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Biomedical subjects

Heather C Allen

Publications and source records attributed to Heather C Allen.

17 recordsLinked to original sources
PubMed2007

Condensing effect of palmitic acid on DPPC in mixed Langmuir monolayers.

The interaction between deuterated dipalmitoylphosphatidylcholine (DPPC-d62) and palmitic acid (PA) in mixed Langmuir monolayers is studied using vibrational sum frequency generation (VSFG) spectroscopy. Palmitic acid is an additive in exogenous lung surfactant preparations such as Survanta and Surfaxin. The effect of PA on the chain conformation and orientation of DPPC in the liquid-expanded and condensed phases is explored. A condensing effect of PA on DPPC is observed with VSFG. At 12 mN/m, DPPC-d62 alone is in the liquid-expanded phase. Adding PA increases the conformational ordering of DPPC chains and causes DPPC to transition from the expanded phase into the condensed phase. At 42 mN/m, DPPC-d62 and PA form a mixed structure in the condensed phase. The presence of PA decreases the chain tilt angle of DPPC, increasing the orientational ordering of DPPC chains. At 42 mN/m, there is also evidence from the frequency red shift of the PO2- symmetric stretch that the carboxyl group of PA forms a hydrogen bond with the phosphate group of DPPC in the condensed phase. From this work the effect of PA on DPPC is 2-fold: (1) PA increases the chain ordering of DPPC and promotes the LE and TC phase separation and (2) due to the miscibility between DPPC and PA in the condensed phase, PA decreases the collapse pressure.

Journal Article↗
PubMed2006

Real-time investigation of lung surfactant respreading with surface vibrational spectroscopy.

The respreading of a lung surfactant monolayer at the air-water interface is investigated with broad bandwidth sum frequency generation (BBSFG) spectroscopy. The lung surfactant mixture contains chain perdeuterated dipalmitoylphosphatidylcholine (DPPC-d62), palmitoyloleoylphosphatidylglycerol (POPG), palmitic acid (PA), and KL4 (a 21-residue polypeptide analogue to the surfactant protein SP-B). DPPC-d62 serves as a probe molecule for the spectroscopic investigation. The BBSFG spectra of DPPC-d62 in the lung surfactant mixture are obtained in the C-D stretching region in real-time during film compression and expansion in a Langmuir trough. The BBSFG intensity of the CD3 stretch peak from DPPC-d62 terminal methyl groups is used as a measure of the interfacial density of DPPC-d62 after careful consideration of orientation effects. For the first time, the interfacial loss of DPPC in a complex lung surfactant mixture is quantified. Spectroscopic results reveal that there is an 18% DPPC-d62 interfacial loss during film respreading. However, the surface pressure-area isotherm measurements demonstrate that there is a rather large trough area reduction (37%) during film expansion. The relatively small interfacial loss of DPPC-d62 and the rather large trough area reduction indicate that the respreading of DPPC and non-DPPC components in the lung surfactant is not uniform and a surface refinement process exists during film compression and expansion. This refinement process results in a DPPC-enriched monolayer with a significant depletion of non-DPPC components after film respreading. Implication for replacement surfactant design from this work is discussed.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

Competition between atmospherically relevant fatty acid monolayers at the air/water interface.

Competition and oxidation of fatty acids spread at the air/water interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. At the air/water interface, a monolayer of oleic acid replaced a monolayer of deuterated palmitic acid at equilibrium spreading pressure. Subsequent oxidation of the oleic acid monolayer with ozone resulted in products more water soluble than the palmitic acid; therefore, the palmitic acid monolayer reformed at the surface. Results indicate that the surfactants on the surface of fat-coated tropospheric aerosols will only possess oxidized acyl chains after all less soluble species in the aqueous subphase have been removed through the processes of replacement at the surface and atmospheric oxidation.

Aerosols↗
PubMed2006

DPPC Langmuir monolayer at the air-water interface: probing the tail and head groups by vibrational sum frequency generation spectroscopy.

Dipalmitoylphosphatidylcholine (DPPC) is the predominant lipid component in lung surfactant. In this study, the Langmuir monolayer of deuterated dipalmitoylphosphatidylcholine (DPPC-d62) in the liquid-expanded (LE) phase and the liquid-condensed (LC) phase has been investigated at the air-water interface with broad bandwidth sum frequency generation (BBSFG) spectroscopy combined with a Langmuir film balance. Four moieties of the DPPC molecule are probed by BBSFG: the terminal methyl (CD3) groups of the tails, the methylene (CD2) groups of the tails, the choline methyls (CH3) in the headgroup, and the phosphate in the headgroup. BBSFG spectra of the four DPPC moieties provide information about chain conformation, chain orientation, headgroup orientation, and headgroup hydration. These results provide a comprehensive picture of the DPPC phase behavior at the air-water interface. In the LE phase, the DPPC hydrocarbon chains are conformationally disordered with a significant number of gauche configurations. In the LC phase, the hydrocarbon chains are in an all-trans conformation and are tilted from the surface normal by 25 degrees. In addition, the orientations of the tail terminal methyl groups are found to remain nearly unchanged with the variation of surface area. Qualitative analysis of the BBSFG spectra of the choline methyl groups suggests that these methyl groups are tilted but lie somewhat parallel to the surface plane in both the LE and LC phases. The dehydration of the phosphate headgroup due to the LE-LC phase transition is observed through the frequency blue shift of the phosphate symmetric stretch in the fingerprint region. In addition, implications for lung surfactant function from this work are discussed.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

