bluuebunny/crossref_metadata_2025 huggingface dataset:
Preach What You Practice. The Security Council and the Legalisation ex post facto of the Unilateral Use of Force
Authors: Österdahl Inger
Published: September 2005

In recent years the UN Security Council has entered the scene of action several times after a unilateral military intervention has already taken place. The Security Council has adopted comprehensive schemes for the reconstruction of the countries intervened in and has authorised both civil and military international presences. Kosovo, Afghanistan and Iraq are examples of such recent situations, and Liberia is an example from the early 1990s. This article makes the argument that, through its resolutions, the Security Council contributes to the legalisation ex post facto of the unilateral interventions, whether it wants to or not. The Security Council is caught in a trap set by those who undertake the intervention without prior Security Council authorisation.The only way the Security Council could escape the retroactive legalising effect of its resolutions would be by clearly stating in the resolution its intention not to authorise the preceding intervention. Even then, it may be that the Security Council could not escape the power of its own practice. A persistent practice of adopting reconstruction resolutions ex post facto would carry greater legal weight than the professed intention not to legalise the preceding unilateral intervention.Still, authorisation ex post facto may be better than no authorisation at all.
Circumstances Justifying Pre-emptive Self-Defence: Thoughts Prompted by the Military Action Against Iraq
Authors: Zedalis Rex
Published: September 2005

The outpouring of literature on pre-emptive self-defence both in advance and in the wake of the 2003 U.S. invasion of Iraq, as well as remarks by UN Secretary-General Kofi Annan in the Fall of 2004 characterizing the invasion as violative of prevailing international legal standards, suggests the continuing importance of considering aspects of pre-emption which have received little attention. In this connection, it is argued that the relevant formulation of the customary legal standard can be seen as aiming at minimizing the likelihood of defensive force being employed by mistake. The implication would thus be that clarity regarding a future threat of attack, not the imminence of the attack itself, affects whether advance defensive action is to be considered justified. Further, it is also argued that, unless one is content to simply stand on legal principle in the abstract, the importance of a threatening State's intention and capacity to attack require detailed examination and a high level of proof before considering putative defensive action to be legitimate. Finally, given the customary international legal standard's requirement that forceful pre-emptive action be taken only when no other means exist to address a threat of attack, a variety of considerations, ranging from access to non-forceful alternatives, to the viability of alternatives that exist and are accessible, demand attention prior to determining that an immediate resort to defensive force should be evaluated as permissible.
Amnesty and International Law
Authors: O'Brien Roderick
Published: September 2005

Amnesties are proving as popular in the twenty-first century as they did in the twentieth. Wherever there is an attempt to end a conflict, there is often an amnesty. The author briefly surveys the characteristics of amnesties, and offers a simple taxonomy. The author next assesses the approach taken in international law to amnesties. The survey draws on the experience of the International Tribunal for the Former Yugoslavia, and the Special Court for Sierra Leone. Subsequently the author looks ahead to the Proposed Extraordinary Chamber for Cambodia and the International Criminal Court. From this survey, two particular topics for international law are addressed: the right to a fair trial, and alternatives to courts (such as Truth and Reconciliation Commissions). Assuming that international law is going to be selective in its treatment of amnesties, the author offers a tentative model for an amnesty which will meet the needs of current international law.
The Emergence of a Shared Identity
Authors: Rousseau David , van der Veen A. Maurits
Published: September 2005

Liberal theorists and, more recently, constructivists have argued that a shared sense of identity will decrease threat perception and increase international cooperation. But what processes lead to the emergence (or collapse) of a shared sense of identity? Drawing on individual-level experiments of identity change and societal-level theories of idea diffusion from the constructivist literature, the authors develop an agent-based computer simulation of identity change. Four findings emerge from the analysis: (1) there is a curvilinear relationship between the complexity of agents'views and the emergence of shared identity, (2) highly unstable environments encourage the emergence of a shared identity, (3) the presence of leaders (i.e., agents with greater influence in the population) in the neighborhood decreases shared identity, and (4) the interaction of complexity, stability, and leadership produces extremely polarized societies.
Maintenance Processes in International Rivalries
Authors: Goertz Gary , Jones Bradford , Diehl Paul F.
Published: September 2005

This article asks a new question: what are the processes that maintain rivalries? The authors argue that rivalries are maintained through the failure of realist strategies and conflict management ones. They focus on stalemate outcomes as both a signal that militarized strategies for dealing with conflict have not succeeded and as reasons for the countries to continue the rivalry. They explore the process of rivalry maintenance, largely from the perspective of the punctuated equilibrium model of rivalries, and examine 1,166 rivalries across the period from 1816 to 1992. They contrast their approach with that of the “repeated conflicts” literature, which only examines the impact of the previous dispute on recurring conflict. The authors find that the most recent conflict does matter, and the longer term history of the rivalry is more important. They also find that the impacts of various factors (e.g., democracy) change over the course of the rivalry.
Keeping the Peace after Secession
Authors: Tir Jaroslav
Published: September 2005

