bluuebunny/crossref_metadata_2025 huggingface dataset:
Complexation of Uranium(VI) with Thiodiacetic Acid in Solution at 10–85 °C
Authors: Di Bernardo Plinio , Zanonato PierLuigi , Bismondo Arturo , Jiang Huijian , Garnov Alexander Yu. , Jiang Jun , Rao Linfeng
Published: September 2006

The protonation of thiodiacetate and its complexation with uranium(VI) in 1.05 mol kg–1 NaClO4 are studied at variable temperatures (10–85 °C). Three UVI complexes (UO2L, UO2HL+, and UO2HL2–, where L is thiodiacetate) are identified in this temperature range. The formation constants and the enthalpies of complexation are determined by potentiometry and calorimetry. The complexation of uranium(VI) with thiodiacetate becomes more endothermic at higher temperatures. However, the complexes become stronger due to increasingly more positive entropies of complexation at higher temperatures, which exceeds the increase in the unfavorable enthalpy of complexation. The values of the heat capacity of complexation (ΔCp°) are 122 ± 16, 302 ± 26, and 242 ± 23 J K–1 mol–1 for UO2L, UO2HL+, and UO2HL2–, respectively. The effect of temperature on the thermodynamics of the complexation is discussed in terms of the electrostatic model and the change in the solvent structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Size‐ and Shape‐Controlled Synthesis and Assembly of a Silver Nanocomplex in UV‐Irradiated TSA Solution
Authors: Yang Liangbao , Shen Yuhua , Xie Anjian , Liang Jianjun , Li Shikuo , Zhang Qingfeng
Published: September 2006

In this paper we describe the size‐controlled synthesis ofa silver nanocomplex based on the reduction of silvernitrate (AgNO3) by UV‐irradiated tungstosilicate acid [H4(SiW12O40), TSA] solution. This method allows the synthesis of ellipsoidal particles with an average size that is tunable between 2.4 and 84 nm by varying the molar ratio of silver nitrate to TSA, the pH of the reaction solution, and the reaction temperature. Silver nanorods can be formed from the ellipsoidal nanoparticles by controlling the aging time. The formation mechanism of these nanorods is also discussed. The nanoparticles are characterized by UV/Vis spectroscopy, FTIR spectroscopy, XRD analysis, XPS, electron diffraction (ED), TEM, and with a Zetasizer instrument. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Lead Halide Layers Linked by trans‐Cu(Gly)2 (Gly = –O2C–CH2–NH2) Pillars in Heterometallic Glycinate Based Organic–Inorganic Hybrids
Authors: Bi Wenhua , Mercier Nicolas , Louvain Nicolas , Latroche Michel
Published: September 2006

The novel hybrid compounds Pb2Cu(O2C–CH2–NH2)2X4 (X = Br, Cl) were prepared and characterized by single‐crystal X‐ray diffraction. TA analysis and DSC measurements show that the compounds are stable up to 200 °C. As in hybrid perovskites, their layered structures are based on metal(II) halide 2D frameworks, which are here covalently linked by trans‐Cu(Gly)2 flat SBUs. These rigid pillars are able to accommodate some of the void that exists in between the PbX2 layers. However, the results from hydrogen absorption experiments that were conducted at 77 K indicate that the hybrids are not good candidates for absorption materials. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
The Preparation and Absolute Configurations of Enantiomerically Pure C4‐Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives
Authors: Buckley Benjamin R. , Page Philip C. Bulman , Chan Yohan , Heaney Harry , Klaes Michael , McIldowie Matthew J. , McKee Vickie , Mattay Jochen , Mocerino Mauro , Moreno Eduardo , Skelton Brian W. , White Allan H.
Published: September 2006

The preparation of a series of diastereoisomeric tetracamphorsulfonates derived from racemic tetramethoxyresorcin[4]arenes was achieved by reactions with an excess of (S)‐(+)‐10‐camphorsulfonyl chloride in pyridine followed by isolation using flash chromatography. Tetradeprotonation of a number of tetramethoxyresorcin[4]arenes using n‐butyllithium in tetrahydrofuran, followed by reactions using (S)‐(+)‐10‐camphorsulfonyl chloride, gave the same tetracamphorsulfonates. Mono‐, di‐ and tricamphorsulfonates were also prepared following selective deprotonation. In the reactions with tetraisopropyloxy‐ and tetracyclopentyloxyresorcin[4]arenes, only the mono‐ and dicamphorsulfonates were formed. X‐ray crystallographic analysis established the absolute configurations of three diastereoisomerically pure tetracamphorsulfonates, including a diastereoisomer prepared from 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene. An additional pair of diastereoisomers was also prepared using (R)‐(–)‐10‐camphorsulfonyl chloride and 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene, for one of which the structure was confirmed by an additional X‐ray structure determination. Hydrolytic removal of the camphorsulfonyl residue(s) from the various diastereoisomers gave enantiomers of known absolute configurations. In some cases, the chiral nonracemic tetraalkoxyresorcin[4]arenes were converted into known tetrabenzoxazine derivatives by using N,N‐bis(methoxymethyl)[(S)‐(–)‐(α‐methylbenzyl)]amine in thermal or microwave‐assisted reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Implicit and explicit attitudes respond differently to increasing amounts of counterattitudinal information
Authors: Rydell Robert J. , McConnell Allen R. , Strain Laura M. , Claypool Heather M. , Hugenberg Kurt
Published: September 2006

