Correlation between cord insertion type and superficial choriovasculature in diamniotic-monochorionic twin placentas.

BACKGROUND: Non-central cord insertion has been associated with diminished chorionic vascular distribution in singleton placentas. The choriovascular correlates of peripheral cord insertion in diamniotic-monochorionic twin placentas remain undetermined. AIM: To study the association between type of cord insertion and choriovascular distribution of both twin territories in diamniotic-monochorionic twin placentas. DESIGN: A prospective cohort of 138 monochorionic placentas was examined at Women and Infants Hospital between 2009 and early 2011. Thirty-five cases (25%), including disrupted placentas, placentas from higher order multiples and placentas from pregnancies complicated by twin-to-twin transfusion syndrome, were excluded. The correlation between cord insertion type and superficial choriovascular distribution was studied in the remaining 103 dye-injected diamniotic-monochorionic placentas. Cord insertion was categorized as paracentral, marginal or velamentous. The choriovascular distribution of each individual twin territory was assessed by analysis of number and density (number per surface area) of perforating chorionic arteries (PCA). RESULTS: In contrast with singleton placentas, there was no correlation between cord insertion type and a twin's own choriovascular distribution in diamniotic-monochorionic placentas. However, a strong correlation was found between the choriovascular distribution of one twin and the cord insertion type of the opposite twin. For a twin with paracentral or marginal cord insertion, the PCA density was significantly higher if the co-twin had a velamentous cord insertion than if the co-twin had a paracentral cord insertion (P < 0.001 and P < 0.05, respectively). Similarly, the PCA density of a twin with velamentous cord insertion tended to be higher if the co-twin had a velamentous, rather than paracentral cord insertion (P = 0.09). CONCLUSIONS: This is the first study to suggest that in diamniotic-monochorionic twin gestations, the choriovascular architecture correlates with the cord insertion type of the co-twin. In general, velamentous cord insertion is associated with expanded choriovascular distribution in the opposite twin territory. Our observations may reflect novel manifestations of twin interdependence in monochorionic pregnancies.

Pulmonary dendritic cells in lungs of preterm infants: neglected participants in bronchopulmonary dysplasia?

Preterm infants are at risk for bronchopulmonary dysplasia (BPD), a chronic lung disease characterized by disrupted alveolar remodeling and microvascular dysangiogenesis. The pathogenesis of BPD is multifactorial, with contributions from antenatal and/or postnatal infection and inflammation. The potential role of dendritic cells, critical immune regulatory cells with potent angiogenic activities, remains undetermined. We studied the prevalence and topography of dendritic cells in postmortem lungs of short- and long-term ventilated preterm infants born between 23 and 29 weeks in gestation. Controls were age-matched infants who had lived less than 12 hours. Dendritic cells were identified by anti-DC-SIGN immunohistochemistry and were co-localized with endothelial and smooth muscle cells by double immunofluorescence. Lungs of early and late control infants without evidence of antenatal infection contained scattered DC-SIGN-positive dendritic cells in the peripheral lung parenchyma. Lungs of early control infants with a history of chorioamnionitis/antenatal infection and lungs of short- or long-term ventilated preterm infants showed a dramatic (more than 3-fold) increase in dendritic cells. Double labeling highlighted a close association between dendritic cells and small- or medium-sized pulmonary vessels. In conclusion, we demonstrated that dendritic cells are an integral component of normal postcanalicular lung development. Antenatal infection and ventilation/BPD are associated with significant pulmonary recruitment of dendritic cells. The recently described angiogenic effects of dendritic cells and their intimate association with the pulmonary microvasculature indicate that dendritic cells may participate in BPD-associated dysangiogenesis. Elucidation of the role of this immunovascular axis may lead to novel therapeutic approaches to BPD.

Analysis of the degradation of a model dental composite.

