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Patterned self-assembled monolayers (SAMs) of alkanethiolates (AT) on Au and Ag substrates were imaged and characterized by scanning photoelectron microscopy (SPEM). The SPEM data showed that weakly bound molecular fragments are desorbed from the irradiated areas upon air exposure in the case of Ag whereas adsorption of airborne molecules from ambient occurs for the Au substrate which might be related to the specific branching patterns of irradiation induced modification of AT/A and AT/Ag .

The combination of traditional surface-spectroscopic methods and microscopic imaging techniques is gaining popularity along with the advances of nanotechnology. Among the available techniques, scanning photoelectron microscopy (SPEM) and photoelectron emission microscopy (PEEM) are two methods recently developed at the Synchrotron Radiation Research Center (SRRC). The SPEM station uses a Fresnel zone-plate optics to focus the soft X-ray beam and form a microprobe. Photoelectrons emitted from the illuminated spot are used to perform micro-photoelectron spectroscopy (μ-PES) measurements or to image the sample. The PEEM station, on the other hand, collects secondary electrons emitted from the sample upon photon irradiation, and uses an all-electrostatic column to magnify the field of view defined by the objective lens. By stepping the photon energy, micro-X-ray absorption spectra (μ-XAS) can be extracted from a sequence of images after proper image processing. [ABSTRACT FROM AUTHOR]

In the present study we investigated the relationship between secondary hyperparathyroidism in renal graft recipients and post-transplantation acute tubular necrosis (ATN). Patients were divided into two groups according to graft function: group A consisted of 28 patients who had an uneventful postoperative period and did not require haemodialysis. Group B comprised 26 patients with primary non-function of the graft due to biopsy-proven ATN who required continued haemodialysis for the first postoperative week or longer (mean 14.2 ±8.7 days). Both groups had comparable donor characteristics, HLA-matching and ischaemia times. All patients were given cyclospo-rin and low-dose prednisolone for immunosuppression. Pretransplant levels of intact PTH were significantly greater in group B than in group A (203.5 ±193.1 pg/ml versus 81.7±45.2 pg/ml, <0.01). Group B patients had more transplant biopsies (50 versus 7) and a longer hospitalization time (33.4 ± 10.9 days versus 21.9 ± 11.9 days, <0.01), although serum creatinine on the day of discharge was higher in group B (1.77 ± 0.51 mg/dl versus 1.5±0.45 mg/dl, P<0.05). We conclude that patients with secondary hyperparathyroidism as assessed by measuring circulating levels of intact PTH have an increased incidence of ATN. [ABSTRACT FROM PUBLISHER]

O K-, Zn L3, and K-edges x-ray absorption near-edge structure (XANES) spectra and scanning photoelectron microscopy (SPEM) spectra were obtained for ZnO nanorods with various diameters. The analysis of the XANES spectra revealed increased numbers of O 2p and Zn 4p unoccupied states with the downsizing of the nanorods, which reflects the enhancement of surface states when the diameter is decreased. Valence-band photoemission spectra show a significant narrowing of the valence band for the 45 nm diameter nanorod. The Zn 3d intensities in the Zn 3d SPEM spectra are drastically diminished for all nanorods as compared to the ZnO reference film, which can be interpreted as a reduction in density of itinerant final states or in transition probability. [ABSTRACT FROM AUTHOR]

Angle-dependent x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy measurements were performed to differentiate local electronic structures at the tips and sidewalls of highly aligned ZnO nanorods. The overall intensity of the O K-edge XANES spectra is greatly enhanced for small photon incident angles. In contrast, the overall intensity of the Zn K-edge XANES is much less sensitive to the photon incident angle. Both valence-band photoemission and O K-edge XANES spectra show substantial enhancement of O 2p derived states near the valence band maximum and conduction band minimum, respectively. The spatially resolved Zn 3d core level spectra from tip and sidewall regions show the lack of chemical shift. All the results consistently suggest that the tip surfaces of the highly aligned ZnO nanorods are terminated by O ions and the nanorods are oriented in the [0001] direction. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