Secession is an attempt to resolve a domestically based territorial dispute by dividing a country's homeland territory into new, secessionist (e.g., Eritrea) and rump (e.g., Ethiopia) states. Yet, the secession may not have resolved the original dispute to the states' satisfaction. In the aftermath of a secession, the leader of the rump state is motivated to use force by the benefits of retaking (some of) the land lost to the secessionist state, while the secessionist state's leader is motivated by the benefits of acquiring even more land. The peaceful versus violent secession process further affects whether these desires escalate into the use of force. The results—based on the examination of the consequences of all twentieth-century secessions—reveal that ethnically based territorial disputes play a much greater role in conflict onset than do their economically or strategically based counterparts and that peaceful secessions lead to peaceful relations.
Leader Age, Regime Type, and Violent International Relations
Authors: Horowitz Michael , McDermott Rose , Stam Allan C.
Published: September 2005

In this article, the authors investigate the relationship between states'political leaders'ages, their regime type, and the likelihood of militarized dispute initiation and escalation. They examine more than 100,000 interstate dyads between 1875 and 2002 to systematically test the relationship between leader age and militarized disputes. The results show that, in general, as the age of leaders increases, they become more likely to both initiate and escalate militarized disputes. In addition, the interaction of age and regime type is significant. In personalist regimes, the general effect reverses; as age increases, the relative risk of conflict declines in comparison to other types of regimes. Increasing leader age in democracies increases the relative risk propensity for conflict initiation at a higher level than for personalist regimes, while the impact of increasing leader age is most substantial in intermediate regimes.
A CEO-Adviser Model of Strategic Decision Making
Authors: Arendt Lucy A. , Priem Richard L. , Ndofor Hermann Achidi
Published: September 2005

Upper echelons research has emphasized decision making either by individual CEOs or by teams of top managers. The authors introduce the CEO-Adviser model as an intermediate model of strategic decision making. The CEO-Adviser model leads to new propositions that have not been explored through the individual CEO or top management team models concerning how context affects the use of formal versus informal advisory systems and how advisers are selected.
The Dimensions and Antecedents of Team Virtuality
Authors: Kirkman Bradley L. , Mathieu John E.
Published: September 2005

Team virtuality is an important factor that is gaining prominence in the literature on teams. Departing from previous research that focused on geographic dispersion, the authors define team virtuality as the extent to which team members use virtual tools to coordinate and execute team processes, the amount of informational value provided by such tools, and the synchronicity of team member virtual interaction. The authors identify the key factors that lead groups to higher levels of team virtuality and the implications of their model for management theory and practice.
Measuring Physical Activity During Pregnancy
Authors: Lindseth Glenda , Vari Patty
Published: September 2005

Few studies exist that identify a useful self-report measure of physical activity for pregnant women. The purpose of this study was to compare the self-report exercise diary with the pedometer and determine if self-report measurement provided useful physical activity measures during pregnancy. The pregnant women’s sleep, parity, and related demographic factors were further analyzed for relationships to the physical activity measures. Physical activity was assessed in a sample of 94 pregnant midwestern U.S. women ages 18 to 38 years. The women wore a pedometer during all waking hours for 3 consecutive days at 14 and 28 weeks of pregnancy for a total of 6 days. During the same 6 days of monitoring, the women kept a diary account of the minutes they exercised per day. The pedometer and self-report exercise diary results correlated significantly (r = 49, p = .02). When examining for usefulness in measuring physical activity, a comparison of the women’s occupational categories revealed no significant differences in self-reported minutes of exercise or pedometer counts per day.
Assessing Cross-Cultural Equivalence Through Confirmatory Factor Analysis
Authors: Hsueh Kuei-Hsiang , Phillips Linda R. , Cheng WenYun , Picot Sandra J. Fulton
Published: September 2005

This article presents a study in which Picot’s caregiver rewards scale (PCRS), originally developed in English, was cross-culturally validated with 137 Chinese adult children family caregivers in the United States using confirmatory factor analysis. A one-factor structure of the 21-item revised Chinese PCRS was supported as indicated by goodness-of-fit index = .94, adjusted goodness-of-fit index = .93, standardized root mean square residual = .09, and chi-square to df ratio = 2.7. Chi-square for this model was (X2 [189, n = 137] = 514, p < .05). The standardized alpha was .90. All factor loadings were significant (p < .00) and above .30. Construct validity was supported by significant associations with caregivers’ filial beliefs (r = .32, p < .01) and caregivers’ filial affection toward parents (r = .23, p < .05). Results suggest that the Chinese PCRS is a summative measure of perceived caregiver rewards with potential for evaluating interventions to reduce perceived burden among adult children family caregivers.
Psychological Distress and Milk Volume in Lactating Mothers
Authors: Hill Pamela D. , Aldag Jean C. , Chatterton Robert T. , Zinaman Michael
Published: September 2005

The purpose of this article is twofold: (a) to compare psychological distress as measured via self-reported perceived stress, sleep, and fatigue levels in lactating mothers of a term infant and mothers of a preterm infant and(b) to determine whether the addition of psychological distress to a previous model predicts milk volume at Postpartum Week 6 by gestation group. The convenience sample of 95 mothers of a preterm infant (31 weeks) and 98 mothers of a term infant completed the Perceived Stress Visual Analogue Scale, Richards-Campbell Sleep Questionnaire, and the Fatigue Visual Analog Scale. Stress, sleep difficulty, and fatigue levels decreased during the 6-week study period for mothers of a term but not for mothers of a preterm infant. Perceived stress, sleep difficulty, and fatigue during the first 6 weeks postpartum were not related to milk volume; thus, the mother’s perceived psychological distress had no apparent effect on lactation.
ANCA-associated vasculitis as paraneoplastic syndrome with colon cancer: a case report
Authors: Díez-Porres L , Ríos-Blanco J J , Robles-Marhuenda A , Gutiérrez-Molina M , Gil-Aguado A , Vázquez-Rodríguez J J
Published: September 2005