UNLABELLED: Dental composites undergo material property changes during exposure to the oral environment and may release compounds of potential toxicity, such as bisphenol A. Degradation of dental composites was studied in a simplified overlayer model in which bisphenol A diglycidyl methacrylate (BisGMA) was covalently bound to a porous silicon oxide surface. It was hypothesized that the chemical structure of this overlayer would allow release of bisphenol A, BisGMA, and the decomposition products thereof, upon exposure to water for an extended period. Liquid chromatography mass spectrometry found leaching of intact BisGMA and several degradation products that contained the bisphenol A moiety from the overlayer into distilled water after 2 wks of aging. The absence of bisphenol A release from the overlayer reduces concerns regarding its potential health risk in dental composites. Nevertheless, health concerns might arise with respect to BisGMA and the leached degradation products, since they all contain the bisphenol A moiety. ABBREVIATIONS: BisGMA, bisphenol A diglycidyl methacrylate; HPLC, high-performance liquid chromatography; LCMS, liquid chromatography mass spectrometry; MA, methacrylic acid; MPS, 3-(trimethoxysilyl) propyl methacrylate; m/z, mass-to-charge ratio; and TIC, total ion chromatogram.

Acardiac twin presenting as fetus amorphous with an attenuated umbilical cord.

Acardiac anomaly sequence is a rare malformation cluster occurring in the setting of monozygotic monochorionic twin pregnancies. In addition to an absent heart (acardia), variable degrees of somatic developmental disruption are present. We describe an extreme example of what we believe to be acardiac twinning, with almost complete absence of gross tissue organization but recognizable microscopic evidence of body-axis establishment and organ formation. The case is also notable for the absence of a grossly identifiable umbilical cord, with attachment to the placental vasculature by 2 vessels invested by amnion but without Wharton's jelly. We discuss the controversy regarding the requirement of an umbilical cord in the definition of acardiac twin and distinguish this case from placental teratoma.

Differentiation of human bone-derived cells grown on GRGDSP-peptide bound titanium surfaces.

Various surface modifications have been applied to titanium alloy (Ti-6Al-4V) implants, in an attempt to enhance osseointegration; crucial for ideal prosthetic fixation. Despite the numerous studies demonstrating that peptide-modified surfaces influence in vitro cellular behavior, there is relatively little data reporting their effects on bone remodeling. The objective of this article was to examine the effects of chemically modifying Ti-6Al-4V surfaces with a common RGD sequence, a 15-residue peptide containing GRGDSP (glycine-arginine-glycine-aspartate-serine-proline), on the modulation of bone remodeling. The expression of proteins known to be associated with osseous matrix and bone resorption were studied during the growth of human bone-derived cells (HBDC) on these peptide-modified surfaces. HBDC grown for 7 days on RGD surfaces displayed significantly increased levels of osteocalcin, and pro-collagen Ialpha1 mRNAs, compared with the production by HBDC grown on the native Ti-6Al-4V. A pattern that was also reflected at the protein levels for osteocalcin, type I collagen, and bone sialoprotein. Moreover, HBDC grown for 7 and 14 days on RGD-modified Ti-6Al-4V expressed significantly higher level of osteoclast differentiation factors and lower levels of osteoprotegerin and IL-6 proteins compared with other surfaces tested. These results suggest that different chemical treatments of implant material (Ti-6Al-4V) surface result in differential bone responses, not only their ability to form bone but also to stimulate osteoclastic formation.

Preparation and analysis of macroporous TiO2 films on Ti surfaces for bone-tissue implants.

This article describes the preparation and analysis of macroporous TiO2 films on Ti surfaces, for application in bone tissue-Ti implant interfaces. These TiO2 bioceramic films have a macroporous structure consisting of monodisperse, three-dimensional, spherical, interconnected pores adjustable in the micron size range. Micron-sized polystyrene (PS) bead templates are used to precisely define the pore size, creating macroporous TiO2 films with 0.50, 16, and 50 microm diameter pores, as shown by scanning electron microscopy. X-ray photoelectron spectroscopy shows the films to be predominantly composed of TiO2, with approximately 10% carbon. X-ray diffraction reveal rutile as the main phase when fired to the optimal temperature of 950 degrees C. Preliminary experiments find that the in vitro proliferation of human bone-derived cells (HBDC) is similar on all three pore sizes. However, higher [3H]thymidine incorporation by the HBDC is observed when they are grown on 0.50- and 16-microm pores compared to the 50-microm pores, suggesting an enhanced cell proliferation for the smaller pores.

Effects of unique ion chemistry on thin-film growth by plasma-surface interactions.

