‐invasive method suitable for detailed molecular analysis, though of low sensitivity. Moreover, the spectral resolution...
Article
The localization of metabolic profiles within a tissue sample is of particular interest when the sampling size is considerably small, i.e. in the order of microgram (μg) scale. Small sampling size is inevitable when the sample availability is limited, or when different metabolic profiles are suspected in small disparate sample regions. Capitalizing...
Article
New sulfide‐functionalized bambus[4]urils ((RS)8BU[4]) and bambus[6]urils ((RS)12BU[6]) have been synthesized through thiol‐ene click coupling reactions (TEC) of allylbambus[n]urils. Synthesis of BU[6] derivatives always requires the use of a template anion (iodide, chloride or bromide) which is enclosed in the cavity of BU[6]. We show that this an...
Article
Cryptophanes, cage-molecules constituted of aromatic bowls, are now well recognized as powerful xenon hosts in 129Xe NMR-based biosensing. In the quest of a dual probe that can be addressed only by NMR we have studied three cryptophanes bearing a tether with an unsaturated bond. The idea behind this is to build probes that can be detected both via...
Data
Toxicity assessment of nano-TiO2 toward E. coli. Survival (normalized to control without nanoparticles) of E. coli, incubated under room light during 3h at 37°C in Seine river water with increasing concentrations of nano-TiO2: P25 (red), R (blue), M (green), A (purple). (PDF)
Data
Comparison of the upfield part of NMR 1H spectra of E. coli MG1655 metabolites as a function of perchloric acid concentration. Downfield part in Fig 1B of the main text. (PDF)
Data
Compiled data for 1H NMR spectrum of Fig 2. For each area: number, maximum and minimum chemical shift, letter for the assignment on Fig 2, assignment, association of metabolite to their class. Classes: NNA: nucleosides, nucleotides and analogues; AA: amino acids; CAH: carbohydrates; OA: organic acids; OM: other metabolites; SDC: superimposition of...
Data
Comparison of the upfield part of NMR 1H spectra of E. coli MG1655 metabolites as a function of the boiling time. Downfield part in Fig 1A of the main text. (PDF)
Data
TEM images of E. coli in contact with R type nano-TiO2. 1000ppm of R (up) or 100 ppm (down). (PDF)
Data
Evolution hydroxyl and superoxide radicals produced by photocatalysis of P25 and R TiO2 nanoparticles. (PDF)
Data
Physicochemical characterization of the TiO2 nanoparticles used in this study. (PDF)
Data
An example of region definition and baseline correction method for integration. Part of the spectrum of Fig 2 of main text, showing region of integration 17 (see S2 Table). (PDF)
Article
In a previous study, it was demonstrated that the toxic impact of titanium dioxide nanoparti-cles on Escherichia coli starts at 10 ppm and is closely related to the presence of little aggregates. It was also assumed that only a part of the bacterial population is able to adapt to this stress and attempts to survive. Proteomic analyses, supported by...
Article
Full-text available
Signal amplification by reversible exchange (SABRE) is a promising method to increase the sensitivity of nuclear magnetic resonance (NMR) experiments. However, SABRE-enhanced NMR 1H signals are short-lived and SABRE is often used to record 1D NMR spectra only. When the sample of interest is a complex mixture, this results in severe overlaps for 1H...
Article
Full-text available
The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a functi...
Article
For optimizing sensitivity and RF excitation, high resolution NMR probes have to be tuned at the Larmor frequency and matched to 50 Ω-transmission lines to which they are connected. For achieving this setting, one usually resorts to the wobulation function which consists in sweeping the frequency of the power source while monitoring and minimizing...
Article
Full-text available
Three optimum conditions for the tuning of NMR probes are compared: the conventional tuning optimum, which is based on radio-frequency pulse efficiency, the spin noise tuning optimum based on the line shape of the spin noise signal, and the newly introduced frequency shift tuning optimum, which minimizes the frequency pushing effect on strong signa...
Article
Full-text available
Four new cucurbiturils CynCB[6] containing n (n = 1, 2, 4, 5) cyclohexyl equatorial units have been synthesized to complete the family of known Cy3CB[6] and Cy6CB[6] derivatives. A new CB[6] member bearing a propanediurea unit has also been prepared. The CB[6] derivatives show better solubility in pure water than native CB[6]. One cyclohexyl unit i...