This research examined the processes by which explicit and implicit attitudes changed to systematically differing levels of counterattitudinal (CA) information. Explicit attitudes changed quickly in response to relatively small amounts of CA information, reflecting rule‐based reasoning. On the other hand, implicit attitudes changed more slowly in the face of CA information, reflecting the progressive accretion of evaluation‐attitude object pairings. Thus, explicit attitudes were extremely malleable and changed quickly when CA information was presented, however, implicit attitudes revealed a slow, linear change trajectory resulting from the on‐going accrual of information about the attitude object. Implications for the processes underlying implicit and explicit attitudes are discussed. Copyright © 2006 John Wiley & Sons, Ltd.
Capillary electrophoresis with a UV light‐emitting diode source for chemical monitoring of native and derivatized fluorescent compounds
Authors: Hapuarachchi Suminda , Janaway Gordon A. , Aspinwall Craig A.
Published: September 2006

We report the utilization of a high power UV light‐emitting diode for fluorescence detection (UV‐LED‐IF) in CE separations. CE‐UV‐LED‐IF allows analysis of a range of environmentally and biologically important compounds, including PAHs and biogenic amines, including neurotransmitters, amino acids, proteins, and peptides, that have been derivatized with UV‐excited fluorogenic labels, e.g., o‐phthalic dicarboxaldehyde/β‐mercaptoethanol (OPA/β‐ME). The 365 nm UV‐LED was used as a stable, low cost source for detection of UV‐excited fluorescent compounds. UV‐LED‐IF was used with both zonal CE separations and MEKC. Native fluorescence detection of PAHs was accomplished with detection limits ranging from 10 nM to 1.3 µM. Detection limits for OPA/β‐ME‐labeled glutamic acid and aspartic acid were 11 and 10 nM, respectively, for off‐line labeling, and 47 and 47 nM, respectively, for on‐line labeling, comparable to UV‐laser‐based systems. Analysis of OPA/β‐ME‐labeled proteins and peptides was performed with 28 and 47 nM detection limits for BSA and myoglobin, respectively.
Modeling annual rainfall: a robust maximum likelihood approach
Authors: Haddad John N. , Nimah Musa N. , Farajallah Nadim
Published: September 2006

Let { Xt} be a zero mean, Gaussian, autoregressive process of order one with parameter α. For a realization (X1,X2,…,Xn)′ of { Xt}, we consider the transformation Yt = Xt/Xt−1, for t = 2,…, n. Then the likelihood function of (Y2,…, Yn) can be derived and is shown to be independent of the parameter σ2. Now, maximum likelihood estimator for α is derived and interval estimates are then computed and used to determine the influence of each data point. Finally, a direct application to precipitation data will be given for illustration. Copyright © 2006 John Wiley & Sons, Ltd.
Maintaining the power balance in an ‘empty network’
Authors: Reza M. , Dominguez A. O. , Schavemaker P. H. , Kling W. L.
Published: September 2006

This paper presents the concept of an ‘empty network’ and shows how the power balance can be maintained in such a system. In this study, an ‘empty network’ is defined as a power system in which no rotating mass is present; all generators are grid‐connected via power electronic interfaces. One generator creates a neat 50 Hz voltage that serves as a frequency reference for the other generators. Consequently, a power unbalance cannot be detected in the classical way, as an altered system frequency. Therefore, in this paper, voltage deviations are used to detect the power unbalances. Simple test systems that consist of 1, 2 and 3 buses are applied on a real time digital simulator (RTDS). A load jump is simulated to cause a power unbalance in the system. The study shows that by using voltage deviations as control signals, the power balance can be maintained in an empty network. Copyright © 2006 John Wiley & Sons, Ltd.
Solving viscoelastic free surface flows of a second‐order fluid using a marker‐and‐cell approach
Authors: Tomé M. F. , Doricio J. L. , Castelo A. , Cuminato J. A. , McKee S.
Published: September 2006

This work is concerned with the numerical simulation of two‐dimensional viscoelastic free surface flows of a second‐order fluid. The governing equations are solved by a finite difference technique based on the marker‐and‐cell philosophy. A staggered grid is employed and marker particles are used to represent the fluid free surface. Full details for the approximation of the free surface stress conditions are given. The resultant code is validated and convergence is demonstrated. Numerical simulations of the extrudate swell and flow through a planar 4:1 contraction for various values of the Deborah number are presented. Copyright © 2006 John Wiley & Sons, Ltd.
A higher‐order Boussinesq‐type model with moving bottom boundary: applications to submarine landslide tsunami waves
Authors: Ataie‐Ashtiani B. , Najafi Jilani A.
Published: September 2006

A two‐dimensional depth‐integrated numerical model is developed using a fourth‐order Boussinesq approximation for an arbitrary time‐variable bottom boundary and is applied for submarine‐landslide‐generated waves. The mathematical formulation of model is an extension of (4,4) Padé approximant for moving bottom boundary. The mathematical formulations are derived based on a higher‐order perturbation analysis using the expanded form of velocity components. A sixth‐order multi‐step finite difference method is applied for spatial discretization and a sixth‐order Runge–Kutta method is applied for temporal discretization of the higher‐order depth‐integrated governing equations and boundary conditions. The present model is validated using available three‐dimensional experimental data and a good agreement is obtained. Moreover, the present higher‐order model is compared with fully potential three‐dimensional models as well as Boussinesq‐type multi‐layer models in several cases and the differences are discussed. The high accuracy of the present numerical model in considering the nonlinearity effects and frequency dispersion of waves is proven particularly for waves generated in intermediate and deeper water area. Copyright © 2006 John Wiley & Sons, Ltd.
Comparing analytical and numerical solution of nonlinear two and three‐dimensional hydrostatic flows
Authors: Casulli Vincenzo , Zanolli Paola
Published: September 2006

New test cases for frictionless, three‐dimensional hydrostatic flows have been derived from some known analytical solutions of the two‐dimensional shallow water equations. The flow domain is a paraboloid of revolution and the flow is determined by the initial conditions, the nonlinear advective terms, the Coriolis acceleration and by the hydrostatic pressure. Wetting and drying is also included.