X-ray absorption near edge structure (XANES) and scanning photoelectron microscopy (SPEM) measurements have been employed to obtain information on the electronic structures of the GaN nanowires and thin film. The comparison of the XANES spectra revealed that the nanowires have a smaller (larger) N (Ga) K edge XANES intensity than that of the thin film, which suggests an increase (decrease) of the occupation of N 2p (Ga 4p) orbitals and an increase of the N (Ga) negative (positive) effective charge in the nanowires. The SPEM spectra showed that the Ga 3d band for the nanowires lies about 20.8 eV below the Fermi level and has a chemical shift of about -0.9 eV relative to that of the thin film. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Angle-dependent x-ray absorption near edge structure (XANES) and scanning photoelectron microscopy (SPEM) measurements have been performed to differentiate local electronic structures of the tips and sidewalls of highly aligned carbon nanotubes. The intensities of both &pi*- and σ*-band C K-edge XANES features are found to be significantly enhanced at the tip. SPEM results also show that the tips have a larger density of states and a higher C 1s binding energy than those of sidewalls. The increase of the tip XANES and SPEM intensities are quite uniform over an energy range wider than 10 eV in contrast to earlier finding that the enhancement is only near the Fermi level. [ABSTRACT FROM AUTHOR]

The biased conductive probe of an atomic force microscope can induce local oxidation in ambience for converting silicon nitride films to silicon oxides with high reaction rate. Spatially resolved photoemission analysis with submicron resolution has been utilized to study the oxidation states of converted silicon oxide patterns in comparison with the surrounding Si[sub 3]N[sub 4] layer. The core level shift of the Si 2p photoelectron peak and the spectral features in the valence band reveal a complete conversion of silicon nitride to silicon oxide at a bias voltage of 10 V, with no remaining nitrogen left. The major oxide is SiO[sub 2]. The observed oxidation states of Si[sup 4+], Si[sup 3+], and Si[sup 2+] show a gradient depth distribution indicating excess silicon in the layer. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The modification of octadecanethiolate self-assembled monolayers on Au and Ag by nitrogen-oxygen downstream microwave plasma with variable oxygen content (up to 1%) has been studied by synchrotron-based high-resolution X-ray photoelectron spectroscopy. The primary processes were dehydrogenation, desorption of hydrocarbon and sulfur-containing species, and the oxidation of the alkyl matrix and headgroup-substrate interface. The exact character and the rates of the plasma-induced changes were found to be dependent on the substrate and plasma composition, with the processes in the aliphatic matrix and headgroup-substrate interface being mostly decoupled. In particular, the rates of all major plasma-induced processes were found to be directly proportional to the oxygen content in the plasma, which can be, thus, considered as a measure of the plasma reactivity. Along with the character of the observed changes, exhibiting a clear dominance of the oxidative processes, this suggests that the major effect of the oxygen-nitrogen downstream microwave plasma is provided by reactive oxygen-derived species in the downstream region, viz. long-living oxygen radicals and metastable species.

Self-assembled monolayers (SAMs) on coinage metal provide versatile modeling systems for studies of interfacial electron transfer, biological interactions, molecular recognition, and other interfacial phenomena. The bonding of enzyme to SAMs of alkanethiols onto gold surfaces is exploited to produce an enzyme chip. In this work, the attachment of trypsin to a SAMs surface of 11-mercaptoundecanoic acid was achieved using water soluble N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide as coupling agent. A two-dimensional liquid-phase separation scheme coupled with mass spectrometry is presented for proteomic analysis of erythrocyte proteins. The application of proteomics, particularly with reference to analysis of proteins, will be described. Surface analyses have revealed that the X-ray Photoelectron Spectroscopy (XPS) C1s and N1s core levels illustrate the immobilization of trypsin. These data are also in good agreement with Fourier Transformed Infrared Reflection-Attenuated Total Reflection (FTIR-ATR) spectra for the peaks at Amide I and Amide II. Using two-dimensional nano-high performance liquid chromatography electrospray ionization tandem mass spectrometry (2D nano-HPLC-ESI-MS/MS) system observations, analytical results have demonstrated the erythrocyte proteins digestion of the immobilized trypsin on the functionalized SAMs surface. For such surfaces, it also shows the enzyme digestion ability of the immobilized trypsin. The experiment results revealed the identification of 272 proteins from erythrocyte protein sample. The terminal groups of the SAMs structure can be further functionalized with biomolecules or antibodies to develop surface-base diagnostics, biosensors, or biomaterials.