Plasma processing is a standard industrial method for the modification of material surfaces and the deposition of thin films. Polyatomic ions and neutrals larger than a triatomic play a critical role in plasma-induced surface chemistry, especially in the deposition of polymeric films from fluorocarbon plasmas. In this paper, low energy CF3+ and C3F5+ ions are used to modify a polystyrene surface. Experimental and computational studies are combined to quantify the effect of the unique chemistry and structure of the incident ions on the result of ion-polymer collisions. C3F5+ ions are more effective at growing films than CF3+, both at similar energy/atom of approximately 6 eV/atom and similar total kinetic energies of 25 and 50 eV. The composition of the films grown experimentally also varies with both the structure and kinetic energy of the incident ion. Both C3F5+ and CF3+ should be thought of as covalently bound polyatomic precursors or fragments that can react and become incorporated within the polystyrene surface, rather than merely donating F atoms. The size and structure of the ions affect polymer film formation via differing chemical structure, reactivity, sticking probabilities, and energy transfer to the surface. The different reactivity of these two ions with the polymer surface supports the argument that larger species contribute to the deposition of polymeric films from fluorocarbon plasmas. These results indicate that complete understanding and accurate computer modeling of plasma-surface modification requires accurate measurement of the identities, number densities, and kinetic energies of higher mass ions and energetic neutrals.

Surface mass spectrometry of molecular species.

This tutorial discusses the predominant methods available for surface mass spectrometry (MS) of molecular species: thermal desorption spectroscopy, laser desorption MS, secondary ion MS, post-ionization of desorbed neutrals and surface matrix-assisted laser desorption/ionization. Each of these has the capability to analyze molecular species that are chemisorbed, physisorbed, covalently bound to or the predominant component of a solid surface. These surface MS methods are briefly described, then their capabilities demonstrated using data predominantly from the authors' work. Comparisons are made with related methods in conventional MS. A very brief discussion is provided on the importance of complementing surface MS data with data from x-ray photoelectron spectroscopy and other surface analysis tools.

Relative dissociation energies of protonated peptides by electrospray ionization/surface-induced dissociation.

Relative dissociation energies (RDEs) are obtained for the major fragment ions produced by electrospray ionization/surface-induced dissociation of singly protonated triglycine, tetraglycine, leucine enkephalin, and leucine enkephalin arginine. A previously described data analysis method (Lim, H.; et al. J. Phys. Chem. B 1998, 102, 4753) is employed to analyze the energy-resolved mass spectra by subtracting out the distribution of energy transferred to the surface, integrating over the distribution of the incident ion energy, and taking into account the precursor ion initial internal energy and kinetic energy distributions. These variables are optimized by anchoring the RDE for the lowest energy fragment of a given precursor ion to its literature values and then using these optimized parameters to obtain the other RDEs. The RDEs of the four major fragments of triglycine vary from 2.4 eV for the b(2) fragment ion to 6.0 eV for the a(2) ion. The RDEs of the four major fragments of tetraglycine vary from 3.2 eV for the y(2) ion to 5.7 eV for the a(2) ion. The leucine enkephalin RDEs range from 1.1 eV for the b(4) ion to 2.1 eV for the b(2) ion. The leucine enkephalin arginine RDEs all lay between 2.5 and 3.5 eV. The overall trend of fragmentation order for all peptides is (y(n), b(n)) < a(n) and is consistent with the results from other experiments. The peptide RDEs presented here are only as accurate as the literature values to which they are anchored. Determination of absolute dissociation energies from SID data will require further refinement of the data analysis method.

Detection of thiazide-based diuretics in equine urine by liquid chromatography/mass spectrometry.

Thiazide-based diuretics are included in the list of banned drugs in the horse-racing industry. One effect of their misuse is increased urine flow, contributing to dilution of other doping agents. Their determination is essential in ensuring compliance to horse-racing regulation. This study evaluates the feasibility of using liquid chromatography/mass spectrometry (LC/MS) with electrospray and atmospheric pressure chemical ionization interfaces to analyze thiazidic diuretics in equine urine samples. Existing LC and gas chromatography/MS methods are limited in their applicability to thiazide analysis. Sample preparation, analyte extraction, chromatographic separation, ion-source collision induced dissociation, solvent composition, ionization mode, and ion polarity are discussed. The practicality of LC/MS for this analysis is demonstrated with actual equine administration samples collected at specified time intervals. Detection limits were 270 ng/mL for chlorothiazide, 131 ng/mL for hydrochlorothiazide, and 384 ng/mL for trichlormethiazide.

