Investigations into Spin- and Unpolarized Secondary Electron-Induced Reactions in Self-Assembled Monolayers of Cysteine.

Cysteine is the simplest thiolated, chiral amino acid and is often used as the anchor for studies of self-assembled monolayers (SAMs) of complex biomolecules such as peptides. Understanding the interaction of SAMs of cysteine with low-energy secondary electrons (SEs) produced by X-rays can further our understanding of radiation damage in biomolecules. In particular, if the electrons are polarized, chiral-selective chemistry could have bearing on the origin of homochirality in nature. In the present paper, we use synchrotron radiation-based X-ray photoelectron spectroscopy to determine the changes that occur in the bonding of self-assembled layers of cysteine on gold as a result of soft X-ray irradiation. To investigate the possibility of chiral selectivity resulting from the interaction of low-energy, spin-polarized SEs (SPSEs), measurements were conducted on cysteine adsorbed on a 3 nm-thick gold layer deposited on a CoPt thin-film multilayer with perpendicular magnetic anisotropy. Time-dependent measurements of the C 1s, N 1s, O 1s, S 2p, and Au 4f core levels are used to follow the changes in surface chemistry and determine reaction cross-sections as a function of SE exposure. Analysis of the data results in cross-sections in the range of 5-7 Mb and suggests possible reaction pathways. Changing the magnetization direction of the CoPt multilayer produces SPSEs with opposite polarity. Some evidence of spin-dependent reactions is indicated but is inconclusive. Possible reasons for the discrepancy are posited.

Electron Spin-Polarization Dependent Damage to Chiral Amino Acid l-Histidine.

The damage of approximately monolayer films of l-histidine by low-energy spin-polarized electrons (SPE) ejected from a magnetized cobalt substrate has been probed using X-ray photoelectron spectroscopy (XPS). Average damage cross sections for N-containing motifs of l-histidine are 25-30 and 2-5 Mb for zwitterions and neutral molecules, respectively. The magnetization direction of the substrate, which controls the ejected SPE helicity, was reversed in situ, and statistically significant differences in the damage cross sections of 10-30% were measured between positive and negative electron helicities. This is the first measurement of spin dichroism (SD) in an amino acid. The differential cross sections suggest that inelastic scattering of SPE with chiral molecules could contribute to the persistence of one enantiomer vs the other under certain irradiation conditions, particularly for the zwitterionic species.

Low energy secondary electron induced damage of condensed nucleotides.

Radiation damage and stimulated desorption of nucleotides 2'-deoxyadenosine 5'-monophosphate (dAMP), adenosine 5'-monophosphate (rAMP), 2'-deoxycytidine 5'-monophosphate (dCMP), and cytidine 5'-monophosphate (rCMP) deposited on Au have been measured using x-rays as both the probe and source of low energy secondary electrons. The fluence dependent behavior of the O-1s, C-1s, and N-1s photoelectron transitions was analyzed to obtain phosphate, sugar, and nucleobase damage cross sections. Although x-ray induced reactions in nucleotides involve both direct ionization and excitation, the observed bonding changes were likely dominated by the inelastic energy-loss channels associated with secondary electron capture and transient negative ion decay. Growth of the integrated peak area for the O-1s component at 531.3 eV, corresponding to cleavage of the C-O-P phosphodiester bond, yielded effective damage cross sections of about 23 Mb and 32 Mb (1 Mb = 10-18 cm2) for AMP and CMP molecules, respectively. The cross sections for sugar damage, as determined from the decay of the C-1s component at 286.4 eV and the glycosidic carbon at 289.0 eV, were slightly lower (about 20 Mb) and statistically similar for the r- and d- forms of the nucleotides. The C-1s component at 287.6 eV, corresponding to carbons in the nucleobase ring, showed a small initial increase and then decayed slowly, yielding a low damage cross section (∼5 Mb). Although there is no statistical difference between the sugar forms, changing the nucleobase from adenine to cytidine has a slight effect on the damage cross section, possibly due to differing electron capture and transfer probabilities.