Self-assembled monolayers (SAMs) on coinage metal provide versatile modeling systems for studies of interfacial electron transfer, biological interactions, molecular recognition and other interfacial phenomena. Recently the bonding of enzyme to SAMs of alkanethiols onto Au electrode surfaces was exploited to produce a bio-sensing system. In this work, the attachment of trypsin to a SAMs surface of 11-mercaptoundecanoic acid was achieved using water soluble N-ethyl-N '-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide as coupling agent. The thickness of SAMs was determined by optical ellipsometer; contact angles of the modified Au surfaces were measured in air using a goniometer. The Second Harmony Generation data displays the last few percents of the alkylthiol molecules adsorbed and produced the complete monolayer by inducing the transition from a high number of gauche defects to an all-trans conformation. Using X-ray Photoelectron Spectroscopy (XPS) and Fourier-Transformed Infrared Reflection-Absorption and Attenuated Total Reflection Spectroscopes (FTIR-RAS and ATR), we examined the chemical structures of samples with different treatments. By matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), we demonstrated the digestion of bovine serum albumin (BSA) on the trypsin-immobilized SAMs surface. Experimental results have revealed that the XPS C1s core levels at 286.3 and 286.5 eV (Amine bond), 288.1 eV (Amide bond) and 289.3 eV (Carboxylic acid) illustrate the immobilization of trypsin. These data were also in good agreement with FTIR-ATR spectra for the peaks valued at 1659.4 cm(-1) (Amide I) and 1546.6 cm(-1) (Amide II). Using MALDI-TOF MS observations, analytical results have demonstrated the BSA digestion of the immobilized trypsin on the functionalized SAMs surface. For such surfaces, BSA was digested on the trypsin-immobilized SAMs surface, which shows the enzyme digestion ability of the immobilized trypsin. The terminal groups of the SAMs structure can be further functionalized with biomolecules or antibodies to develop surface-base diagnostics, biosensors, or biomaterials.

Modification of octadecanethiolate self-assembled monolayers on Au by nitrogen-oxygen or argon-oxygen downstream microwave plasma with a low oxygen content (estimated below several percent) has been studied by synchrotron-based high-resolution X-ray photoelectron spectroscopy and water contact angle measurements. For both types of plasma, the primary processes were found to be the loss of conformational and orientational order and the oxidation of the alkyl matrix and headgroup-substrate interface. At the same time, the film modification occurred much faster and with different intermediates for the nitrogen plasma than for the argon plasma. The reasons for these differences are considered in terms of the different reactivities and different efficiencies of the energy transfer between the plasma constituents in these two types of plasma.

Self-assembled monolayers (SAMs) on coinage metal provide versatile modeling systems for studies of interfacial electron transfer, biological interactions, molecular recognition, and other interfacial phenomena. Recently, the bonding of enzyme to SAMs of alkanethiols onto Au electrode surfaces was exploited to produce a bio-sensing system. In this work, the attachment of trypsin to a SAMs surface of 11-mercaptoundecanoic acid was achieved using water soluble 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysulfosuccinimide as coupling agent. Experimental results have revealed that the X-ray Photoelectron Spectroscopy (XPS) C1s core levels at 286.3 and 286.5 eV (C with N), 288.1 eV (amide bond), and 289.3 eV (carboxyl) illustrate the immobilization of trypsin. These data were also in good agreement with Fourier-Transformed Infrared Reflection-Attenuated Total Reflection (FTIR-ATR) spectra for the peaks valued at 1659.4 cm(-1) (amide I) and 1546.6 cm(-1) (amide II). Using electrospray ionization tandem mass spectrometry (ESI-MS/MS) observations, analytical results have demonstrated the platelet proteins digestion of the immobilized trypsin on the functionalized SAMs surface. For such surfaces, platelet proteins were digested on the trypsin-immobilized SAMs surface, which shows the enzyme digestion ability of the immobilized trypsin. The terminal groups of the SAMs structure can be further functionalized with biomolecules or antibodies to develop surface-base diagnostics, biosensors, or biomaterials.

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

An increasing gap between supply and demand of donor kidneys for transplantation exists. There is concern regarding the allocation of scarce organs to elderly patients, because the benefit obtained by the transplant may be less in elderly compared with younger recipients. It was the objective of this study to determine differences in patient and organ survival between organ recipients >65 yr and 50 to 64 yr of age at transplantation. A retrospective cohort of 627 patients >50 yr who received a kidney transplant between 1993 and 2000 was assembled. Detailed information on patient demographics, comorbidities, and immunological and donor characteristics was ascertained before transplantation. Five-year patient and graft survival were evaluated by Kaplan-Meier survival curves and multivariate Cox proportional-hazard models. Five-year patient mortality was similar between patients aged >65 and 60 to 64 at transplantation (relative risk [RR] = 1.07; 95% confidence interval [CI], 0.66 to 1.74). Patients aged 50 to 59 yr showed a clear trend toward lower 5-yr mortality (RR = 0.66; 95% CI, 0.43 to 1.03). Compared with patients >65 yr, 5-yr graft loss was not different in patients aged 60 to 64 (RR = 1.28; 95% CI, 0.82 to 2.02) or those aged 50 to 59 yr at transplantation (RR = 1.02; 95% CI, 0.68 to 1.53). After thorough control for confounding, 5-yr graft survival was not materially different by age group. Discrimination against older candidates for kidney transplantation on age-related grounds alone is not warranted.