Coexistence of a vasculitis and a neoplastic disease is rare and the pathogenesis is unknown. Most of these associations refer to leukocytoclastic or poliarteritis nodosa (PAN)-type vasculitis and hematological malignancies. There are few reports of vasculitis in patients with solid tumours and there are also few reports of paraneoplastic ANCA-associated vasculitis. We report a case of p-ANCA-positive vasculitis with peripheral nerve involvement associated with a colon cancer. Vasculitis resolved after corticoid treatment and surgical removal of the tumour.
High sensitivity C-reactive protein in systemic lupus erythematosus: relation to disease activity, clinical presentation and implications for cardiovascular risk
Authors: Barnes E V , Narain S , Naranjo A , Shuster J , Segal M S , Sobel E S , Armstrong A E , Santiago B E , Reeves W H , Richards H B
Published: September 2005

Measurement of high sensitivity C-reactive protein (hs-CRP), has been used in the assessment of disease activity in numerous rheumatic conditions including systemic lupus erythematosus (SLE). However, the utility of hs-CRP measurement in patients with lupus is uncertain. This study examined if hs-CRP can be used to assess disease activity, severity and cardiovascular risk in SLE. Serum samples from 601 visits of 213 SLE patients and 134 controls were analysed for hs-CRP by nephelometry. Detailed demographic data were obtained from all subjects and medication history and key laboratory parameters were collected. Disease activity was assessed using the SLEDAI. High sensitivity CRP was not associated with disease activity (SLEDAI), number of ACR SLE criteria or presence of any particular organ involvement. hs-CRP levels were significantly correlated with standard cardiovascular risk factors including body weight ( P = 0.0002), hypertension ( P = 0.001), and apolipoprotein A-I ( P < 0.0001). Interestingly an inverse correlation was seen between hs-CRP levels and antimalarial use ( P = 0.0018). Our results suggest that measurement of hs-CRP, though not valuable as marker of disease activity in SLE may be of some use in the assessment of cardiovascular risk. We speculate that antimalarials may help to reduce cardiovascular risk in patients with SLE.
The frequency of high/moderate lipoprotein risk factor for coronary artery disease is significant in juvenile-onset systemic lupus erythematosus
Authors: Hayata A LS , Borba E F , Bonfá E , Kochen J AL , Goldenstein-Schainberg C
Published: September 2005

To determine the prevalence of dyslipoproteinemia on a large juvenile systemic lupus erythematosus (jSLE) cohort, we selected 40 patients after rigorous exclusion criteria. Lipoprotein levels were determinated after 12 hours fast and risk levels for CAD were defined by standards of the Brazilian Guidelines for dyslipoproteinemia according to US-NCEP. All individuals were under steroid therapy and chloroquine and 43% had active disease. Thirty patients (75%) had high-risk levels for CAD (23 isolated low HDL, while in seven subjects low HDL was associated to high TG in four, high LDL in one, high TG/LDL in one and high TC/LDL in one). Remarkably, overall analysis revealed that 85% patients were included in high/medium risk levels group (29% for TC, 29% for LDL, 88% for HDL, and 18% for TG) and these disturbances occured mainly in the first four years of disease. Unexpectedly, one-third of the patients presented two or more high/medium lipoprotein risk factors. Independently, active jSLE was associated to TG (OR = 3.2; P < 0.001) and had a tendency towards reduction on HDL (OR = 8.5; P = 0.056). Considering improvements on jSLE outcome, the increased frequency of high/medium lipoprotein risk levels for CAD reinforces the need of prevention measures in order to minimize deleterious effects of this disturbance.
Characterization and Properties of Green Emitting Ca3SiO4Cl2:Eu2+ Powder Phosphor for White Light-emitting Diodes
Authors: Liu Jie , Lian Hongzhou , Sun Jiayue , Shi Chunshan
Published: September 2005

An efficient green emitting phosphor, Eu2+-doped Ca3SiO4Cl2, is reported. Its excitation band is extending from 260 to 470 nm, which is coupled well with the emission of UV LED (350–410 nm) and blue LED (450–470 nm). It exhibits a strong green emission centered at 505 nm with chromatic coordination (0.25, 0.57), which indicates that it could be a good green phosphor candidate for creating white light in phosphor-converted white LEDs.
A Novel One-pot Synthesis of 2H-4-Chlorochromenes via the Vilsmeier Reaction of 2′-Hydroxychalcones
Authors: Kumar Kalvi Hemanth , Perumal Paramasivan Thirumalai
Published: September 2005

A novel versatile one-pot synthesis of 2H-4-chlorochromenes from 2′-hydroxychalcones have been developed. This method has been investigated for the synthesis of 2H-4-chlorochromen-2-ylpyrazoles.
A New Type of Orally Active Insulin-mimetic Vanadyl-porphyrin Complex: meso-Tetrakis({4-sulfonatophenyl}porphyrinato)oxovanadium(IV)
Authors: Saha Tapan Kumar , Adachi Yusuke , Yoshikawa Yutaka , Yasui Hiroyuki , Sakurai Hiromu
Published: September 2005