Non-aqueous solvation of n-octanol and ethanol: spectroscopic and computational studies.

Raman spectroscopy was used to examine the interactions of the free O-H bonds in n-octanol and ethanol with the organic solvents carbon tetrachloride (CCl(4)), cyclohexane, and benzene. These spectra reveal that the solvents CCl(4) and cyclohexane have a small effect on the free O-H peak of alcohols, whereas benzene as a solvent significantly red-shifts the free O-H band. Calculated spectra were generated via MP2/6-31G* calculations and the B3LYP/6-31+G**//MP2/6-31G*-derived Boltzmann populations of each ethanol complex and are consistent with the experimental results. Additional spectra were calculated using Boltzmann populations derived from single-point energies at the polarizable continuum model (PCM) level with the B3LYP/6-31+G** level of theory to take overall solvent effects into account, and these simulated spectra are also largely consistent with the experimental results. Analysis of the computational results reveals a lengthening of the O-H bond from the O-H interaction with the delocalized electronic structure of benzene as well as a bimodal distribution of the free O-H peak of the alcohol/benzene mixtures due to two distinctly different types of alcohol/benzene complexes.

Journal Article↗
PubMed2006

Ethylenediamine at air/liquid and air/silica interfaces: protonation versus hydrogen bonding investigated by sum frequency generation spectroscopy.

The adsorption process on mineral oxide surfaces is one of the most important factors influencing the migration and distribution of contaminants in the environment. Although there have been numerous studies carried out at the macroscopic scale, there is a lack of molecular-scale interfacial information. The molecular-scale information is often crucial for the determination of sorption mechanisms. In this study, sum frequency generation spectroscopy (SFG), a surface specific vibrational spectroscopy, has been employed to investigate the adsorption of ethylenediamine (H2N(CH2)2NH2, EDA) onto the amorphous SiO2 surface and EDA protonated products at air/liquid interfaces. The SFG spectra of EDA adsorbed on the silica surface and the singly protonated EDA solution are similar in both CH and NH stretching regions. These spectral similarities indicate that EDA molecules are strongly chemisorbed to the silica surface through the protonation of one EDA amine group by surface silanol OH groups, thereby forming a (H2N(CH2)2NH3)+(O-Si[triple bond])- surface complex. The SFG results also indicate that the surface acidity of the silanol OH groups (pKa (HOSi[triple bond])) is between the two pKa values of EDA (in the range of 7.56-10.71) at the air/silica interface.

Air↗
PubMed2005

Air-liquid interfaces of aqueous solutions containing ammonium and sulfate: spectroscopic and molecular dynamics studies.

Investigations of the air-liquid interface of aqueous salt solutions containing ammonium (NH(4)(+)) and sulfate (SO(4)(2-)) ions were carried out using molecular dynamics simulations and vibrational sum frequency generation spectroscopy. The molecular dynamics simulations show that the predominant effect of SO(4)(2-) ions, which are strongly repelled from the surface, is to increase the thickness of the interfacial region. The vibrational spectra reported are in the O-H stretching region of liquid water. Isotropic Raman and ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopies were used to study the effect of ammonium and sulfate ions on the bulk structure of water, whereas surface sum frequency generation spectroscopy was used to study the effect of these ions on the interfacial structure of water. Analysis of the interfacial and bulk vibrational spectra reveal that aqueous solutions containing SO(4)(2-) perturb the interfacial water structure differently than the bulk and, consistent with the molecular dynamics simulations, reveal an increase in the thickness of the interfacial region.

Journal Article↗
PubMed2005

Unified molecular picture of the surfaces of aqueous acid, base, and salt solutions.

The molecular structure of the interfacial regions of aqueous electrolytes is poorly understood, despite its crucial importance in many biological, technological, and atmospheric processes. A long-term controversy pertains between the standard picture of an ion-free surface layer and the strongly ion specific behavior indicating in many cases significant propensities of simple inorganic ions for the interface. Here, we present a unified and consistent view of the structure of the air/solution interface of aqueous electrolytes containing monovalent inorganic ions. Molecular dynamics calculations show that in salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the interface, whereas the anions, such as halides or hydroxide, exhibit a varying surface propensity, correlated primarily with the ion polarizability and size. The behavior of acids is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids (unlike bases and salts) reduce the surface tension of water. The results of the simulations are supported by surface selective nonlinear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The ion specific propensities for the air/solution interface have important implications for a whole range of heterogeneous physical and chemical processes, including atmospheric chemistry of aerosols, corrosion processes, and bubble coalescence.