Itinerant ferromagnetism in the As 4p conduction band of Ba_{0.6}K_{0.4}Mn_{2}As_{2} identified by X-ray magnetic circular dichroism.

X-ray magnetic circular dichroism (XMCD) measurements on single-crystal and powder samples of Ba_{0.6}K_{0.4}Mn_{2}As_{2} show that the ferromagnetism below T_{C}≈100 K arises in the As 4p conduction band. No XMCD signal is observed at the Mn x-ray absorption edges. Below T_{C}, however, a clear XMCD signal is found at the As K edge which increases with decreasing temperature. The XMCD signal is absent in data taken with the beam directed parallel to the crystallographic c axis indicating that the orbital magnetic moment lies in the basal plane of the tetragonal lattice. These results show that the previously reported itinerant ferromagnetism is associated with the As 4p conduction band and that distinct local-moment antiferromagnetism and itinerant ferromagnetism with perpendicular easy axes coexist in this compound at low temperature.

The relationship between interfacial bonding and radiation damage in adsorbed DNA.

We have performed a comparison of the radiation damage occurring in DNA adsorbed on gold in two different configurations, when the DNA is thiolated and bound covalently to the substrate and when it is unthiolated and interacts with the substrate through the bases. Both molecules were found to organize so as to protrude from the surface at ~45 degrees. Changes in the time-dependent C 1s and O 1s X-ray photoelectron (XP) spectra resulting from irradiation were interpreted to arise from cleavage of the phosphodiester bond and possibly COH desorption. By fitting the time-dependent XP spectra to a simple kinetic model, time constants were extracted, which were converted to cross sections and quantum yields for the damage reaction. The radiation induced damage is significantly higher for the thiolated DNA. N 1s X-ray absorption spectrum revealed the N-C=N LUMO is more populated in the unthiolated molecule, which is due to a higher degree of charge transfer from the substrate to this LUMO in the unthiolated case. Since the N-C=N LUMO of the thiolated molecule is comparatively less populated, it is more effective in capturing low energy electrons resulting in a higher degree of damage.

Elemental and magnetic sensitive imaging using x-ray excited luminescence microscopy.

We demonstrate the potential of x-ray excited luminescence microscopy for full-field elemental and magnetic sensitive imaging using a commercially available optical microscope, mounted on preexisting synchrotron radiation (SR) beamline end stations. The principal components of the instrument will be described. Bench top measurements indicate that a resolution of 1 µm or better is possible; this value was degraded in practice due to vibrations and/or drift in the end station and associated manipulator. X-ray energy dependent measurements performed on model solar cell materials and lithographically patterned magnetic thin film structures reveal clear elemental and magnetic signatures. The merits of the apparatus will be discussed in terms of conventional SR imaging techniques.

Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by x-ray absorption spectroscopy.

We report a comprehensive study of the defects in room-temperature ferromagnetic (RTFM) Cu-doped ZnO thin films using x-ray absorption spectroscopy. The films are doped with 2 at.% Cu, and are prepared by reactive magnetron sputtering (RMS) and pulsed laser deposition (PLD), respectively. The results reveal unambiguously that atomic point defects exist in these RTFM thin films. The valence states of the Cu ions in both films are 2(+). In the film prepared by PLD, the oxygen vacancies (V(O)) form around both Zn ions and Cu ions in the hexagonal wurtzite structure. Upon annealing of the film in O(2), the V(O) population reduces and so does the RTFM. In the film prepared by RMS, the V(O)s around Cu ions are not detected, and the V(O) population around Zn ions is also smaller than in the PLD-prepared film. However, zinc vacancies (V(Zn)) are evidenced. Given the low doping level of spin-carrying Cu ions, these results provide strong support for defect-mediated ferromagnetism in Cu-doped ZnO thin films.

Charge order in LuFe2O4: an unlikely route to ferroelectricity.

We present the refinement of the crystal structure of charge-ordered LuFe2O4, based on single-crystal x-ray diffraction data. The arrangement of the different Fe-valence states, determined with bond-valence-sum analysis, corresponds to a stacking of charged Fe bilayers, in contrast with the polar bilayers previously suggested. This arrangement is supported by an analysis of x-ray magnetic circular dichroism spectra, which also evidences a strong charge-spin coupling. The nonpolar bilayers are inconsistent with charge order based ferroelectricity.