Article
Full-text available
We report on multiple echo measurements in hyperpolarized liquids using optically pumped spin-1/2 noble gas atoms: either 129Xe dissolved in cyclohexane or 3He dissolved in superfluid 4He. An NMR pulse sequence 90◦ − τ − 90◦ (with slice-selective flipping pulses for 129Xe experiments) was used and long echo trains have been observed in the presence...
Article
For detection of biological events in vitro, sensors using hyperpolarized (129)Xe NMR can become a powerful tool, provided the approach can bridge the gap in sensitivity. Here we propose constructs based on the non-selective grafting of cryptophane precursors on holo-transferrin. This biological system was chosen because there are many receptors on...
Article
Full-text available
Xenon–cucurbituril binding: The smallest member of the cucurbituril family is able to slowly trap xenon in water even at room temperature with quite a high binding constant. At higher temperatures, the binding is weaker and the exchange kinetics higher, inducing potential applications for the reversible trapping of gases.
Article
The known xenon-binding (±)-cryptophane-111 (1) has been functionalized with six [(η(5)-C(5)Me(5))Ru(II)](+) ([Cp*Ru](+)) moieties to give, in 89% yield, the first water-soluble cryptophane-111 derivative, namely [(Cp*Ru)(6)1]Cl(6) ([2]Cl(6)). [2]Cl(6) exhibits a very high affinity for xenon in water, with a binding constant of 2.9(2) × 10(4) M(-1)...
Article
Spin-noise appeal: Detection of NMR spin-noise is very appealing when dilute hyperpolarized species are considered. Continuous monitoring of the noise absorption at the Larmor frequency enables determination of T(1) and T(2)*, independently of the static magnetic field. An inductively coupled microcoil located inside the NMR tube (see picture) allo...
Article
Full-text available
The synthesis and functionalisation of zeolite nanoparticles designed for laser-polarized Xe-129 NMR experiments in solution are described. These nanoparticles were functionalized by using original synthesis pathways through semicarbazide COCHO chemistry in order to ensure anchoring of a peptide for targeting biological receptors and attachment of...
Article
Xe-129 MRI is applied to cage molecules in which hyperpolarized xenon exhibits a specific spectral signature. In a few tens of seconds a net spatial discrimination is achieved between xenon in two different hosts dissolved in two immiscible media at submillimolar concentrations by using a gradient echo sequence with interleaved frequency selection....
Article
The interaction of xenon with cryptophane derivatives is analyzed by NMR by using either thermal or hyperpolarized noble gas. Twelve hosts differing by their stereochemistry, cavity size, and the nature and the number of the substituents on the aromatic rings have been included in the study, in the aim of extracting some clues for the optimization...
Article
The cover picture illustrates the observation of multiple chaotic maser emissions in NMR. In their article on page 1395, Marion et al. show that dissolved 129Xe—in which the nuclear magnetization enhanced by optical pumping (apparatus shown in background, credit Stropa/CEA) is anti-aligned with the static magnetic field—is able to emit spontaneousl...
Article
Full-text available
We report a new phenomenon observed when the magnetization of dissolved hyperpolarized (129)Xe is intense and opposite to the Boltzmann magnetization. Without radio-frequency (rf) excitation, the system spontaneously emits a series of rf bursts characterized by very narrow bandwidths (0.03 Hz at 138 MHz). This chaotic NMR-maser illustrates the incr...
Article
We describe the effects observed on 1H and 129Xe NMR spectra resulting from the presence of laser-polarized xenon at high concentration in a deuterated solvent. We show that the large xenon polarization modifies proton signal intensities due to heteronuclear dipolar cross-relaxation, while the huge xenon magnetization per unit volume induces sizeab...
Article
DNA sensor: A xenon host composed of a cryptophane structure with a DNA strand (see picture) serves to detect its complementary strand in the micromolar range through laser-polarized 129Xe NMR spectroscopy.
Article
The smallest cryptophane ever synthesized, cryptophane-1.1.1 (1), whose internal volume is estimated to be 81 A(3), exhibits the highest binding constant (10000 M-1 at 293 K) in organic solution for xenon encapsulation determined to date. The very slow kinetics of decomplexation on the NMR time scale results in an extremely sharp Xe-129 NMR signal...