Acids↗
PubMed2005

Adsorption of 4-picoline and piperidine to the hydrated SiO2 surface: probing the surface acidity with vibrational sum frequency generation spectroscopy.

Vapor adsorption is an important process influencing the migration and the fate of many organic pollutants in the environment. In this study, vibrational sum frequency generation (SFG) spectroscopy was used to study the adsorption of two surface acidity probe molecules, 4-picoline (pKa = 5.94) and piperidine (pKa = 11.24), onto the amorphous SiO2 surface. The adsorption of 4-picoline onto the silica surface occurs by forming weak hydrogen bonds between the nitrogen atoms of 4-picoline molecules and the hydrogen atoms of surface silanol OH groups. Piperidine molecules are strongly chemisorbed onto the SiO2 surface through the protonation of piperidine molecules by surface silanol OH groups. The SFG results indicate that the surface acidity constant of silanol OH groups (pKa-(HOSi triple bond)) is in the range of 5.94-11.24 at the air/solid interface. Although this range of surface acidity constants is quite wide, it is possible to narrow it by choosing probe molecules with a smaller pKa range. Together with theoretical prediction methods, adsorption studies using vibrational SFG spectroscopy are capable of quantifying the surface acidity of mineral oxides by carefully choosing the acidity probe molecules.

Adsorption↗
PubMed2005

Spectroscopic and computational studies of aqueous ethylene glycol solution surfaces.

The combination of Monte Carlo, ab initio, and DFT computational studies of ethylene glycol (EG) and EG-water hydrogen-bonding complexes indicate that experimental vibrational spectra of EG and EG-water solution surfaces have contributions from numerous conformations of both EG and EG-water. The computed spectra, derived from harmonic vibrational frequency calculations and a theoretical Boltzmann distribution, show similarity to the experimental surface vibrational spectra of EG taken by broad-bandwidth sum frequency generation (SFG) spectroscopy. This similarity suggests that, at the EG and aqueous EG surfaces, there are numerous coexisting conformations of stable EG and EG-water complexes. A blue shift of the CH2 symmetric stretch peak in the SFG spectra was observed with an increase in the water concentration. This change indicates that EG behaves as a hydrogen-bond acceptor when solvated by additional water molecules. This also suggests that, in aqueous solutions of EG, EG-EG aggregates are unlikely to exist. The experimental blue shift is consistent with the results from the computational studies.

Computer Simulation↗
PubMed2005

Adsorption of ethylene glycol vapor on (alpha-AI2O3 (0001) and amorphous SiO2 surfaces: observation of molecular orientation and surface hydroxyl groups as sorption sites.

Vapor adsorption is an important process influencing the migration and the fates of many organic pollutants in the environment. In this study, adsorption of ethylene glycol (EG) vapor onto single crystal alpha-Al2O3 (0001) and fused SiO2 (amorphous) surfaces was studied with sum frequency generation spectroscopy, a well-suited surface specific technique for probing interfacial phenomena atthe molecular scale. Air-aqueous EG solutions were also investigated to compare to the adsorption at the air-solid interface in the presence of water vapor. The gauche conformer of EG molecules dominates the air-aqueous EG solution interface, and EG molecules act as hydrogen acceptors at the air-liquid interface. Water and surface hydrophilic/ hydrophobic properties play important roles for the adsorption of EG onto silica and alumina surfaces. The adsorbed EG molecules interact in different ways at the two different oxide surfaces. EG molecules weakly physisorb onto the alpha-Al2O3 (0001) surface by forming relatively weak hydrogen bonds with surface water molecules. On the silica surface, the suppression of the silanol OH stretching peak indicates that EG molecules form hydrogen bonds with silanol OH groups.

Adsorption↗
PubMed2004

Piperidine adsorption on hydrated alpha-alumina (0001) surface studied by vibrational sum frequency generation spectroscopy.

The adsorption of piperidine vapor on the hydrated alumina (alpha-Al2O3, corundum) (0001) surface was investigated using vibrational broad bandwidth and scanning sum frequency generation (SFG) spectroscopy. The interfacial vibrational signature in the C-H stretching region of piperidine at the alumina (0001) surface is shown to be a sensitive spectroscopic probe revealing the adsorption mechanism. The neat piperidine surface, aqueous piperidine surface, and aqueous piperidium chloride surface were also investigated in the C-H stretching region by SFG to establish vibrational reference frequencies. After piperidine adsorption, piperidine vapor was removed and piperidine was found to be chemisorbed onto the alumina (0001) surface through protonation by surface hydroxyl groups. The O-H stretching region of the alumina surface before and after piperidine adsorption was also investigated, and the results revealed the decrease of the surface number density of alumina surface hydroxyl groups.