X-ray- and electron-induced infrared emission spectroscopy.

We demonstrate the use of Fourier transform infrared (IR) spectroscopy for midinfrared emission measurements following x-ray or electron excitation. Spectra from an InAs low band-gap semiconductor film, which emits in the IR from 3000 to 3400 cm(-1), are presented. There is good agreement between the present results and previously published laser-excited spectra. Using focused beams, it should be possible to perform sub-diffraction-limited IR imaging. In addition, simultaneous structural and electronic analysis could be performed using the x-ray or electron excitation probes.

Surface-stabilized nonferromagnetic ordering of a layered ferromagnetic manganite.

An outstanding question regarding the probing or possible device applications of correlated electronic materials (CEMs) with layered structure is the extent to which their bulk and surface properties differ or not. The broken translational symmetry at the surface can lead to distinct functionality due to the charge, lattice, orbital, and spin coupling. Here we report on the case of bilayered manganites with hole doping levels corresponding to bulk ferromagnetic order. We find that, although the hole doping level is measured to be the same as in the bulk, the surface layer is not ferromagnetic. Further, our low-energy electron diffraction and x-ray measurements show that there is a c-axis collapse in the outermost layer. Bulk theoretical calculations reveal that, even at fixed doping level, the relaxation of the Jahn-Teller distortion at the surface is consistent with the stabilization of an A-type antiferromagnetic state.

Chiral-selective chemistry induced by spin-polarized secondary electrons from a magnetic substrate.

We demonstrate for the first time that low-energy spin-polarized secondary electrons, produced by irradiation of a magnetic substrate, can induce chiral-selective chemistry. Our approach was to perform detailed measurements of the reaction rate for x-ray induced, secondary electron photolysis of a model chiral compound, (R)- or (S)-2-butanol, adsorbed on a magnetized Permalloy substrate. The results showed that there is an enhancement of approximately 10% in the rate of CO bond cleavage that depends on the chirality of the molecule and the spin polarization of the substrate secondary electrons.

Long-term hearing preservation after acoustic neuroma surgery.

The past two decades have evidenced a remarkable improvement in the capacity of otologic surgeons to treat cerebellopontine angle tumors. Advances in instrumentation because of technologic changes, coupled with better surgical training, have contributed to a highly successful rate of tumor removal. The capability to extirpate the tumor now permits the otologic surgeon to attempt simultaneous preservation of the facial and cochlear nerve functions. Just as middle ear surgery improved to the point in the 1950s that reconstruction as well as disease eradication became possible, so can surgeons now consider preservation of function of the inner ear. It is now technically feasible--in some instances--to attempt to preserve hearing in tumors of the eighth nerve. Several studies have provided evidence that the cochlear nerve can be anatomically and functionally preserved when neuromas involve either the inferior or superior vestibular nerves. However, other studies assert that grossly intact nerves may contain microscopic islands of tumor cells intermingled with nerve fibers. If viable tumor cells were allowed to remain behind, one would expect them to grow; this would result in loss of hearing function and tumor recurrence, as evidenced by computed tomography (CT) or magnetic resonance imaging (MRI). This article will discuss the issues of cochlear nerve preservation and tumor excision, and review our experience over the past decade.

Alterations in [3H]desmethylimipramine binding in the aged rat brain: an in vitro autoradiographic demonstration.

Using in vitro autoradiographic receptor binding, the present report provides a descriptive analysis of [3H]desmethylimipramine ([3H]DMI) binding in the aged rat brain. Small circular patches of intense [3H]DMI binding were present within the caudate nucleus in every aged brain examined. Occasionally, similar patches of label were present in restricted cortical regions of aged brains. Comparable patches of [3H]DMI binding were never observed in young brains used in these investigations. Additional evidence suggests that these age-dependent changes in [3H]DMI binding are anatomically restricted to the loci indicated above.

