Common features in the microscopic dynamics of hydration water on organic and inorganic surfaces.

The microscopic dynamics of hydration water exhibits some universal features that do not depend on the nature of the hydrated surface. We show that the hydration level dependence of the dynamic transition in the mean squared atomic displacements measured by means of elastic neutron scattering is qualitatively similar for hydration water in inorganic and organic hosts. The difference is that the former are 'rigid', whereas the dynamics of the latter can be enhanced by the motions of the hydration water. The overall hydration level appears to be the main parameter governing the magnitude of the mean squared atomic displacements in the hydration water, irrespective of the details of the hydrated host.

Investigating the quartz (1010)/water interface using classical and ab initio molecular dynamics.

Two different terminations of the (1010) surface of quartz (α and ß) interacting with water are simulated by classical (CMD) (using two different force fields) and ab initio molecular dynamics (AIMD) and compared with previously published X-ray reflectivity (XR) experiments. Radial distribution functions between hydroxyl and water show good agreement between AIMD and CMD using the ClayFF force field for both terminations. The Lopes et al. (Lopes, P. E. M.; Murashov, V.; Tazi, M.; Demchuk, E.; MacKerell, A. D. J. Phys. Chem. B2006, 110, 2782-2792) force field (LFF), however, underestimates the extent of hydroxyl-water hydrogen bonding. The ß termination is found to contain hydroxyl-hydroxyl hydrogen bonds; the quartz surface hydroxyl hydrogens and oxygens that hydrogen bond with each other exhibit greatly reduced hydrogen bonding to water. Conversely, the hydroxyl hydrogen and oxygens that are not hydrogen bonded to other surface hydroxyls but are connected to those that are show a considerable amount of hydrogen bonding to water. The electron density distribution of an annealed surface of quartz (1010) obtained by XR is in qualitative agreement with electron densities calculated by CMD and AIMD. In all simulation methods, the interfacial water peak appears farther from the surface than observed by XR. Agreement among AIMD, LFF, and XR is observed for the relaxation of the near-surface atoms; however, ClayFF shows a larger discrepancy. Overall, results show that for both terminations of (1010), LFF treats the near-surface structure more accurately whereas ClayFF treats the interfacial water structure more accurately. It is shown that the number of hydroxyl and water hydrogen bonds to the bridging Si-O-Si oxygens connecting the surface silica groups to the rest of the crystal is much greater for the α than the ß termination. It is suggested that this may play a role in the greater resistance to dissolution of the ß termination than that of the α termination.

Low-hazard metallography of moisture-sensitive electrochemical cells.

A low-hazard approach is presented to prepare metallographic cross-sections of moisture-sensitive battery components. The approach is tailored for evaluation of thermal (molten salt) batteries composed of thin pressed-powder pellets, but has general applicability to other battery electrochemistries. Solution-cast polystyrene is used to encapsulate cells before embedding in epoxy. Nonaqueous grinding and polishing are performed in an industrial dry room to increase throughput. Lapping oil is used as a lubricant throughout grinding. Hexane is used as the solvent throughout processing; occupational exposure levels are well below the limits. Light optical and scanning electron microscopy on cross-sections are used to analyse a thermal battery cell. Spatially resolved X-ray diffraction on oblique angle cut cells complement the metallographic analysis.

Zn2+ and Sr2+ adsorption at the TiO2 (110)-electrolyte interface: influence of ionic strength, coverage, and anions.

The X-ray standing wave technique was used to probe the sensitivity of Zn2+ and Sr2+ ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile (alpha-TiO2) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn2+ and Sr2+ reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 A changes over the full compositional range). The lack of any specific anion coadsorption upon probing with Br-, coupled with the insensitivity of Zn2+ and Sr2+ cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn2+ and Sr2+ show a maximum Stern-layer coverage of approximately 0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters.

Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

Function and subnuclear distribution of Rpp21, a protein subunit of the human ribonucleoprotein ribonuclease P.