Antenna coupling microwave plasma enables a highly oxidative treatment of the outmost surface of polypropylene (PP) nonwoven fabric within a short time period. Subsequently, grafting copolymerization with acrylic acid (AAc) makes the plasma-treated fabric durably hydrophilic and excellent in water absorbency. With high grafting density and strong water affinity, the pAAc-grafted support greatly becomes feasible as an intensive absorbent and as a support to promote heparin immobilization through amide bonds. For heparin immobilized in acidic condition, the carbonate groups of the molecule tend to dissolve and passive encapsulation of the molecule prevents its functional groups from bonding with the carboxylic acid of pAAc. This effect leads to inhibit the immobilization process and consequently reduces the quantity as well as the bioactivity of the immobilized heparin. In alkaline processing environment, the oxidized uronic acid residues in heparin-related glycans are presumably cleaved and the removal of some oxidized residuals before immobilization process is likely to reduce the chain length of heparin. In the latter case, anticoagulant Factors X and XII, but not thrombin, are unaffected. Anticoagulant activity test using activated partial thromboplastin time (aPTT) is more sensitive in assessing heparin-immobilized surfaces, since it corresponds to Factor X and initiates the inhibition of Factor XII and thrombin. Likewise, platelets adhesion on the surfaces decreases as the process shifted from acidic to alkaline condition, whereas the hydrophilic character of the grafted pAAc markedly contributes to extend physical insertion of platelets. The immobilized heparin has a great part of original bioactivity, depending on the pH of the processing environment and the immobilized quantity. Relative bioactivity based upon aPTT tests is partially held longer than 90 days for the sample prepared in the alkaline or neutral environment.

Exposure to ultra-violet (UV)-C radiation is a frequently used method to prevent bacteria from invasion of blood-contact biomedical products. Potential damage induced by UV radiation to collagen is of concern due to the decay of bioactivity, considerably correlated with structural alterations. Our current investigation studies the collagen-bonded non-woven polypropylene (PP) fabric surface. In this experiment, antenna-coupling microwave plasma is utilized to activate PP fabric and then the sample is grafted with acrylic acid (AAc). Type III collagen is immobilized by using water soluble 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide as coupling agent. The collagen-bonded samples with sample temperature ca. 4 degrees C are then exposed to UV-254nm radiation for different time intervals. By using fourier-transformed infrared with attenuated total reflection (FTIR-ATR) and XPS (X-ray photoelectron spectroscopy), we examine the chemical structures of samples with different treatments. Coomassie brilliant blue G250 method is utilized to quantify the immobilized collagen on the PP fabric surfaces. Blood-clotting effects are evaluated by activated partial thromboplastin time, thrombin time, and fibrinogen concentration tests. By means of cell counter and scanning electron microscopy we count red blood cells and platelets adhesion in the modified porous matrix. Our experimental results have demonstrated that with pAAc-grafting of ca. 173 microg cm(-2) and immobilized collagen of 80.5+/-4.7 microg cm(-2), for human plasma incubated samples of various intervals of UV-254 nm radiation, fibrinogen concentration decreases in human plasma, while platelets and red blood cells adhesions increase before UV radiation. However, the required time for thrombination shows significant change for UV radiation exposure of less than 20 h (alpha = 0.05). The decay of bioactivity for the UV-irradiated, collagen-bonded surfaces is thus evaluated. Surface analyses indicate that the decrease of R-COOH (derivated from grafted-pAAc or de-carboxylation of collagen), amides degradation (broken-NH), and phenylalanine scission (terminated by -OH, tyrosine formation) may gradually damage collagen by increasing the intervals of UV radiation. These effects considerably influence the bioactivity of the collagen-bonded fabric. The XPS measurements of C 1s core levels at 288.4 eV (O = C-NH) and at 289.1 eV (O = C-O) illustrate significant decreases of intensity after radiation time ca. 44 h. It is clear that UV-254 nm radiation exposure for ca. 20 h has the potential impact to moderate the bioactivities of collagen and therefore act as a vital factor to accelerate biodegradation.