Radiographic imaging for the cochlear implant.

Imaging plays an essential role in evaluating the cochlear implant candidate and the results of implantation. Eighteen candidates for cochlear implantation were reviewed for this study. Fourteen received implants; all but one, intracochlear devices. Based on the trial use of multiple techniques, a protocol has been established for the use of radiography in implant studies. The protocol suggests preoperative high resolution semiaxial computed tomographic scanning, intraoperative anteroposterior transorbital plain films if there is doubt concerning the electrode placement, and postoperative plain films in cases of unexpected poor device performance. In cases with complications, postoperative CT scanning may be required.

An evaluation of spatial information processing in aged rats.

The spatial learning abilities of young, middle-age, and senescent rats were investigated in two experiments using several versions of the Morris water maze task. In Experiment 1, Long-Evans hooded rats were trained to find a submerged escape platform hidden within the water maze. During this phase of testing, aged rats exhibited acquisition deficits compared with either young or middle-age subjects. With continued training, however, all age groups eventually achieved comparable asymptotic levels of performance. Subsequent testing in Experiment 1 revealed that following original training, aged rats were not impaired in learning a novel escape location or in their ability to locate a visible, cued escape platform. In an attempt to identify the basis of the age-related impairments observed in Experiment 1, naive young and aged rats in Experiment 2 were initially tested for their ability to locate a cued escape platform in the water maze. During this phase of testing, the escape latencies of both young and aged rats rapidly decreased to equivalent asymptotic levels. Subsequent analyses revealed that following cue training, young subjects exhibit a significant spatial bias for the region of the testing apparatus where the platform was positioned during training. In contrast, aged rats showed no spatial bias. Training was continued in Experiment 2 using a novel submerged platform location for each subject. During these place training trials, the escape latencies of senescent rats were longer than those of young subjects. These impairments were also accompanied by a lack of spatial bias among aged rats relative to young control subjects.(ABSTRACT TRUNCATED AT 250 WORDS)

Cholesteatoma vs. cholesterol granuloma of the petrous apex.

Lesions involving the petrous apex are rarely encountered in clinical practice. This directly affects the ability of the otolaryngologist to diagnose and effectively treat these lesions. Greater physician awareness and increased technologic capability are leading to more effective management of pathologic conditions involving this area of the temporal bone.

Head and neck presentations of acquired immunodeficiency syndrome.

Since December 1980, over 3000 cases of acquired immunodeficiency syndrome (AIDS) have been reported. The charts of 102 patients admitted to the New York University Medical Center with a diagnosis of AIDS were reviewed with particular emphasis on presenting signs, symptoms, and laboratory values. Symptoms tended to be nonspecific and most often resembled those of an upper respiratory infection. Over 71% of the patients presented with at least two of the following four signs: diffuse adenopathy, oral and facial lesions consistent with Kaposi's sarcoma, white oral lesions, and anergy. Laboratory findings included leukopenia, increased erythrocyte sedimentation rate, thrombocytopenia, and anemia. The in-hospital mortality rate was 26%. The current status of our knowledge concerning AIDS is reviewed and discussed. The frequency and types of presenting signs and symptoms in the head and neck are reported to alert the otolaryngologic community to this entity.

Role of noradrenergic function in the opiate antagonist facilitation of spatial memory.

Animals previously trained to criterion on an eight-arm radial maze task received either bilateral 6-hydroxydopamine lesions of the dorsal noradrenergic bundle (DNB) or control surgery. Following a 3-week recovery period, the animals were trained on the same radial maze in two novel environments. By a within-subjects design, in one of these environments animals received posttraining systemic treatment with the opiate antagonist naloxone; in the other novel environment, they received vehicle injection. In animals that received control surgery, opiate antagonist treatment produced a reliable enhancement of performance. Although the DNB-lesion animals did not differ from the control-surgery animals under the saline treatment condition, denervation of forebrain norepinephrine (NE) was found to prevent the memory enhancing effect of posttraining naloxone administration. These results provide further support that enhanced retention obtained with opiate antagonist administration is dependent upon intact NE function.