Vanadyl-meso-tetrakis(4-sulfonatophenyl)porphyrin, VOTPPS, was synthesized and evaluated for its in vitro and in vivo insulin-mimetic activities in streptozotocin (STZ)-induced diabetic mice. Based on the high in vitro insulin-mimetic activity in terms of inhibition of free fatty acid release and enhancement of glucose-uptake in adipocytes, and matallokinetic parameters, VOTPPS was revealed to have a significant hypoglycemic activity in STZ-mice following a single oral gavage of the complex. VOTPPS is thus found to be the first example for orally active vanadyl-porphyrin complex to treat type 1 diabetic animals.
Outstanding Vapochromism and pH-dependent Coloration of Dicyano(4,4′-dicarboxy-2,2′-bipyridine)platinum(II) with a Three-dimensional Network Structure
Authors: Kato Masako , Kishi Shinobu , Wakamatsu Yuki , Sugi Yoshiko , Osamura Yoko , Koshiyama Tamami , Hasegawa Miki
Published: September 2005

Dicyano(4,4′-dicarboxy-2,2′-bipyridine)platinum(II) forms pH-dependent polymorphs of various colors and displays outstanding vapochromism followed by luminescence changes upon exposure to certain organic vapors. The high sensitivity of the complex to vapor and pH is related to its three-dimensional network structure, which includes large cavities formed by hydrogen bonds and Pt···Pt interactions.
Synthesis of Bis(phenoxyimine) Ti Alkyl Complexes and Observation of Living Species by 1H NMR Spectroscopy
Authors: Makio Haruyuki , Oshiki Toshiyuki , Takai Kazuhiko , Fujita Terunori
Published: September 2005

Synthesis of [C6F5N=CH(2-O-C6H3-3-R)]2TiMeX (R: tBu; X: Br (2), R: tBu; X: Me (3), R: H; X: Me (4)) was achieved by the reaction of methylated titanium halides with sodium salts of the phenoxyimine ligands. These complexes can be activated with equimolar amounts of B(C6F5)3 or Ph3CB(C6F5)4 to form methyl cationic species, which, upon addition of a small amount of ethylene monomer allows room temperature observation of cationic polymeryl species.
Gradual Two-step Spin Crossover Behavior of Binuclear Iron(III) Complex Bridged by trans-1,2-Bis(4-pyridyl)ethylene
Authors: Kitashima Ryoko , Imatomi Shinya , Yamada Masahiro , Matsumoto Naohide , Maeda Yonezo
Published: September 2005

A binuclear iron(III) complex bridged by trans-1,2-bis(4-pyridyl)ethylene, [LFeIII(vibpy)FeIIIL](BPh4)2, showed a gradual two-step spin crossover behavior, where H2L is bis(3-methoxysalicylideneaminopropyl)methylamine and BPh4− is tetraphenylborate. The single-crystal X-ray analysis at the intermediate state revealed that one of the two FeIII ions of the binuclear complex is in the high-spin (HS) state and the other is in the low-spin (LS) state. The HS and LS sites independently form layers and these HS and LS layers alternately stack.
The KBr Pellet: A Useful Technique for Obtaining Infrared Spectra of Inorganic Species
Authors: Gendreau R. M. , Burton R.
Published: September 2005

The reproducibility of the KBr pelleting technique for inorganic sulfates was assessed using a Fourier transform infrared spectrometer. Day-to-day variation in peak frequencies of selected bands had standard deviations ranging from 0. to 1.5 cm−1. This 1 cm−1 standard deviation was shown to be due to changes in bandshape, probably due to variations in sample preparation from operator to operator. It was concluded that the reproducibility of sulfates in KBr is sufficient to allow the design of computerized spectral matching programs to identify specific sulfate species based on band frequencies and intensities.
Evaluation of the Axially Viewed (End-on) Inductively Coupled Argon Plasma Source for Atomic Emission Spectroscopy
Authors: Demers D. R.
Published: September 2005

A comparison of an “end-on” viewed argon inductively coupled plasma (ICP) operated in the horizontal position with the conventional “side-on” viewed argon ICP was carried out using the same experimental setup. The end-on ICP required an air cutoff stream located toward the tip of the luminous discharge, to protect the optics and to increase linearity ranges, and the orifice diameter of the central tube of the torch was widened to 1.9 mm, to improve line/background ratios. With the end-on viewed plasma the linearity ranges, the susceptibility to solute vaporization and to ionization matrix effects, and the detection limits in an organic solvent were insignificantly different from those observed with the side-on viewed plasma. Detection limits with aqueous samples were always significantly lower with the end-on viewed plasma, usually five- to tenfold lower, in a few instances, 20-fold lower. With the end-on viewed plasma the optimal observation region for both single and simultaneous multielement analysis is one and the same and is extremely easy to locate.
Inexpensive Temperature Feedback Controller for the Varian 63 CRA
Authors: Siemer Darryl D.
Published: September 2005

Construction details and the performance of a temperature feedback circuit added to the power suppy of a Varian model 63 furnace atomizer are discussed. The circuit incorporates a photo transistor temperature transducer and approximately $25 worth of readily available electronic components to implement both a variable temperature ramp rate and a variable maximum temperature function. The normal mode of operation can be selected if desired.
Calibrating Raman Spectrometers with Plasma Lines from the Argon Ion Laser
Authors: Craig Norman C. , Levin Ira W.
Published: September 2005