Some specific properties of the exact solutions are discussed under different hypothesis and relative importance of the forcing terms. These solutions are proposed for testing the stability, the accuracy and the efficiency of numerical models to be used for simulating environmental hydrostatic flows.

The computed solutions obtained with a semi‐implicit finite difference—finite volume algorithm on unstructured grid are compared with the corresponding analytical solutions in both two and three space dimension. Excellent agreement are obtained for the velocity and for the resulting water surface elevation. Comparison of the computed inundation area also shows a good agreement with the analytical solution with degrading accuracy observed when the inundation area becomes relatively large and for long simulation time. Copyright © 2006 John Wiley & Sons, Ltd.
The relative stress scale, a useful instrument to identify various aspects of carer burden in dementia?
Authors: Ulstein Ingun , Bruun Wyller Torgeir , Engedal Knut
Published: September 2006

Objective

To identify carer and patient characteristics associated with various aspects of burden of care.

Method

The burden on 196 carers, each caring for one patient with dementia, was rated by means of the Relative Stress Scale (RSS). Patients were assessed with the Mini Mental State Examination (MMSE), the Disability Assessment for Dementia (DAD) and the Neuropsychiatric Inventory (NPI).

Results

Factor analysis of the RSS resulted in three subgroups: ‘emotional distress’, ‘social distress’ and ‘negative feelings’. The total NPI score contributed to the explanation of the RSS total score and the three RSS subgroup scores with an explanatory power of 37% for total RSS, 34% for emotional distress, 27% for social distress and 20% for negative feelings. In multiple regression analysis, total NPI, DAD%, the carer being a wife and the hours spent caring per week, contributed to the explanation of total RSS with an explanatory power of 48%. Total NPI, the carer being a female and the hours spent caring, explained 38% of the variance in ‘emotional distress’. Total NPI, the DAD%‐score, contact with the patient on a daily basis and the hours spent caring, explained ‘social distress’ (49%). ‘Negative feelings’ were associated with total NPI, younger patients and the carer being a wife (27%).

Conclusions

The RSS offers an opportunity to differentiate between different patterns of distress. This facilitates the creation of tailored intervention to reduce the strain of caring. Copyright © 2006 John Wiley & Sons, Ltd.
Old age mental health services in England: implementing the National Service Framework for Older People
Authors: Tucker Sue , Baldwin Robert , Hughes Jane , Benbow Susan , Barker Andrew , Burns Alistair , Challis David
Published: September 2006

Background

There is much variation in the services provided for older people with mental health problems. In England, the National Service Framework for Older People (NSFOP) sought to address these inconsistencies and improve care. This study describes the situation three years after its publication.

Methods

A postal survey of old age psychiatrists collected data on the NSFOP mental health model: the range of specialist mental health provision, the nature of the specialist:generic service interface and the degree of interdisciplinary/interagency working.

Results

Three hundred and eighteen (72%) consultants responded. Considerable differences existed in the deployment of key professionals within community teams, with more than a third lacking ring‐fenced social work time. Few services had dedicated rehabilitation beds and nearly a third lacked separate facilities for people with organic and functional illnesses. Increasing numbers of consultants had access to a memory clinic and there was some suggestion that liaison services were developing, but little indication of increased support for care homes. Several services had yet to agree protocols with primary care, or to implement measures promoting effective information‐sharing and integrated care, and there was little evidence that the introduction of the Single Assessment Process (SAP) had significantly changed practice. Although just over half of consultants reported that mental health services were improving, less than a quarter considered community provision adequate.

Conclusions

Three years after the publication of the NSFOP there remained significant gaps in services for older people with mental health problems and substantial variation in provision between districts. Copyright © 2006 John Wiley & Sons, Ltd.
Synthesis, structure, and transition metal complexes of amphiphilic 1,5‐diaza‐3,7‐diphosphacyclooctanes
Authors: Karasik Andrey A. , Naumov Roman N. , Balueva Anna S. , Spiridonova Yulia S. , Golodkov Oleg N. , Novikova Helen V. , Belov Gennadii P. , Katsyuba Sergey A. , Vandyukova Elena E. , Lönnecke Peter , Hey‐Hawkins Evamarie , Sinyashin Oleg G.
Published: September 2006

Amphiphilic 1,5‐diaza‐3,7‐diphosphacyclooctanes have been synthesized by condensation of hydrophobic primary arylphosphines, formaldehyde, and functionalized hydrophilic primary arylamines (5‐aminoisophthalic acid and the sodium salt of sulfanilic acid). These compounds readily form P,P‐chelate complexes with [PtCl2(cod)], which are stable in water. The catalytic activity of palladium catalysts with 1,5‐diaza‐3,7‐diphosphacyclooctane ligands was studied in the copolymerization of ethylene and carbon monoxide. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:499–513, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20272
Monosodiumoxyorganoalkoxysilanes: Synthesis and properties
Authors: Rebrov E. A. , Muzafarov A. M.
Published: September 2006