Article
The presence of highly concentrated dissolved laser-polarized xenon (approximately 1mol/L, polarization up to 0.2) induces numerous effects on proton and xenon NMR spectra. We show that the proton signal enhancements due to (129)Xe-(1)H cross-relaxation (SPINOE) and overall shifts of the proton resonances due to the average dipolar shift created by...
Article
Full-text available
This manuscript is a summary of my activities from my PhD, until the fist years of my research in the French technological research institute, namely the CEA. Particularly, the following items are mentioned: the NMR characterization of biomolecules such as sugars, proteins, either dia or paramagnetic, water-protein interactions, cellular metabolism...
Poster
Full-text available
Journées Nationales Nanosciences et Nanotechnologies, 6-8 Novembre 2006, Besançon
Article
Peculiar nuclear spin systems can be polarized at a level of thousands times the value obtained at thermal equilibrium, for instance by optical pumping. When concentrated, these systems create a sizeable average dipolar field which is experienced by any nuclear spin. We propose to use these distant dipolar fields for performing a polarization trans...
Article
Full-text available
Cryptophanes bearing OCH(2)COOH groups in place of the methoxy groups represent a new class of xenon-carrier molecules soluble in water at biological pH. By using (1)H and (129)Xe NMR (thermally- and laser-polarized dissolved gas), the structural and dynamical behaviors of these host molecules as well as their interaction with xenon are studied. Th...
Article
The interaction of xenon with beta-cryptogein, a basic 10 kDa protein belonging to the elicitin family, has been studied by using dissolved thermal and laser-polarized gas in liquid-state NMR. 13C and 1H chemical-shift-mapping experiments were unfruitful, the proton lines only experienced a slight narrowing but no significant frequency variation wh...
Article
Wild-type bacteriophage T4 lysozyme contains a hydrophobic cavity with binding properties that have been extensively studied by X-ray crystallography and NMR. In the present study, the monitoring of 1H chemical shift variations under xenon pressure enables the determination of the noble gas binding constant (K = 60.2 M(-1)). Although the interactio...
Article
A highly-regioselective DIBAL-promoted hexa-de-O-methylation on the secondary rim of permethylated β-cyclodextrin directly gave an one-step access to 2A, 3B, 2C, 3D, 2E, 3F-hexahydroxy-heptakis (2, 3, 6-tri-O-methyl) β-cyclodextrin, the position of six free hydroxy groups being unambiguously determined by NMR analyses. To cite this article: Y. Chen...
Article
The hydrophobic cavity of Lipid Transfer Protein 1 from Nicotiana tabacum is investigated in detail by NMR using xenon as a spy. The analysis of the (129)Xe chemical shifts and self-relaxation times gives evidence of protein-xenon interaction. Thermodynamics of the binding is characterized through the study of aliphatic (1)H and (13)C chemical shif...
Article
The study of the interaction between xenon and two cryptophane derivatives in organic solution has been carried out through 1H and 129Xe NMR. The cage molecules constituted by the grafting of (−)-camphanic acid are diastereomers through the orientation of the ethylenedioxy linkers joining the cyclotriveratrylene moieties. The availability of laser-...
Article
Molecular hydrophobic cavities can be mapped thanks to the detection of magnetization transfer from laser polarized xenon to nearby protons. This so called SPINOE approach is described. The study of the spin dynamics during this experiment and its consequences on the practical implementation are detailed. We show that thanks to the knowledge of the...
Article
A regioselective DIBAL-promoted tetra-O-demethylation on the secondary rim of the permethylated β-cyclodextrin gave a straightforward access to the 2A, 3B, 2D, 3E tetrol. To cite this article: X. Luo et al., C. R. Chimie 7 (2003).
Article
Longitudinal relaxation times T1 of laser-polarized xenon in water solutions containing α-cylodextrin and wheat nonspecific lipid transfer protein have been measured. By monitoring the xenon signal decay curves at different solute concentrations and different xenon pressures, we have been able to estimate the binding constant of xenon in the molecu...
Article
Position of the prisoner: Accurate location of xenon atoms in cage molecules (see picture) is derived by specific through-space magnetization transfer from laser-polarized gas to protons using a new NMR pulse sequence.