The majority of the plasma lines of the argon ion laser are shown to be transitions of the argon ion. These lines are useful for calibrating Raman spectrometers. A table is given of the plasma lines, including relative intensities, wavelengths (in standard air), wavenumber ( in vacuo), and wavenumber shifts relative to the 488.0 and 514.5 nm laser lines. Spectra showing the relative intensities of these lines are also shown.
Analysis of X-ray Photoelectron Spectra through Their Even Derivatives
Authors: Pavlath Attila E. , Millard Merle M.
Published: September 2005

The analysis of organic and inorganic surfaces can be carried out very effectively with the aid of x-ray photoelectron spectroscopy. In many cases, however, the presently available methods and techniques for data treatment resolutions are not suitable for the qualitative and quantitative identification of the various forms of a given atom on the same surface. The number of components and a good approximation of their original position in the composite curve must be known to use the available curve fitting procedures, otherwise the evaluation can be unreliable. It is suggested that the second and higher even derivatives of the composite could provide these data. The possibility of applying even derivatives of composite curves in combination with a nonlinear least square curve fitting program was investigated. It was found that depending on the noise background of the spectra, the resolution could be improved through this method. The resolution is dependent on the half-width of the component curves, their separation, and ratio. Both Gaussian and Lorentzian curves can be resolved, but the resolution of the latter is easier. The resolution is increasing with higher derivatives; however, increased smoothing must be applied at each step to neutralize the influence of the noise background.
Evaluation of Spectral Interferences Associated with a Direct Current Plasma-Multielement Atomic Emission Spectrometer (DCP-MAES) System
Authors: Johnson G. W. , Taylor H. E. , Skogerboe R. K.
Published: September 2005

Spectral interferences associated with a direct current plasma combined with a 20-element, direct reading echelle spectrometer have been characterized. The results indicate that molecular emission interferences due to entrained air are generally negligible, but the presence of high carbon concentrations may cause problems for two elements. Spectral interferences due to the presence of high concentrations (500 mg/l) of Ca, K, Mg, and Na were also studied. No problems were noted for Na or K while an interference due to atomic emission of Mg was observed. Calcium was responsible for stray light interferences due to near scatter and to reflections occurring in the secondary optics. The latter were eliminated by masking techniques and the former were compensated for via the use of a simple procedure. Overall, the spectral interferences encountered appear to be less severe than those reported for an inductively coupled plasma-direct reading spectrometer system.
Some Wider Uses of Group Frequencies
Authors: Bellamy L. J.
Published: September 2005

This paper discusses current and potential uses of group frequencies for purposes other than analysis or the identification of compounds or groups. These include the study of chemical mechanisms, of changes in bond angles, of vibrational coupling, and of the relationship between group frequency shifts and changes in other properties of the bonds. Some suggestions are offered on the structure of liquid water.
Raman Spectra of Gases. XXII. (CH3)3SiCl, (CD3)3SiCl and Some Normal Coordinate Calculations on (CH3)3SiNCO and (CH3)3SiNCS
Authors: Durig J. R. , Jalilian M.
Published: September 2005

The Raman spectra (0 to 3600 cm−1) of gaseous (CH3)3SiCl and (CD3)3SiCl have been recorded. It was possible to resolve the symmetric and antisymmetric SiC3 deformations. The spectra are discussed in detail and previous vibrational assignments are compared. A normal coordinate calculation has been carried out utilizing a modified simple valence force field. The extent of the vibrational coupling has been determined. It is believed that the main force constants should be transferable to other substituted trimethylsilyl compounds and this transferability is demonstrated by some normal coordinate calculations for trimethylsilylisocyanate and trimethylsilylisothiocyanate.
The Determination of Absolute Infrared Intensities with a Fourier Transform Spectrometer
Authors: Scanlon Kerin , Laux Leo , Overend John
Published: September 2005

In principle it is apparent that Fourier transform infrared spectroscopy offers a number of significant advantages in the determination of infrared intensities integrated over the rotational fine structure in vibration-rotation bands. One expects that there should be no problem with photometric accuracy; yet, before embarking on a systematic program of study, we believe it important to establish that the method will work in practice. As a test case we have chosen the V2 fundamental of CO2 at 673 cm−1 since this is, in our experience, as difficult a band as any when it comes to measuring integrated intensities. We have, using a Digilab FTS-20 spectrometer, determined a value of the integrated intensity, Γ2 = 7901 ± 105 cm2/mol which should be compared with the value previously determined on a dispersive instrument, Γ2 = 7882 ± 110 cm2/mol. We have also determined a value of Γ3 = 25,300 ± 570 cm2/mol for the integrated intensity of the antisymmetric stretching fundamental.
Quantitative Infrared Spectroscopic Measurements of Mixtures without External Calibration
Authors: Koenig Jack L. , Kormos Donald
Published: September 2005

A general spectroscopic method for the analysis of mixtures that does not require external calibration has been developed. The method is based on the obtaining of absorbance ratio spectra and the determination of a concentration ratio at frequencies unique to each component. The method is applied to mixtures hexane and cyclohexane.
Analytical Band Model for SO2 Transmittance in the Infrared
Authors: Pierluissi Joseph H. , Demshur Paul
Published: September 2005