Rpp21, a protein subunit of human nuclear ribonuclease P (RNase P) was cloned by virtue of its homology with Rpr2p, an essential subunit of Saccharomyces cerevisiae nuclear RNase P. Rpp21 is encoded by a gene that resides in the class I gene cluster of the major histocompatibility complex, is associated with highly purified RNase P, and binds precursor tRNA. Rpp21 is predominantly localized in the nucleoplasm but is also observed in nucleoli and Cajal bodies when expressed at high levels. Intron retention and splice-site selection in Rpp21 precursor mRNA regulate the intranuclear distribution of the protein products and their association with the RNase P holoenzyme. Our study reveals that dynamic nuclear structures that include nucleoli, the perinucleolar compartment and Cajal bodies are all involved in the production and assembly of human RNase P.

Inhibition of Escherichia coli viability by external guide sequences complementary to two essential genes.

Narrow spectrum antimicrobial activity has been designed to reduce the expression of two essential genes, one coding for the protein subunit of RNase P (C5 protein) and one for gyrase (gyrase A). In both cases, external guide sequences (EGS) have been designed to complex with either mRNA. Using the EGS technology, the level of microbial viability is reduced to less than 10% of the wild-type strain. The EGSs are additive when used together and depend on the number of nucleotides paired when attacking gyrase A mRNA. In the case of gyrase A, three nucleotides unpaired out of a 15-mer EGS still favor complete inhibition by the EGS but five unpaired nucleotides do not.

Paravertebral venous plexus distention (Batson's): an inciting etiologic agent in lumbar radiculopathy as observed by venous angiography.

Can the paravertebral plexus of veins adjacent to the spinal nerve root within the narrow confines of the lateral neural canal be a collateral generator of radicular pain when no other evidence of spinal pathology is evident? A patient with complaints of intractable lumbar radiculopathy and an otherwise unremarkable clinical neuromusculoskeletal examination, as well as normal imaging and electrodiagnostic studies, is reviewed with special reference to symptomatic and paravertebral venous responses to both a Valsalva maneuver and dipyridamole infusion as imaged by magnetic venous angiography.

Localization in the nucleolus and coiled bodies of protein subunits of the ribonucleoprotein ribonuclease P.

The precise location of the tRNA processing ribonucleoprotein ribonuclease P (RNase P) and the mechanism of its intranuclear distribution have not been completely delineated. We show that three protein subunits of human RNase P (Rpp), Rpp14, Rpp29 and Rpp38, are found in the nucleolus and that each can localize a reporter protein to nucleoli of cells in tissue culture. In contrast to Rpp38, which is uniformly distributed in nucleoli, Rpp14 and Rpp29 are confined to the dense fibrillar component. Rpp29 and Rpp38 possess functional, yet distinct domains required for subnucleolar localization. The subunit Rpp14 lacks such a domain and appears to be dependent on a piggyback process to reach the nucleolus. Biochemical analysis suggests that catalytically active RNase P exists in the nucleolus. We also provide evidence that Rpp29 and Rpp38 reside in coiled bodies, organelles that are implicated in the biogenesis of several other small nuclear ribonucleoproteins required for processing of precursor mRNA. Because some protein subunits of RNase P are shared by the ribosomal RNA processing ribonucleoprotein RNase MRP, these two evolutionary related holoenzymes may share common intranuclear localization and assembly pathways to coordinate the processing of tRNA and rRNA precursors.

Rpp14 and Rpp29, two protein subunits of human ribonuclease P.