The reaction of organoalkoxysilanes with sodium hydroxide was studied in detail. Studies indicate that this reaction involves more than one stage and involves rather complex multistep process, which leads to the formation of both monosodiumoxyorganoalkoxysilanes (MSOAS) and several secondary products. Analysis of experimental evidence makes it possible to advance the mechanism behind this phenomenon and to define the optimum conditions for the preparation of pure MSOAS with high yields. Different MSOAS were synthesized and their basic physicochemical properties were studied. MSOAS are shown to constitute multifunctional reagents with chemically independent functional groups, and their reaction with trimethylchlorosilane selectively proceeds via ONa groups, whereas their interaction with triethylesilanol and higher alcohols proceeds exclusively via OAlk groups. Exchange interaction between MSOAS and organoalkoxysilanes via ONa and OAlk groups was found and studied in detail. Temperature corresponding to the onset of thermal degradation of MSOAS was estimated to be equal to ∼180–190°C. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:514–541, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20280
Outcome of craniofacial resection in patients 70 years of age and older
Authors: Ganly Ian , Gross Neil D. , Patel Snehal G. , Bilsky Mark H. , Shah Jatin P. , Kraus Dennis H.
Published: September 2006

Background

Craniofacial resection (CFR) for patients over 70 years of age is uncommon. This study examines a cohort of 36 patients who had CFR at a single institution with the aim of reporting mortality, complications, and outcome.

Methods

Thirty‐six patients 70 years of age and older were identified from a prospective database of 234 patients who had CFR at a single institution. The median age was 72 years (range, 70–87). Seventeen (47%) patients had had prior single‐modality or combined treatment, which included surgery in 14 (40%), radiation in 13 (36%), and chemotherapy in 2 (6%). Thirty‐five patients had a malignant tumor and 1 patient a benign tumor; 15 (42%) had high‐grade, 17 (47%) intermediate‐grade, and 4 (11%) low‐grade pathology. The margins of resection were close or microscopically positive in 18 (50%). Adjuvant radiotherapy was given in 15 (42%) and chemotherapy in 1 (3%). Complications were classified into overall, local, central nervous system (CNS), systemic, and orbital. Overall survival (OS) and disease‐specific survival (DSS) were determined using the Kaplan–Meier method. Outcomes were compared with patients less than 70 years of age.

Results

Postoperative mortality occurred in 6 (17%) patients and postoperative complications occurred in 23 (64%) patients. Local wound complications occurred in 11 (30%), CNS in 12 (33%), systemic in 6 (17%), and orbital in 1 (3%). Postoperative mortality and complications were significantly higher in patients 70 years of age and older compared with patients less than 70 years of age (17% versus 1.5%, p = .0005; 64% versus 36%, p = .003, respectively). With a median follow‐up of 27 months (range, 1–237), the 3 year OS and DSS were significantly poorer than patients less than 70 years of age (OS: 53% versus 69%, p = .0004; DSS: 61% versus 70%, p = .01) due to increased medical comorbidity (53% versus 24%, p = .001) and poorer histology (high‐, intermediate‐, low‐grade histology: 42%, 47%, 11% versus 26%, 47%, 27%, p = .05, respectively) in patients over 70 years of age.

Conclusion

CFR in patients 70 years of age and older is associated with increased mortality, increased incidence of complications, and a poorer overall and disease‐specific 3‐year survival, compared with patients less than 70 years of age. The survival was likely due to increased medical comorbidity and adverse histology. These factors must be taken into account when considering an elderly patient for craniofacial resection. © 2006 Wiley Periodicals, Inc. Head Neck, 2006
Downregulation of the KIP family members p27KIP1 and p57KIP2 by SKP2 and the role of methylation in p57KIP2 inactivation in nonsmall cell lung cancer
Authors: Pateras Ioannis S. , Apostolopoulou Kalliopi , Koutsami Marilena , Evangelou Kostas , Tsantoulis Petros , Liloglou Triantafillos , Nikolaidis Giorgos , Sigala Fragiska , Kittas Christos , Field John K. , Kotsinas Athanassios , Gorgoulis Vassilis G.
Published: September 2006

Knowing the status of molecules involved in cell cycle control in cancer is vital for therapeutic approaches aiming at their restoration. The p27KIP1 and p57KIP2 cyclin‐dependent kinase inhibitors are nodal factors controlling normal cell cycle. Their expression in normal lung raises the question whether they have a mutual exclusive or redundant role in nonsmall cell lung cancer (NSCLC). A comparative comprehensive analysis was performed in a series of 70 NSCLCs. The majority of cases showed significantly reduced expression of both members compared to normal counterparts. Low KIP protein levels correlated with increased proliferation, which seems to be histological subtype preponderant. At mechanistic level, degradation by SKP2 was demonstrated, in vivo and in vitro, by siRNA‐methodology, to be the most important downregulating mechanism of both KIPs in NSCLC. Decreased p57KIP2‐transcription complements the above procedure in lowering p57KIP2‐protein levels. Methylation was the main cause of decreased p57KIP2‐mRNA levels. Allelic loss and imprinting from LIT1 mRNA contribute also to decreased p57KIP2 transcription. In vitro recapitulation of the in vivo findings, in A549 lung cells (INK4A‐B(−/−)), suggested that inhibition of the SKP2‐degradation mechanism restores p27KIP1 and p57KIP2 expression. Double siRNA treatments demonstrated that each KIP is independently capable of restraining cell growth. An additional demethylation step is required for complete reconstitution of p57KIP2 expression in NSCLC. © 2006 Wiley‐Liss, Inc.
A simple combined floating and anchored collagen gel for enhancing mechanical strength of culture system
Authors: Harada Ichiro , Kim Sung‐Gon , Cho Chong Su , Kurosawa Hisashi , Akaike Toshihiro
Published: September 2006