An application is made of numerical computer techniques to the modeling of molecular absorption by atmospheric sulfur dioxide in the infrared region. The general transmittance function used in the widely accepted code called Lowtran is adopted, through an analytical approximation available in the literature for water vapor, ozone, and the uniformly mixed absorbers. The transmittance data used in the development were generated from simulated line spectra calculated with a tape tabulation of line parameters for the trace gases. The constants describing the function, as well as the spectral parameters at 5 cm−1 intervals, are provided in order to allow for direct calculation of sulfur dioxide transmittance in typical concentrations over the infrared region of absorption.
Investigation of Chrome Ores Using X-Ray Diffraction, X-Ray Fluorescence, and Mössbauer Spectroscopy
Authors: Eng George , May Leopold , Mills Albert , Bober Alvin , Adams James M.
Published: September 2005

The main mineral component of chrome ore that contains chromium is chromite. Certain legal and trade restrictions required the development of analytical techniques that would be useful in determining the country of origin of a chrome ore. Ores from 13 countries were examined by x-ray diffraction, x-ray fluorescence for chromium and iron content, and Mössbauer spectroscopy of iron sites. The 13 countries could be divided into four groups based on the chromium and iron content via x-ray fluorescence. The x-ray diffraction spectra could be used to identify the country of origin within three of the groups. Within the fourth group of countries, the x-ray diffraction spectra can be used to differentiate three subgroups, one of which includes only one country. Mössbauer spectroscopy is used to differentiate the countries within the remaining subgroups. A schema is presented for the identification of the ores from the 13 countries.
Comparison of Interference Effects for Manganese in Constant Temperature vs Pulse-Type Electrothermal Atomization
Authors: Hageman Lynn , Mubarak Ahmed , Woodriff Ray
Published: September 2005

The application of electrothermal atomization techniques for atomic absorption spectroscopy has increased many fold in recent years. Along with this widespread application, matrix interferences in pulse-type electrothermal atomizers have been observed. Until recently, very few interference studies have involved constant temperature electrothermal atomizers. In this paper a comparison is made of interferences in pulse-type vs constant temperature atmoziers for various metal chlorides on the Mn atomic absorption signal. The results show no interferences in the constant temperature system while significant matrix interferences are observed in the pulse type unit. It is proposed that the observed differences are due mainly to the rate at which volatilized analyte attains atomization temperature and the residence time in the hot environment.
Reduced Fluorescence from Tris-(8-Quinolinolato) Aluminum(III) in the Presence of its Fe(III) Analog
Authors: Milham Paul J. , Hudson Alun W. , Maguire Michael J. , Haddad Kamel S. , Short Colin C.
Published: September 2005

Chloroform (CHCl3) solutions of tris(8-quinolinolato) Al(III) (AlQ3), when excited at 395 nm, fluoresce at 520 nm. Addition of tris(8-quinolinolato) Fe(III) (FeQ3) to these solutions decreases the fluorescence: the ratio of the fluorescent intensity in the presence of FeQ3, to that in its absence, is exponentially related to [FeQ3] and independent of [AlQ3]. We hypothesized that the main cause of this effect was FeQ3 absorption of the exciting and emitted radiations. The hypothesis was tested in two ways: first, by calculating fluorescence losses using FeQ3 absorbance measured at 395 and 520 nm; and second, by measuring fluorescence losses when the AlQ3 was in one optical cell, and the FeQ3 in others, which were located in either the excitation or emission paths, or both. Comparison between all the results showed that they were not significantly different (P0.01), thus verifying the hypothesis.
An Inductive-Coupled Plasma Atomic-Emission Spectrometric Method for Routine Water Quality Testing
Authors: Garbarino J. R. , Taylor H. E.
Published: September 2005

Induction-coupled plasma atomic-emission spectrometry offers an ideal method for simultaneous multielement analysis of natural water samples. The Water Resources Division of the U.S. Geological Survey currently employs this technique for quantitative analysis of 17 major and trace constituents. These include analysis of Ba, Be, Cd, Co, Cu, Fe, Pb, Li, Mn, Sr, Mo, V, Zn, Ca, Mg, Na, and SiO2 in a routine production mode, in which an excess of 1000 determinations can be made in a normal working day. Comparability studies with conventional single-element methods of analysis, such as atomic absorption spectrometry and colorimetric techniques, show essentially equivalent accuracy and precision, frequently at much higher sensitivity.
Application of Second-Derivative UV-Absorption Spectrometry to Polynuclear Aromatic Compound Analysis
Authors: Hawthorne Alan R. , Thorngate John H.
Published: September 2005

The increased awareness of the deleterious effects of polynuclear aromatic (PNA) compounds emphasizes the need for instruments that are capable of monitoring these compounds and also are suitable for use in health protection programs. Second-derivative UV-absorption spectrometry with least-squares spectral analysis shows promise as a method for analyzing vapor phase PNA's, as well as solutions containing these compounds. Detection limits of a few parts per billion are attainable for many PNA compounds. Examples are given showing the analytical capabilities of this procedure.
On the Digital Computer Method of Spectral Line Analysis
Authors: Nomura Hiroyasu , Koda Shinobu , Miyahara Yutaka
Published: September 2005