Journal Article↗
PubMed2003

The air-liquid interface of benzene, toluene, m-xylene, and mesitylene: a sum frequency, Raman, and infrared spectroscopic study.

The air-liquid interface and the liquid-phase of benzene, toluene, 1,3-dimethylbenzene, and 1,3,5-trimethylbenzene are studied using broad bandwidth sum frequency generation spectroscopy, Raman and infrared spectroscopy. A vibrationally resonant sum frequency response is observed from these surfaces in spite of the small hyperpolarizabilities, in particular, the zero and near-zero hyperpolarizabilities of benzene and 1,3,5-trimethylbenzene. The orientation of the aromatic rings of these compounds at their air-liquid interfaces is tilted relative to the surface plane. Thus, on average, the plane of the aromatic ring does not lie in the interfacial plane. Comparison of the square root of the sum frequency intensity to that of the Raman multiplied bythe infrared intensity provides additional information about the molecular environment at their respective air-liquid interface.

Air Pollutants↗
PubMed2003

Octreotide abolishes the acute decrease in bone turnover in response to oral glucose.

Feeding or oral intake of glucose results in an acute suppression of bone turnover. This does not appear to be mediated by insulin. Several gastrointestinal hormones modulate bone turnover in vitro and may mediate this response. We examined whether inhibiting the production of gastrointestinal hormones using octreotide could block glucose-mediated suppression of bone turnover. Fifteen subjects were each studied on four occasions in a randomized, single-blind, crossover study after receiving 1) oral placebo, iv saline; 2) oral glucose, iv saline; 3) oral glucose, iv octreotide; or 4) iv octreotide alone. We measured serum C-terminal telopeptide of type I collagen, urinary N-terminal telopeptide of type I collagen, osteocalcin, procollagen type I N-terminal propeptide, PTH, insulin, ionized calcium, and glucose over 4 h. All bone turnover markers decreased significantly after oral glucose (P < 0.001). At 120 min serum C-terminal telopeptide decreased by 45 +/- 2%, urinary N-terminal telopeptide by 31 +/- 7%, osteocalcin by 16 +/- 1%, and procollagen type I N-terminal propeptide by 8 +/- 1%. There was no significant decrease in bone turnover in response to oral glucose during octreotide infusion. Octreotide alone resulted in a significant increase in all bone turnover markers (P < 0.05) and PTH (P < 0.01). We conclude that octreotide completely abolishes the bone turnover response to glucose intake and increases PTH secretion. The apparent bone turnover response to feeding is probably mediated by an octreotide-inhibitable endocrine factor.

Administration, Oral↗
PubMed2002

Diffuse reflection broad bandwidth sum frequency generation from particle surfaces.

We report the first vibrational sum frequency generation (VSFG) spectroscopic study from particle surfaces of powdered solids using a modified SFG approach, diffuse reflection broad bandwidth sum frequency generation (DR-BBSFG). The DR-BBSFG spectrum of sodium dodecyl sulfate (SDS, C(12)H(25)SO(4)Na) powdered solids was obtained. Five peaks were resolved by calculated fits. Possible origins of the SFG response from SDS particle surfaces are discussed. Potential applications of DR-BBSFG spectroscopy are addressed.

Journal Article↗
PubMedDate not supplied

New insights into lung surfactant monolayers using vibrational sum frequency generation spectroscopy.

At the air-water interface, interfacial molecular structure, intermolecular interactions, film relaxation and film respreading of model lung surfactant monolayers were studied using vibrational sum frequency generation (VSFG) spectroscopy combined with a Langmuir film balance. Chain-perdeuterated dipalmitoylphosphatidylcholine (DPPC-d62), palmitoyloleoyl-phosphatidylglycerol (POPG), palmitic acid (PA) and tripalmitin were investigated. In the DPPC-d62-PA binary monolayer, PA showed a condensing effect on the DPPC chains. On the contrary, in the DPPC-d62-POPG binary monolayer, POPG showed a fluidizing effect on the DPPC chains. In the ternary monolayer system of DPPC-d62-POPG-PA, the balance between the fluidizing and the condensing effect was also observed. In addition, the film relaxation behavior of DPPC-d62 and the enhanced film stability of DPPC-d62 caused by the addition of tripalmitin were observed. Real-time VSFG was also employed to study the respreading properties of a complex lung surfactant mixture containing DPPC-d62, POPG, PA and KL4 (a mimic of SP-B) peptide, which revealed DPPC enrichment after film compression.

1,2-Dipalmitoylphosphatidylcholine↗