In this study, a simple combined method consisting of floating and anchored collagen gel in a ligament or tendon equivalent culture system was used to produce the oriented fibrils in fibroblast‐populated collagen matrices (FPCMs) during the remodeling and contraction of the collagen gel. Orientation of the collagen fibrils along single axis occurred over the whole area of the floating section and most of the fibroblasts were elongated and aligned along the oriented collagen fibrils, whereas no significant orientation of fibrils was observed in normally contracted FPCMs by the floating method. Higher elasticity and enhanced mechanical strength were obtained using our simple method compared with normally contracted floating FPCMs. The Young's modulus and the breaking point of the FPCMs were dependent on the initial cell densities. This simple method will be applied as a convenient bioreactor to study cellular processes of the fibroblasts in the tissues with highly oriented fibrils such as ligaments or tendons. © 2006 Wiley Periodicals, Inc. J Biomed Mater Res, 2007
Coupled atomic charge selectivity for optimal ligand‐charge distributions at protein binding sites
Authors: Bhat Sathesh , Sulea Traian , Purisima Enrico O.
Published: September 2006

Charge optimization as a tool for both analyzing and enhancing binding electrostatics has become an attractive approach over the past few years. An interesting feature of this method for molecular design is that it provides not only the optimal charge magnitudes, but also the selectivity of a particular atomic center for its optimal charge. The current approach to compute the charge selectivity at a given atomic center of a ligand in a particular binding process is based on the binding‐energy cost incurred upon the perturbation of the optimal charge distribution by a unit charge at the given atomic center, while keeping the other atomic partial charges at their optimal values. A limitation of this method is that it does not take into account the possible concerted changes in the other atomic charges that may incur a lower energetic cost than perturbing a single charge. Here, we describe a novel approach for characterizing charge selectivity in a concerted manner, taking into account the coupling between the ligand charge centers in the binding process. We apply this novel charge selectivity measure to the celecoxib molecule, a nonsteroidal anti‐inflammatory agent binding to cyclooxygenase 2 (COX2), which has been recently shown to also exhibit cross‐reactivity toward carbonic anhydrase II (CAII), to which it binds with nanomolar affinity. The uncoupled and coupled charge selectivity profiles over the atomic centers of the celecoxib ligand, binding independently to COX2 and CAII, are analyzed comparatively and rationalized with respect to available experimental data. Very different charge selectivity profiles are obtained for the uncoupled versus coupled selectivity calculations. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006
Ab initio studies on isomers of macropolyhedral borane ions [B20H18]n (n = 0, –2, –4)
Authors: Zhang Jian , Zhang Mingyu , Zhao Yuanyuan , Chen Baoguo , Sun Chia‐Chung
Published: September 2006

Various isomers of macropolyhedral borane ions [B20H18]n (n = 0, −2, −4) are investigated by using the density functional theory methods at RB3LYP/6‐31+G* and RB3LYP/6‐31G* levels to obtain the optimized geometries, harmonic vibrational frequencies, electron structures, and the stability order. The calculated results show that optimized bond lengths are consistent with the available experimental values and the natural populations, taking [a2‐B20H18]4− (4) as an example, are also in agreement with NMR spectra. The calculated vibrational frequencies are all real, so all of these isomers could be stable, among which [a2‐B20H18]2− (3) and [a2‐B20H18]0 (7) are considered for the first time in this paper. On the basis of the contour maps of molecular orbitals, the delocalized characteristic of molecular orbitals and the possible redox mechanism of these ions are also discussed. Moreover, the analysis on counting of skeletal bonding electrons shows that the isomers (1)–(6) obey the electronic requirement predicted by the mno rule, whereas the newly predicted isomer (7) does not match the mno rule. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006
Finance and development: why should causation matter?
Authors: Lawrence Peter
Published: September 2006

The discussion on the relationship between financial development and growth has swung from an initial consensus that financial development follows, or is at least inter‐related with growth, to an almost consensual belief that sustained growth follows from financial development. This paper argues that the relationship is too complex to allow for such generalised assertions. Further, the evidence brought out in contemporary and historical research to support the new consensus is flawed. New research directions need to establish which financial policies work, especially at the micro‐level, and when, and to re‐focus on the issue of the role finance can play in supporting productive investment. Copyright © 2006 John Wiley & Sons, Ltd.
Accurate‐mass identification of chlorinated and brominated products of 4‐nonylphenol, nonylphenol dimers, and other endocrine disrupters
Authors: Thurman E. Michael
Published: September 2006

