Monolayer Properties of Uronic Acid Bicatenary Derivatives at the Air-Water Interface: Effect of Hydroxyl Group Stereochemistry Evidenced by Experimental and Computational Approaches

in Physical Chemistry Chemical Physics [=PCCP] (2011), 13(33), 1529115298

By screening uronic acid-based surfactant interfacial properties, the effect of the hydroxyl group stereochemistry (OH-4) on the conformation of bicatenary (disubstituted) derivatives at the air–water ... [more ▼]

By screening uronic acid-based surfactant interfacial properties, the effect of the hydroxyl group stereochemistry (OH-4) on the conformation of bicatenary (disubstituted) derivatives at the air–water interface has been evidenced by experimental and computational approaches. Physical and optical properties of a monolayer characterized by Langmuirfilmbalance, Brewster angle microscopy, and ellipsometry at 20°C reveal that the derivative of glucuronate (C14/14–GlcA) forms a more expanded monolayer, and shows a transition state under compression, in the opposite to that of galacturonate (C14/14–GalA). Both films are very mechanically resistant (compression modulus > 300m Nm-1) and stable (collapse pressure exceeding 60mNm-1), while that of C14/14–GalA exhibits a very high compression modulus up to 600mNm-1 like films in the solid state. Computational approaches provide single and assembly molecular models that corroborate the molecule expansion degree and interactions data from experimental results. Differences in the molecular conformation and film behaviours of uronic acid bicatenary derivatives at the air–water interface are attributed to the intra-H-bonding formation, which is more favourable with an OH-4 in the axial (C14/14–GalA) than in the equatorial position (C14/14–GlcA). [less ▲]

Implementing quantum algorithms in hyperfine levels of ultracold polar molecules by optimal control

in Physical Chemistry Chemical Physics [=PCCP] (2011), 13

Zwitterionic i-motif structures are preserved in DNA negatively charged ions produced by electrospray mass spectrometry

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12

DNA cytosine-rich strands can fold into an intercalated motif (i-motif) structure. The i-motif is formed by mutually intercalated duplexes containing proton-mediated C-H(+)-C (cytosine-proton-cytosine ... [more ▼]

DNA cytosine-rich strands can fold into an intercalated motif (i-motif) structure. The i-motif is formed by mutually intercalated duplexes containing proton-mediated C-H(+)-C (cytosine-proton-cytosine) base pairs. Negatively charged ions of DNA i-motifs produced by electrospray mass spectrometry are therefore zwitterionic if the base pairing motif is preserved in the gas phase. Here we used IRMPD spectroscopy and ion mobility spectrometry to assess whether i-motif structures were preserved in the gas phase. We first investigated the IRMPD spectral signature of the tetramer [dC(6)](4), which can only be formed via C-H(+)-C base pairing, compared to the single strand dC(6). The IR signature of i-motif formation is an apparent broadening of the band at 1650 cm(-1). DFT calculations show this apparent broadening is actually due to blue-shifts of the NH(2) scissoring modes and red shifts of C[double bond, length as m-dash]O stretching modes. We then investigated the gas-phase conformations of the telomeric sequence d(CCCAAT)(3)CCC, that can form an intramolecular i-motif, by performing IRMPD spectroscopy and ion mobility spectrometry as a function of the charge state. We show that the negative ions of the lowest charge states correspond to a preserved i-motif structure. This is the first demonstration of the native extraction of solution-phase zwitterionic nucleic acids using negative electrospray ionization. [less ▲]

Controlled full adder-subtractor by vibrational computing

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12(48), 15628-15635

Adsorption of polyampholyte copolymers at the solid/liquid interface: the influence of pH and salt on the adsorption behaviour

in Physical Chemistry Chemical Physics [=PCCP] (1999), 1(17), 3853-3856

Polyampholytes are macromolecules that contain oppositely charged groups. We have studied the adsorption of the polyampholyte diblock copolymer poly(methacrylic acid)-block-poly((dimethylamino)ethyl ... [more ▼]

Polyampholytes are macromolecules that contain oppositely charged groups. We have studied the adsorption of the polyampholyte diblock copolymer poly(methacrylic acid)-block-poly((dimethylamino)ethyl methacrylate), PMAA-b-PDMAEMA, on oxidized silicon surfaces. The amount of polymer adsorbed from aqueous solution of different pH and salt concentration was measured by ellipsometry. The influence of the added salts NaCl, Na2SO4 and CaCl2 was determined. In every case adsorption took place, although the polyampholyte and the substrate exhibit the same sign of net charge. For all types of salt, the adsorbed amount shows two maxima close to the isoelectric point (IEP) of the polymer as a function of pH. Directly at the IEP of the polyampholyte, no adsorption was found. The measured dependences can be explained by the adsorption of one or the other of the two blocks depending on acidity and ionic strength. Furthermore, the lateral structure of the dried films was investigated by scanning force microscopy (SFM). [less ▲]