The clinical management of cytomegalovirus infection and disease in renal transplant recipients has recently been significantly improved with the availability of data on prophylaxis with oral ganciclovir and valacyclovir. In addition, significant progress in early diagnosis and the quantitation of viral load has been achieved. The influence of novel immunosuppressants on the clinical course of cytomegalovirus infection has been clarified to some extent by recent clinical data. The identification of risk factors for cytomegalovirus disease beyond seroconstellation and immunosuppression is an ongoing process that might lead to a more targeted use of antiviral agents, given the risk of ganciclovir resistance. The understanding of the effects of cytomegalovirus on long-term graft outcome still needs to be deepened in order to design cytomegalovirus-specific interventions to improve graft survival.

We report on a 50-year-old man with rapidly progressive glomerulonephritis and carcinoma of the hypopharynx. Because cancer treatment was followed by remission of proteinuria and complete restoration of renal function, a causal relationship between tumor and glomerular injury seems possible.

Background: Although specific therapy is available with ganciclovir, cytomegalovirus (CMV) disease remains a major problem after renal transplantation especially in CMV seronegative recipients of organs of seropositive donors (D+R-)., Methods: In an open-labeled prospective controlled trial we evaluated the effect of long-term oral ganciclovir prophylaxis (3 g/day for 3 months posttransplantation) in a cohort of 31 CMV-high risk (D+R-) renal transplant recipients (GC) compared with a cohort of 28 high-risk patients with targeted CMV prophylaxis (CO) receiving i.v. ganciclovir during antirejection therapy. Primary end-points were CMV infection, diagnosed by pp65 antigenemia assay or serologic method, and CMV disease. Additionally severity of CMV disease quantified by a scoring system was evaluated., Results: CMV prophylaxis significantly reduced the incidence of CMV infection (CO: 75%, GC: 45%; P<.05) and CMV disease (CO: 60%, GC: 29%; P<.05) without relevant side effects and without any clinical suspicion of ganciclovir resistance. Severity of CMV disease as quantified by a scoring system was reduced from 8.3+/-6.7 points in controls to 3.3+/-2.6 points in ganciclovir-treated patients (P<.05). Mortality did not differ significantly between the two groups (CO: n=3, GC: n=1; NS). However, there was one lethal CMV disease and a second death possibly attributable to CMV disease in the control group, whereas in ganciclovir-treated patients there was no CMV-associated fatal outcome., Conclusion: Long-term oral ganciclovir prophylaxis is effective and safe in CMV high-risk renal transplant recipients.

The Synchrotron Radiation Research Center (SRRC) and the Institute of Atomic and Molecular Sciences (IAMS) have initiated a project to construct a scanning photoelectron spectromicroscopy end station at SRRC (SRRC-SPEM). High-brightness soft X-rays will be provided by the U5 undulator beamline. Zone-plate-based soft X-ray optics will be used to focus the beam to form the microprobe. A hemispherical sector analyser with multichannel detection capability will collect the photoelectrons. A total of up to 32 images can be acquired concurrently. The apparatus is also equipped with a sample distribution system for in situ sample preparation and characterization in conjunction with other surface spectroscopic techniques.

Recent studies showed contradictory results concerning the efficacy of oral acyclovir in the prevention or amelioration of cytomegalovirus (CMV) disease after renal transplantation (TX). This study evaluated the incidence and severity of CMV disease within the first year after TX in high-risk renal transplant recipients (CMV-seropositive donor, seronegative recipient) treated prophylactically with oral acyclovir (800 to 3200 mg/day) over a period of 12 wk (ACY, N = 22), compared with high-risk patients randomly assigned as controls (CO, N = 10). Follow-up for CMV infection included serological determination of CMV-specific immunoglobulin G and immunoglobulin M antibodies, antigen detection in peripheral blood leukocytes (PP 65), shell vial culture (blood), and virus isolation/early antigen detection (urine). Severity of CMV disease was quantified by a scoring system for CMV-related symptoms. Nine patients (40.1%) in the acyclovir group and four patients (40%) in the control group developed CMV disease. Neither severity (ACY, 11.4 versus CO; 12.5 points score), nor duration of disease (ACY, 21 days; CO, 22 days), nor transplant function at the end of the observation period differed significantly. The onst of CMV disease was not delayed significantly in acyclovir-treated patients compared with controls (ACY, 47 +/- 34 days versus CO, 27 +/- 14 days after TX, not significant). Our results show no beneficial effect of oral acyclovir prophylaxis in CMV high-risk renal transplant recipients.