LC/ToF‐MS was used to identify new chlorination and bromination products of 4‐nonylphenol (4‐NP), such as 4‐NPBr2, 4‐NPBrCl, 4‐NP dimer (2 isomers), 4‐NPCl dimer (2 isomers), 4‐NPBr dimer, and a series of methoxy bromo and chloro 4‐NPs from a laboratory study of nonylphenol chlorination. The identification procedure used the exact mass, exact mass of the isotope cluster, and their relative intensities, at an average mass accuracy of ∼1 ppm. The products were produced by a simulated study of industrial cleaning procedures where 4‐NP, nonylphenol ethoxylate (NPEO‐1 and 2), and nonylphenol carboxylate (NPEC‐1) were in contact with sodium hypochlorite solutions (with and without bromide) of various strengths (possible environmental scenarios) at neutral pH. The formation of the products was measured as a function of chlorine concentration, and it was found that 4‐NP was the most reactive, producing 4‐NPCl, 4‐NPCl2, 4‐NP (dimers), and the 4‐NPCl (dimers). In the presence of bromide ions, a mixture results with products of 4‐NPBr2, 4‐NPCl, 4‐NPCl2, 4‐NPBrCl, 4‐NPBr, and a 4‐NPBr dimer. Less reactive to halogenation was NPEO, which formed only the monochloro and monobromo products, and the least reactive was NPEC. A simple stereochemical model is used to explain halogenation reactivity for the family of 4‐NPs and NPEOs at neutral pH. The presence of halogenated 4‐NP dimers (bromo and chloro diphenyl ethers) is discussed as a possible source of new endocrine disrupters. Copyright © 2006 John Wiley & Sons, Ltd.
Prehistoric Anasazi ceramics studied by micro‐Raman spectroscopy
Authors: Striova Jana , Lofrumento Cristiana , Zoppi Angela , Castellucci Emilio Mario
Published: September 2006

In this project, micro‐Raman (µ‐Raman) spectroscopy has been used as a means to investigate the pigments employed in decoration of Anasazi pottery. Analysis of Raman spectra revealed the presence of organic‐ (amorphous carbon), iron‐ and/or manganese‐based pigments in line with the known pictorial materials used by Anasazi people. The results were also complemented by studies employing a scanning electron microscope equipped with a microanalysis energy dispersive X‐ray detection (SEM/EDX) system, which proved helpful mainly while identifying the manganese‐based minerals (i.e. pyrolusite). Knowledge of the pigments augments our understanding of the materials favored by the different production centers and of the artistic skills of ceramic producers. Copyright © 2006 John Wiley & Sons, Ltd.
Optimum acquisition of Raman spectra in pigment analysis with IR laser diode and pulsed UV irradiation
Authors: López‐Gil Alejandro , Ruiz‐Moreno Sergio , Miralles Judith
Published: September 2006

Fluorescence, due to the binding media, is the main problem that one encounters in the molecular analysis of artistic pigments using Raman spectroscopy. With the object of minimizing this problem, we propose the use of a semiconductor IR laser in Raman spectral acquisition and the application of local irradiation with a pulsed UV laser on the analysis zone. The Raman analysis with an IR source shows advantages compared to that with visible lasers, such as the reduction of fluorescence and its shot noise, although a price has to be paid in the form of the small intensity of the obtained spectra with the same acquisition time. Also, in this paper we demonstrate that controlled levels of pulsed UV radiation over the analyzed painting (pigment + binding media) can improve even more the Raman spectral quality obtained with the IR laser, which leads us to conclude that the local use of a pulsed UV laser, prior to Raman analysis with the IR source, can bring optimum quality results in pigment identification. The spectral quality of these experimental results for different pigments has been measured by calculating in each case the signal‐to‐noise ratio (SNR) of the corresponding spectra. From a quantitative point of view, in some practical cases (chromium yellow and ultramarine blue) an SNR improvement of 16 dB is achieved when pulsed UV irradiation and IR laser Raman analysis are used instead of a simple Raman analysis with a visible laser. Copyright © 2006 John Wiley & Sons, Ltd.
Experimental confirmation by Raman spectroscopy of a PbSnSb triple oxide yellow pigment in sixteenth‐century Italian pottery
Authors: Sandalinas C. , Ruiz‐Moreno S. , López‐Gil A. , Miralles J.
Published: September 2006

The sixteenth and seventeenth‐century Venetian manuscripts on glassmaking contain a number of recipes on yellow pigment production, later named ‘anime’, based on PbSn and/or PbSb oxides. Since antiquity, these oxides have been employed intermittently as opacifying and colouring agents to obtain coloured glasses, enamels and pigments.

In 1998, different laboratories provided evidence of the existence of a ‘non‐standardized’ yellow pigment (PbSnSb triple oxide) very close in composition and structure to both the PbSn type II (silicoestannate) and PbSb (antimonate) oxides. This PbSnSb yellow pigment was identified by SEM‐EDX in seventeenth‐century Italian paintings.

In previous studies, the authors of the present work have investigated with Raman spectroscopy the presence of PbSnSb oxide (pyrochlore structure) in some Italian paintings of the seventeenth century, using as standard a synthesized pyrochloric triple oxide (Pb2SnSbO6.5).