In HeLa cells, the tRNA processing enzyme ribonuclease P (RNase P) consists of an RNA molecule associated with at least eight protein subunits, hPop1, Rpp14, Rpp20, Rpp25, Rpp29, Rpp30, Rpp38, and Rpp40. Five of these proteins (hPop1p, Rpp20, Rpp30, Rpp38, and Rpp40) have been partially characterized. Here we report on the cDNA cloning and immunobiochemical analysis of Rpp14 and Rpp29. Polyclonal rabbit antibodies raised against recombinant Rpp14 and Rpp29 recognize their corresponding antigens in HeLa cells and precipitate catalytically active RNase P. Rpp29 shows 23% identity with Pop4p, a subunit of yeast nuclear RNase P and the ribosomal RNA processing enzyme RNase MRP. Rpp14, by contrast, exhibits no significant homology to any known yeast gene. Thus, human RNase P differs in the details of its protein composition, and perhaps in the functions of some of these proteins, from the yeast enzyme.

Computed tomography-guided biopsy of the spine. A review of 103 patients.

STUDY DESIGN: A retrospective study of 103 computed tomography-guided biopsies of the spine. These represent a consecutive series of patients with spinal lesions or disorders observed over a 32-month period. OBJECTIVES: To determine the diagnostic accuracy and clinical usefulness of computed tomography-guided biopsies with respect to major influencing variables. SUMMARY OF BACKGROUND DATA: Computer tomographic-guided biopsy of the spine is considered a safe, accurate, and relatively inexpensive examination technique. A study comparing its diagnostic accuracy with respect to all the variables of age, gender, radiographic appearance, spinal level, tissue type, or pathologic diagnosis has not been done. METHODS: Biopsy specimens were sent for cytologic and histologic analysis. Bacteriologic studies were performed when clinically indicated. The biopsy results were analyzed for adequacy and diagnostic accuracy, i.e., the ability to generate a tissue sample adequate for pathologic examination and one that yields diagnostic information. RESULTS: The mean age of patients was 60 years, with a range of 4-91 years. The spines of 52 males and 51 females were studied. There were eight cervical, 28 thoracic, 53 lumbar, and 14 sacral lesions used as biopsy sites. The radiographic appearance of spinal lesions were lytic in 74 cases, blastic in four cases, and mixed in two cases. Tissues undergoing biopsy included bone (63 cases), soft tissue (35 cases), and mixed specimens (five cases). The pathologic examinations revealed 18 infections, 23 primary neoplasms, 34 metastases, and 19 normal tissues. An adequate specimen for pathologic examination was obtained in 90 biopsies (87%). A diagnosis was achieved in 67 of 94 patients (71%). Diagnostic rates obtained in thoracic level biopsies were lower than those from biopsies of other spinal levels (P = .007). CONCLUSION: Computed tomography-guided biopsy is an important tool in the evaluation of spinal lesions. A positive biopsy result may preclude the need for open surgical intervention. This study included one of the largest series of patients in the medical literature. In addition, it determined the diagnostic rates of this procedure with respect to the major influencing variables. Thoracic-level biopsies have a diagnostic rate that is significantly lower than that of other spinal levels. No significant correlation was found between diagnostic accuracy and age, gender, radiographic appearance, tissue type, or eventual diagnosis.

Mapping in three dimensions of regions in a catalytic RNA protected from attack by an Fe(II)-EDTA reagent.

The accessibility of the ribose groups in the phosphodiester chain of M1 RNA, the catalytic subunit of ribonuclease P from Escherichia coli, has been probed with an Fe(II)-EDTA reagent when the RNA is alone in solution, when it is in a complex with a tRNA precursor substrate, and when it is in the holoenzyme complex with its cofactor, C5 protein. The regions found to be protected under these various conditions, as well as those previously identified in other chemical probing experiments, have been mapped on a three-dimensional working model of M1 RNA and are generally compatible with the previously proposed placement of the substrate on the enzyme and with previous data and inferences regarding the interactions of C5 protein with M1 RNA. On the basis of the accessibilities of the C(4') atoms, refinements have been introduced in the model to accommodate the Fe(II)-EDTA protection data. The protein cofactor makes contact with several helical regions of the catalytic RNA on the opposite side of the surface to which substrates bind.

Nucleotide sequences of the RNA subunit of RNase P from several mammals.