Article
The hydration properties of the oxidized form of horse heart cytochrome c have been studied by 1H NMR spectroscopy. Two-dimensional, homonuclear ePHOGSY-NOESY experiments are used to map water–protein interactions. The detected NOEs reveal interactions between nonexchangeable protein protons and both water protons and labile protein protons which e...
Article
The ferredoxin from Chromatium vinosum (CvFd) exhibits sequence and structure peculiarities. Its two Fe4S4(SCys)4 clusters have unusually low potential transitions that have been unambiguously assigned here through NMR, EPR, and Mössbauer spectroscopy in combination with site-directed mutagenesis. The [4Fe-4S]2+/1+ cluster (cluster II) whose coordi...
Article
In the frame of a broad study on the structural differences between the two redox forms of cytochromes to be related to the electron transfer process, the NMR solution structure of horse heart cytochrome c in the reduced form has been determined. The structural data obtained in the present work are compared to those already available in the literat...
Article
Full-text available
The backbone (15)N-(1)H (1)J values have been measured for oxidized and reduced cytochrome b(5) at 500 and 800 MHz. Their field dependence, due to increasing partial orientation of the molecule in solution at high magnetic fields, provides structural constraints relative to the orientation of the NH bond vector with respect to the principal directi...
Article
The hydration properties of the oxidized form of horse heart cytochrome c have been studied by 1H NMR spectroscopy. Application of ePHOGSY (enhanced protein hydration observed through gradient spectroscopy) experiments over a paramagnetic molecule provided firm spectroscopic evidence of the presence of a water molecule in the heme crevice. A few in...
Article
The rate constants for the intramolecular electron transfer between the two [4Fe-4S] clusters of a series of native and genetically engineered ferredoxins have been determined by proton magnetic resonance (1H NMR) spectroscopy. The measurement relies on the properties of the signals assigned to beta-protons of the coordinating cysteines when the pr...
Article
The accuracy of the solution structures determined by NMR is often poor around paramagnetic centers because the properties of the near protons are strongly perturbed by the electronic spin. The structural information contained in the relaxation rates of these protons has been extracted here by measuring the longitudinal relaxation times with the in...
Article
Elimination from water of lindane, a common soil insecticide whose occurrence in groundwaters used as sources of drinking water is of great concern, was shown to be achieved by the TiO2-UV system. Gas chromatography-mass spectrometry analyses of a photocatalytically treated aqueous solution initially containing 3.44 mmol/L (=1g/L) lindane indicated...
Article
The 2[4Fe-4S] ferredoxin from Chromatium vinosum has been investigated by H-1 and C-13 nuclear magnetic resonance. H-1 NMR sequence-specific assignments have been obtained for a large majority of the residues. They indicate that the protein folds along a pattern similar to that previously evidenced for shorter 2[4Fe-4S] ferredoxins. However, C. vin...
Chapter
Lindane is a common soil insecticide. Despite its low solubility, it is found in groundwaters which are used as sources of drinking water at some sites. Therefore, it is a pollutant of great concern as it may reasonably be anticipated to be a carcinogen. Its destruction by various oxidants has been studied and lindane has been found to be recalcitr...
Article
Full-text available
Ce manuscrit résume mes activités de recherche en thèse, dans mes différents séjours post-doctoraux et mes premières années de recherche au Commissariat à l'Energie Atomique. Elles concernent la caractérisation de biomolécules par RMN, comme des sucres, des protéines, dia ou paramagnétiques. Le manuscrit aborde aussi la caractérisation des interact...

Questions

Question (1)
Question
Hi. I have fitted 11 experimental curves in two ways, giving me two series of 11 couples of estimate values and associated standard deviations.
Here are some values to make things clearer:
Method 1, estimate values: 12.48,18.09,11.57,15,11.84,12.94,14.89,15.93,18.05,12.59,11.57
standard deviations: 0.97,0.53,0.88,0.7,0.11,0.91,1.17,0.96,0.42,0.41,0.22
Method 2, estimate values: 10.81,17.4,7.43,13.5,11.22,10.17,14.91,16.49,18.91,12.51,11.46
standard deviations: 1.93,1.22,1.42,1.35,0.16,1.15,1.14,0.92,0.24,0.24,0.16
I would like to find a statistical test that indicates whether resulting estimates of one of the method are significantly higher than the other.
Thank in advance

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