In this paper, we provide evidence for the first molecular identification with Raman spectroscopy of said pigment in Italian pottery from the sixteenth century. We have identified this pigment in two pieces of decorated pottery: a ‘plate’ manufactured in Casteldurante and attributed to Andrea Negroponte style (c 1550), and a Venetian ‘albarello’ (pharmacy jar) attributed to Domenego (c 1570–1580). We have synthesized the reference compound in accordance with the theoretical formula of the pyrochloric triple oxide (Pb2SnSbO6.5). The Raman spectra obtained with this material provided molecular information identical to the yellow pigment measured in the two Italian ceramics. To conclude, the experimental results presented here indicate one simple fact: Pb–Sn–Sb triple oxide yellow pigment has been used during the sixteenth and seventeenth centuries without distinction both in Italian ceramics and paintings. Copyright © 2006 John Wiley & Sons, Ltd.
Raman spectroscopy investigations of the weathering alteration of a predazzite marble mouflon of the Indus Valley Culture
Authors: Twilley John
Published: September 2006

A recumbent ram carved in the style of Mohenjo Daro was examined by a variety of scientific methods in order to clarify questions regarding its condition and the possible recarving of certain details. Testing consisted of microstructural and compositional analysis of the stone and mineral accretions found on it utilizing the complementary methods of Raman spectroscopy, scanning electron microscopy/X‐ray spectrometry, Fourier‐transform infrared spectroscopy and optical petrography. The case demonstrates both the strengths and weaknesses of Raman spectroscopy, and argues for the need for an integrated analytical approach. Significant deviations from the nominal Raman emission wavenumbers were found for both the primary minerals and their weathering products. Consistent differences in Raman spectra between primary and secondary forms of calcite allowed their differentiation in the weathering zone. Exceptionally clear phases led to occasional difficulties in the analysis of petrographic sections due to the excitation of Raman emission from grains below, or adjacent to, the grain of interest. The ram, previously misidentified as a sandstone, was found to have been carved from a marble‐like stone of mixed mineral composition known as predazzite. Despite a deceptively simple appearance, the ram possesses abundant evidence of natural alteration of the carved surface. This alteration takes several forms, including transformation of brucite into hydromagnesite by hydration and carbonation; the loss, by dissolution, of hydromagnesite from the subsurface with resulting void formation; the replacement of subsurface hydromagnesite by void‐filling aragonite or calcite; and the formation of calcite incrustations atop parts of the stone surface. Surface pores produced by weathering create the appearance of sandstone or porous limestone, rock types that are quite different from the much rarer predazzite. The identification of similar artworks as sandstone or limestone should be viewed with skepticism, as published identifications are often not the result of actual mineralogical study. New avenues of archaeometric research, including the determination of the geological source of the stone, should be possible for sculptures of this type on the basis of the fact that predazzites are relatively rare and limited in geological extent. If multiple quarry sites exist in the Indus Valley region, they should be amenable to differentiation by techniques that have proven successful for marbles of the Mediterranean, such as electron paramagnetic resonance spectroscopy, grain size analysis, and carbonate stable isotope analysis. Copyright © 2006 John Wiley & Sons, Ltd.
Raman microscopic investigation of paint samples from the Rosalila building, Copan, Honduras
Authors: Goodall Rosemary A. , Hall Jay , Viel Rene , Ricardo Agurcia F. , Edwards Howell G. M. , Fredericks Peter M.
Published: September 2006

Micro‐Raman spectroscopy was applied to the study of multiple layered wall paints from the Rosalila temple, Copan, Honduras, which dates to the Middle Classic period (A.D. 520 to 655). Samples of red, green and grey paint and a thick white overcoating were analysed. The paint pigments have been identified as hematite, celadonite or green earth and a combined carbon/mica mixture. By combining Raman spectroscopy with micro‐ATR infrared spectroscopy and environmental scanning electron microscopy (ESEM), a detailed study has been made of the materials and processes used to make the stucco and paints. The use of green earth as a green pigment on Maya buildings has not been reported before. The combination of carbon and muscovite mica to create a reflective paint is also a novel finding. Copyright © 2006 John Wiley & Sons, Ltd.
On the Raman spectrum of Maya blue
Authors: Sánchez del Río Manuel , Picquart Michel , Haro‐Poniatowski Emmanuel , van Elslande Elsa , Hugo Uc Victor
Published: September 2006

Maya blue is a marvelous pigment with extraordinary properties. It was invented by the Maya around VII–VIII century and used by many Mesoamerican peoples in prehispanic times. It is made by encapsulating natural indigo into an inorganic clay matrix of palygorskite. The palygorskite–indigo mixture becomes acid‐resistant when a moderate thermal treatment is applied. The chemical reasons of the unusual stability of the pigment and the exact mechanism of interaction between the indigo and the clay are not well understood. We present a Raman study of different preparations of Maya blue and other mixtures of indigo with other inorganic materials. We found that the unheated mixture of indigo with palygorskite presents the same Raman spectrum as Maya blue, indicating that the differences with respect to the indigo spectrum are not due to the interaction produced during the thermal treatment, which makes the mixture acid‐resistant. Moreover, indigo mixed with other clays, like sepiolite or montmorillonite, presents a Raman spectrum very similar to that of Maya blue. Some chemical mechanisms that could explain these spectra, and the suitability of Raman spectroscopy for identifying Maya blue are discussed. Copyright © 2006 John Wiley & Sons, Ltd.
Non‐destructive micro‐Raman and X‐ray fluorescence spectroscopy on pre‐Eyckian works of art—verification with the results obtained by destructive methods
Authors: Fremout Wim , Saverwyns Steven , Peters Famke , Deneffe Dominique
Published: September 2006