A new digital computational method of spectral line shape analysis is reported. In the present method, the parameters of object functions are directly found to fit the experimental values on the basis of a nonlinear least squares method. The present method is available for curve fitting of experimental results if the functions are expressed in analytical form. As an example, the results of resolving the recorded Raman spectra into the component line shapes is presented. The agreement of the recorded Raman spectra with that composed of the resolved lines is excellent.
On-Line Identification of Gas Chromatographic Fractions by a Raman Multichannel Spectrometer
Authors: D'Orazio M.
Published: September 2005

A Raman multichannel system is described which is feasible for the on-line identification of fractions separated by gas chromatographic columns. In Raman multichannel systems, the sensor, i.e., the laser focus, is small enough and the possible recording times are short enough to avoid any affliction of the separation process, even with capillary columns in use. At the measurements described, capillary columns with a length of 15 m and an inner diameter of 0.25 mm were employed. The detection limit was at about 1 to 10 nl of one fraction corresponding to about 1 to 10% of the total amount of sample suited for capillary columns.
Investigation into the Operating Characteristics of a “Microarc” Atmospheric-Pressure Glow Discharge
Authors: Bystroff R. I. , Layman L. R. , Hieftje G. M.
Published: September 2005

Details of the processes occurring during sample atomization from a “microarc” discharge have been studied photometrically, by use of high-speed color cinematography and through current-voltage waveforms. The microarc studied here is an atmospheric-pressure inert-gas glow discharge supported between 0.25 mm diameter tungsten wires; quiescent argon-1% H2 provides reactive-sputtering conditions and improved behavior in the presence of oxygen impurities. Excitation temperatures of ca. 5000°K are measured for the argon glow. Samples of Na, Al, and Sr illustrate the influence of volatile, refractory, insulating, and electron-emitting sample properties on the temporal-spatial-electrical behavior of the discharge. The step-by-step events occurring in the discharge are described qualitatively and a variety of processes are invoked to explain sample volatilization, including sputtering, chemical reactions, and purely thermal effects. In the first stages of the discharge, instabilities are related to the placement and insulating character of deposits. With heating, electron emission becomes important in directing the discharge to or away from the sample; abnormal glow wandering and glow-to-arc transitions can ensue. Improved stability is achieved by uniformly depositing multi-element samples along the electrode, which localizes the initial discharge and promotes ablative cooling of the sample and electrode.
A Study of the Interaction of Pb-Sn Solder with O2, H2O, and NO2 by X-Ray Photoelectron (ESCA) and Auger (AES) Spectroscopy
Authors: Okamoto Yasuaki , Carter William J. , Hercules David M.
Published: September 2005

An ESCA and AES study of the corrosion of 1:1 Pb-Sn solder is reported. The solder was reacted at room temperature with O2 (1 Torr), H2O (10 Torr), 100 ppm of NO2 in N2 (1 atm), and the latter at 50% relative humidity. Pb and Sn foils were examined under similar conditions. The Pb/Sn ratios observed by ESCA and AES for unmelted solder are close to those expected from bulk composition. After melting, a 50% decrease in Pb/Sn was obtained by ESCA; no AES signal for Pb was observed. Before melting, 90% of the Pb and 100% of the Sn were oxidized; after melting 18% Pb and 70% Sn were oxidized. Exposure of solder to O2 (1 Torr) resulted in a Pb/Sn ratio which decreased as a function of time to a minimum value, rapidly increased through a maximum around 60 min and then decreased to an equilibrium value. The O/(Pb + Sn) ratio increased rapidly to an equilibrium value. The interaction of solder with 10 Torr of H2O vapor for 5 min resulted in surface enrichment of Sn with the formation of Sn and Pb oxides. The results obtained with dry NO2 were similar to those with O2; Pb/Sn decreased rapidly to a minimum and went through a small maximum to an equilibrium value. The distribution of species determined by ESCA before and after the reaction were essentially the same as for O2 except the oxidation of Pb was suppressed. No nitrogen species were observed. Solder exposed to at 100 ppm of NO2 in N2 50% relative humidity gave similar results to O2 and dry NO2. The Pb/Sn maximum occurred at a reaction time approximately 2 to 3 times that of O2 and dry NO2 (40 to 60 min). Two nitrogen species were observed for solder treated with 100 ppm of NO2 in N2 at 50% relative humidity; binding energies were ∼404 and 400 eV. These have been attributed to NO2− and NO−, respectively. Mechanisms are proposed for reaction of solder with O2, dry NO2, and NO2 at 50% relative humidity.
Vibrational Spectroscopic Investigation of Glycine Binding in a Zirconium—Aluminum—Glycine Antiperspirant Material
Authors: Oertel Richard P. , Rush Rhonda M.
Published: September 2005

Through use of Raman and infrared spectroscopy, we have determined the mode of incorporation of glycine, a gelation inhibitor, in a complex antiperspirant material (ZAG) containing zirconium and aluminum hydroxy chlorides. Most of the vibrational modes of glycine are affected upon inclusion of this component in ZAG. Our spectral analysis indicates that the glycine in ZAG exists as the dipolar ion, coordinated to metal ions through the COO− end and hydrogen bonded to various constituents through the NH3+ end. Almost all of the glycine in solid ZAG is bound in this fashion, as is more than half of the glycine in a 50% (by wt.) aqueous ZAG solution. This binding could well contribute to the gelation-inhibiting property of the glycine in aqueous ZAG by interfering with the extended hydroxy and oxy bridging that commonly exists in solutions containing Zr(IV) and Al(III). Several spectral features of the bound glycine dipolar ion, most especially a prominent Raman and infrared band near 1475 cm−1, are discussed in detail for the first time.
Structural Changes in a Sulfur-Resistant Methanation Catalyst as Determined from Infrared Spectra
Authors: Stencel J. M. , Heinz R. E. , Bradley E. B.
Published: September 2005