Thin hydroxyapatite coatings via sol-gel synthesis.

Production of hydroxyapatite coatings using an alkoxide-based sol-gel route requires control of solution aging time and heating schedule. 31P nuclear magnetic resonance spectroscopy was used to investigate the changes during aging of the sol and thermal gravimetric analysis employed to study the behavior of the xerogels as a function of temperature, while final products were determined using X-ray diffraction. Results from 31P nuclear magnetic resonance spectroscopy and thermal analysis revealed that sols must be aged for at least 24 h to complete the reaction of the two reactants. Deposition of the sol for coating production will then yield monophasic hydroxyapatite. Coatings produced from sols aged for less than 24 h yielded calcium oxide in addition to hydroxyapatite. Prefiring is necessary to remove most of the residual organic materials. Final heating up to 800 degrees C produces crystallization at 550 degrees C and removal of the remaining organic constituents for the formation of a thin hydroxyapatite layer.

Surface mass spectrometry of biotinylated self-assembled monolayers.

Biotin and biotinylated self-assembled monolayers (SAMs) on gold have been investigated using time-of-flight secondary ion mass spectrometry, direct laser desorption, laser desorption with 193 nm photoionization of ion- and laser-desorbed species, and laser desorption with vacuum ultraviolet (VUV, 118 nm) photoionization. Our results indicate that direct laser desorption and laser desorption combined with 193 nm multiphoton ionization can detect a chromophoric molecule like biotin that is covalently bound to a SAM. However, secondary ion mass spectra were dominated by fragmentation, and ion desorption/193 nm photoionization detected no species related to biotin. The dominant features of the laser desorption/VUV mass spectra were neat and Au-complexed dimers of intact and fragmented biotinylated SAM molecules. Multiphoton and single-photon ionization of laser-desorbed neutrals from biotinylated SAMs both led to the production of ions useful for chemical analysis of the monolayer. Multiphoton ionization with ultraviolet radiation was experimentally less challenging but required a chromophore for ionization and resulted in significant fragmentation of the adsorbate. Single-photon ionization with VUV radiation was experimentally more challenging but did not require a chromophore and led to less fragmentation. X-ray photoelectron spectra indicated that the biotinylated SAM formed a disordered, 40-60 Å thick monolayer on Au. Additionally, projection photolithography with a Schwarzschild microscope was used to pattern the biotinylated SAM surface and laser desorption/photoionization was used to detect biotinylated adsorbates from the ∼10 µm sized pattern.

Laser desorption ion trap mass spectrometry of self-assembled monolayers.

It is demonstrated that laser desorption ion trap mass spectrometry (LD-ITMS) can be successfully applied to the chemical analysis of a monolayer of adsorbates on a solid surface. Negative ion spectra obtained from LD-ITMS of self-assembled monolayers adsorbed from solutions of alkanethiols (CH3(CH2)nSH with n=5, 9, and 15) onto polycrystalline gold surfaces displayed clear ion peaks corresponding to the sulfonate adsorbate species. Sulfonate ions with the general formula CH3(CH2)n SO3 were detected at m/z 165, 221, and 305, respectively, and were derived from the partial oxidation of the corresponding alkanethiol self-assembled monolayers. Little fragmentation and no clustering was observed in these mass spectra. These results indicate that the sensitivity of LD-ITMS is sufficient to allow its application to a wide array of problems in surface science.

Evaluation of gas-liquid chromatography for the rapid diagnosis of amniotic fluid infection: a preliminary report.

Gas-liquid chromatography has been proposed as a possible tool in the rapid diagnosis of amniotic fluid infections. The analysis is based on the identification of specific organic acids derived from bacterial metabolism when organisms are present within the amniotic fluid. We retrospectively subjected 69 samples of amniotic fluid which had been obtained by transabdominal amniocentesis to analysis by gas-liquid chromatography. Forty-seven samples were derived from patients who either were in premature labor or had premature rupture of membranes with associated premature labor. Twenty-two specimens which served as a comparison group were obtained from patients who underwent amniocentesis for assessment of fetal maturity. The results obtained from chromatographic analysis are presented, and the possible applications of this technique to the clinical situation are discussed.