The applicability of non‐destructive techniques such as micro‐X‐ray fluorescence spectroscopy, which reveals atomic composition, and fibre‐coupled micro‐Raman spectroscopy, which reveals molecular information, is explored on three pre‐Eyckian works of art: a small shrine of Saint Ursula, two small panels depicting the Saints Arnulf, Godeleva, Livinus and Margaret and the relic holder with fragment of the veil of the Holy Virgin. The results are consistent with those obtained by destructive means—optical microscopy (OM), SEM‐EDX and micro‐Raman spectroscopy on embedded stratigraphic samples. In the case of multilayered paint, however, the results of the non‐destructive techniques are difficult to interpret and much information about the original layers is lost. In those cases, non‐destructive methods need to be supplemented by a limited number of stratigraphic samples, while the former—when well considered—limit the number of samples needed for a broad study. Copyright © 2006 John Wiley & Sons, Ltd.
Raman spectroscopy in art and archaeology
Authors: Bellot‐Gurlet Ludovic , Pagès‐Camagna Sandrine , Coupry Claude
Published: September 2006

This paper gives a short overview of the Special Issue on Raman Spectroscopy in Art and Archaeology, with the papers collected after the ‘3rd International Conference on the Application of Raman Spectroscopy in Art and Archaeology’ held at the University Pierre et Marie Curie‐Paris 6, Paris, France, from 31 August to 3 September, 2005. The contributions present an extended view of the work in the field, from technical developments and special analytical procedures to various applications. Copyright © 2006 John Wiley & Sons, Ltd.
Leaching of aluminium from utensils during cooking of food
Authors: Semwal Anil D , Padmashree A , Khan Mohammed A , Sharma Gopal K , Bawa Amrinder S
Published: September 2006

The use of aluminium utensils for cooking provides an important route for aluminium metal to enter foods. Leaching of aluminium from utensils made of aluminium, indalium (alloy of aluminium), stainless steel and hard anodised aluminium was studied under different conditions of pH and boiling time. Low pH was found to enhance leaching of aluminium from the utensils. The leaching was found to be the highest during first‐time preparation (new utensils) of all the foods as compared with second‐and third‐time preparations using the same utensils. Leaching of aluminium during the preparation of various traditional Indian foods was found to be negligible in hard anodised aluminium utensils, indicating the advantage of using such vessels for food preparation over simple aluminium and indalium utensils. Cereals contribute a smaller amount of aluminium to the total daily intake than legumes. Copyright © 2006 Society of Chemical Industry
Drying temperature, endogenous antioxidants and capsaicinoids affect carotenoid stability in paprika (red pepper spice)
Authors: Daood Hussein G , Kapitány József , Biacs Péter , Albrecht Katalin
Published: September 2006

The major carotenoids and carotenoid esters in Capsicum annuum L. during thermal dehydration of pepper and storage of the ground product (paprika) were examined with special focus on the role of endogenous antioxidants such as vitamins E and C and capsaicinoids, the pungent materials in hot spice red pepper. A high‐performance liquid chromatographic (HPLC) method was developed to achieve excellent separation and accurate detection of different carotenoid classes including free xanthophylls, monoesters, carotenes and di‐esters. The newly developed method included gradient elution on a reversed‐phase column with increasing proportions of isopropanol. The results indicated that presence of capsaicinoids in pungent pepper had a favourable effect on the stability of carotenoids during thermal drying. Among various di‐esters those of lutein and zeaxanthine, as well as the mono‐ester of β‐cryptoxanthin were more stable than those of capsorubin and capsanthin, pointing to the possible role of epoxide and carbonyl groups in the susceptibility of carotenoids. An Arrhenius plot for degradation of carotenoids, tocopherols and ascorbic acid as a function of drying temperature showed linear relationships for all components, with ascorbic acid being the most sensitive. During storage in a refrigerator for 3 months the paprika showed high degradation of all the examined carotenoids particularly in samples prepared from pods dried at high temperatures (90 and 100 °C). An exception was for β‐cryptoxanthin mono‐ester and violaxanthin di‐esters in a non‐pungent variety. The amounts of these carotenoids lost during storage were slightly affected by the change in drying temperature. Strong correlation was found between retention of colour in stored paprika and the initial content of ascorbic acid, but not with that of tocopherols or capsaicinoids. Copyright © 2006 Society of Chemical Industry
Effect of cold‐shock treatment on chilling injury in mango (Mangifera indica L. cv. ‘Wacheng’) fruit
Authors: Zhao Zhilei , Jiang Weibo , Cao Jiankang , Zhao Yumei , Gu Yuhong
Published: September 2006

To investigate how cold shock may affect chilling injury in mango fruit (Mangifera indica L. cv. ‘Wacheng’), the fruit were treated for 3, 4 or 5 h at 0 °C, or treated for 8, 10 or 12 h at 4 °C, respectively, then transferred to 20 °C for 20 h prior to being stored at 2 °C, 85–95% RH. The chilling injury index of mango treated at 0 °C for 4 h was 59.7% lower than that of the control fruit directly stored at 2 °C, 85–95% RH. Some attributes were assayed in the fruit treated at 0 °C for 4 h. Ion leakage of the cold‐shock fruit at 0 °C for 4 h was 16% or 10% lower than that of the control on day 9 or day 12 of storage, respectively. Malondialdehyde content of the cold‐shocked fruit was 70% or 50% lower than that of the control on day 6 or day 12 of storage at 2 °C, respectively. Activities of catalase, ascorbate peroxidase, and contents of glutathione and phenolic compounds in the fruit during storage were all markedly enhanced by the cold‐shock treatment, whereas activities of superoxide dismutase, glutathione reductase and content of ascorbic acid in the mango were slightly influenced by the cold‐shock treatment. These results suggest that cold‐shock treatment may hold promise as an alternative approach to reduce chilling injury in mango fruit during cold storage. Copyright © 2006 Society of Chemical Industry