The infrared spectrum of a sulfur-resistant NiO/Cr2O3/MgAl2O4 methanation catalyst is presented and compared to the spectra of the catalyst after it was reduced, sulfided, and tested for methanation activity. The molecular structure of the catalyst is shown to be represented by NiO and MgO dispersed in a quasi-tridimensional Cr—O—Al network. Reduction and sulfiding reorders this network and alters the AlOn coordination while reducing Cr6+ to Cr3+ or Cr2+. The sulfided and methanation-tested catalyst has intense sulfate absorption indicative of sulfur which is coordinated with NiCr and/or NiMg sites.
Maclaurin Series Truncation Errors as Related to the Treatment of Fluorescence vs Concentration Data
Authors: Lam R. B. , Leary J. J.
Published: September 2005

The Maclaurin series remainder term is used to evaluate the linear approximation of e−x which relates concentration and fluorescence. The error associated with linear and higher order approximations is also treated. A method is described for calculating the error in the linear approximation given the sample concentration and molar absorptivity. The same approach is applicable to the calculation of the maximum concentration consistent with a prespecified error in the linear approximation.
The Functional Form of the Emulsion Calibration Curve
Authors: Woodyard Jack R. , Piper B. C. , Stever K. R.
Published: September 2005

The Federal Bureau of Mines has derived a mathematical expression for the emulsion calibration curve used in optical emission spectroscopy. Employing a two-step preliminary curve method, an approximation of the first derivative of the calibration curve is formed and integrated. The final equation is

[Formula: see text]

where I is the line intensity, S is the transform that linearizes the preliminary curve, and α and β are constants.
Effectiveness of Interference Filters for Reduction of Stray Light Effects in Atomic Emission Spectrometry
Authors: Fassel Velmer A. , Katzenberger Joseph M. , Winge Royce K.
Published: September 2005

Quantitative data are presented on the effectiveness of interference filters for reduction or elimination of stray light effects in optical spectrometers employed for trace atomic emission analyses. Specific attention is focused on those analyte species that contribute significant stray light at wavelengths far removed from the offending radiation. For simultaneous multielement determinations with a polychromator, band reflection filters are shown to provide an attractive means of eliminating stray light effects arising from the very intense Ca lines emitted in an inductively coupled plasma. For the spectrometers used in the present study, a major fraction of the background shifts caused by changing concentrations of Mg arose from real background contributions rather than from stray light.
Intensified Charge Coupled Device-Based Fiber-Optic Monitor for Rapid Remote Surface-Enhanced Raman Scattering Sensing
Authors: Alarie J. P. , Stokes D. L. , Sutherland W. S. , Edwards A. C. , Vo-Dinh T.
Published: September 2005

This paper describes the development of an intensified charge coupled device (ICCD)-based fiber-optic monitor for remote Raman and surface-enhanced Raman (SERS) sensing. Both Raman and SERS data were obtained with the use of a fiber-optic probe design incorporating 20-m optical fibers carrying the Raman signal. Spectra were obtained in 5 milliseconds for Raman and 9 ms for SERS. The proposed system could be used for a highly sensitive portable Raman system for rapid and remote chemical sensing.
Quantitative Analysis of Adsorbed Serum Albumin on Segmented Polyurethane Using FT-IR/ATR Spectroscopy
Authors: Jeon J. S. , Sperline R. P. , Raghavan S.
Published: September 2005

FT-IR attenuated total reflection (ATR) spectroscopy was applied to quantitatively determine the extent of bovine serum albumin adsorbed onto a biomedical-grade poly(ether)urethane film deposited on a ZnSe internal reflection element (IRE). The method of adsorption density determination was based on the optical principles for a stratified medium consisting of three layers. The spectral peak area due to bulk solution was less than 1% of total peak area. The measured adsorption density of albumin in a flowing system was 3.9 μg/cm2 at a solution concentration of 4.5 g/100 mL.
On the Use of Raman Spectroscopy in the Characterization of Iodine in Charge-Transfer Complexes
Authors: Deplano Paola , Devillanova Francesco A. , Ferraro John R. , Isaia Francesco , Lippolis Vito , Mercuri Maria Laura
Published: September 2005

FT-Raman spectra of some polyiodides and of a series of D · I2 charge-transfer complexes (where D is a molecule containing the thione or selone groups as donors), all characterized by x-ray diffraction, are reported. For the adducts with the thione compounds, which can be considered weak or medium-weak complexes, an empirical linear correlation between the frequency of the v(I-I) stretching vibrations and the d(I-I) bond distances has been found. Some polyiodides show FT-Raman spectra that are indistinguishable with respect to those displayed by the neutral complexes of weak or medium-weak strength; in such cases, the polyiodide can be regarded as a diiodine molecule, perturbed by an I n ( n = 1,3,…) donor. Polyiodides of this type show Raman absorptions falling in the linear correlation.