Sequences of the RNA subunit of RNase P from five primate and two rodent species have been determined. The extent of the differences among these sequences and the corresponding RNA from human tissue correlates to known phylogenetic relationships. All the sequences can be drawn in a secondary structure with common features.

Spinal pedicle fixation. Confirmation of an image-based technique for screw placement.

Although many advances in the technique of pedicle screw insertion have been made, there still exist unacceptable rates of perforations through the pedicle cortex. Successful placement of a pedicle screw requires accurate identification of the entry point, correct transverse and sagittal plane angulation, safe preparation of a pilot hole, and appropriate depth of insertion. The authors propose that a technique of pedicle screw insertion using posteroanterior image intensification angled in the axis of the pedicle to define the entry point and guide insertion would improve the accuracy of this procedure. This study tests the accuracy of pedicle screw placement using this technique. Ninety pedicle screws were placed in human cadaveric lumbar spines. All specimens were then dissected and split longitudinally to assess accuracy of pedicle insertion by both visual and palpatory means. Five of 90 (5.5%) pedicle screws were found to have perforated the pedicle. Three of these were at L1, two of which were due to the transverse pedicle diameter being smaller than the screw diameter. Therefore, a 3.4% incidence of pedicle perforation due to malpositioning and a 2.1% incidence of pedicle perforation secondary to pedicle/screw size discrepancy was determined. This technique may lead to significant improvements over recently reported rates of pedicle screw perforations; however, this in vitro condition eliminated many potentially complicating factors that might be encountered in the clinical setting.

A prospective study to identify high-yield criteria associated with acute intracranial computed tomography findings in head-injured patients.

We conducted a multicenter, prospective study of head-injured patients to identify high-yield clinical criteria for acute intracranial injuries. Emergency patients with a history of blunt head trauma occurring within 2 weeks and who underwent nonenhanced cranial computed tomography (CT) were entered onto the study during a 12-month period. Of the 264 patients, 32 (12%) had abnormal CT findings. Nine high-yield variables were associated with abnormal CT findings: alcohol use before injury, antegrade amnesia, prolonged loss of consciousness, anisocoria and/or fixed and dilated pupils, abnormal Babinski reflex, focal motor paralysis, cranial nerve deficit, Glasgow coma scale score of less than 15, and clinical signs of basilar skull fracture. Patients 2 years old or younger or older than 60 years of age showed a significantly greater prevalence of abnormal CT findings than patients of other ages.

Computed tomography of congenital spondylolisthesis of the sixth cervical vertebra.

Congenital anomalies of the cervical spine occur relatively commonly. An interesting anomaly is congenital spondylolisthesis of the sixth cervical vertebra. We are presenting a case of this anomaly as imaged with plain radiography and computed tomography. We have also reviewed the previous literature and attempted to clarify distinctions between bilateral cervical spondylolysis with spondylolisthesis and other cervical spine lesions.

Imaging of the absent cervical pedicle.

The absent cervical pedicle is an interesting congenital anomaly which has been described in several previous case reports. Of primary importance is its recognition to avoid confusion with more clinically significant abnormalities such as fracture or an enlarged neural foramen. Although many cases can be diagnosed from the plain radiographic findings alone, it is occasionally necessary to employ another imaging modality for more definitive evaluation. We describe two cases of absent cervical pedicle imaged with computed tomography and magnetic resonance imaging.

Intracranial gumma mimicking a tuber cinereum tumor.

The brain magnetic resonance (MR) and computed tomography (CT) finding in a 37-year-old patient with a history of persistent headache and secondary hypogonadism and with a strongly positive blood and cerebrospinal fluid (CSF) fluorescent treponemal antibody-absorption (FTA-ABS) test is reported. A focal enhancing mass was demonstrated involving the tuber cinereum. The mass was markedly reduced after the completion of a course of intravenous administration of penicillin G treatment. This case is interesting because of its rare incidence and unique neuroradiological findings.