bluuebunny/crossref_metadata_2025 huggingface dataset:
Repetitive behaviors in CHARGE syndrome: Differential diagnosis and treatment options
Authors: Bernstein Veronika , Denno Laurie S.
Published: February 2005

Twenty‐nine students with CHARGE syndrome were evaluated using the Compulsive Behavior Checklist (CBC). Most of the students obtained a high score for repetitive behaviors, averaging 11.5 repetitive behaviors per student. Most students' repetitive behaviors significantly interfered with their daily routine. Thirty‐four percent of the students responded to redirection with aggression toward themselves or others. Many of these behaviors do not respond well to traditional behavioral techniques. Through observation, definitions, and using functional analysis of behavior, repetitive behaviors were assigned to one of four categories. Each category has different treatment options. A case study of an adolescent girl with CHARGE syndrome who has profound deafness, colobomas, and moderate cognitive delay is presented. She displayed severe behavior challenges and significant medical issues. The course of treatment is outlined over 5 years. Behavior management, medical management, and psychiatric management were used in regulating her behavior, medical issues, and anxiety disorder. Close coordination between disciplines and excellent family involvement led to a very positive outcome. The student, now 19 years old, has made progress in her educational program and has been able to experience more community integration. © 2005 Wiley‐Liss, Inc.
Titelbild: Glycoviruses: Chemical Glycosylation Retargets Adenoviral Gene Transfer (Angew. Chem. 7/2005)
Authors: Pearce Oliver M. T. , Fisher Kerry D. , Humphries Julia , Seymour Leonard W. , Smith Alberto , Davis Benjamin G.
Published: February 2005

Zuckerspezifische Mechanismen der Zelltransfektion lassen sich durch gezielte Glycosylierung der Oberfläche von ikosaederförmigen Adenoviren erzeugen, wie auf dem Titelbild gezeigt ist. In ihrer Zuschrift auf S. 1081 ff. beschreiben L. W. Seymour, B. Davis et al., wie Derivate von Adenoviren mit Galactose oder Mannose selektiv menschliche Makrophagen statt menschlicher Endothelzellen transfizieren und welche Perspektiven diese drastische Zieländerung für die Gentherapie eröffnen könnte.
Chasing Molecules That Were Never There: Misassigned Natural Products and the Role of Chemical Synthesis in Modern Structure Elucidation
Authors: Nicolaou K. C. , Snyder Scott A.
Published: February 2005

Over the course of the past half century, the structural elucidation of unknown natural products has undergone a tremendous revolution. Before World War II, a chemist would have relied almost exclusively on the art of chemical synthesis, primarily in the form of degradation and derivatization reactions, to develop and test structural hypotheses in a process that often took years to complete when grams of material were available. Today, a battery of advanced spectroscopic methods, such as multidimensional NMR spectroscopy and high‐resolution mass spectrometry, not to mention X‐ray crystallography, exist for the expeditious assignment of structures to highly complex molecules isolated from nature in milligram or sub‐milligram quantities. In fact, it could be argued that the characterization of natural products has become a routine task, one which no longer even requires a reaction flask! This Review makes the case that imaginative detective work and chemical synthesis still have important roles to play in the process of solving nature's most intriguing molecular puzzles.
Cover Picture: Glycoviruses: Chemical Glycosylation Retargets Adenoviral Gene Transfer (Angew. Chem. Int. Ed. 7/2005)
Authors: Pearce Oliver M. T. , Fisher Kerry D. , Humphries Julia , Seymour Leonard W. , Smith Alberto , Davis Benjamin G.
Published: February 2005

Sugar‐specific mechanisms of cell transfection can be created by the controlled glycosylation of the surfaces of adenoviruses, which have an icosahedral structure, as depicted in the cover picture. In their Communication on page 1057 ff., L. W. Seymour, B. Davis, and co‐workers describe how derivatives of adenoviruses with galactose or mannose selectively transfect human macrophages rather than the standard human endothelia and how this dramatic retargeting holds promise for gene therapy.
Use of the cell wall protein Pir4 as a fusion partner for the expression of Bacillus sp. BP‐7 xylanase A in Saccharomyces cerevisiae
Authors: Andrés Isabel , Gallardo Oscar , Parascandola Palma , Javier Pastor F.I. , Zueco Jesús
Published: February 2005

Xylanase A from Bacillus sp. BP7, an enzyme with potential applications in biotechnology, was used to test Pir4, a disulfide bound cell wall protein, as a fusion partner for the expression of recombinant proteins in standard or glycosylation‐deficient mnn9 strains of Saccharomyces cerevisiae. Five different constructions were carried out, inserting in‐frame the coding sequence of xynA gene in that of PIR4, with or without the loss of specific regions of PIR4. Targeting of the xylanase fusion protein to the cell wall was achieved in two of the five constructions, while secretion to the growth medium was the fate of the gene product of one of the constructions. In all three cases localization of the xylanase fusion proteins was confirmed both by Western blot and detection with Pir‐specific antibodies and by xylanase activity determination. The cell wall‐targeted fusion proteins could be extracted by reducing agents, showing that the inclusion of a recombinant protein of moderate size does not affect the way Pir4 is attached to the cell wall. Also, the construction that leads to the secretion of the fusion protein permitted us to identify a region of Pir4 responsible for cell wall retention. In summary, we have developed a Pir4‐based system that allows selective targeting of an active recombinant enzyme to the cell wall or the growth medium. This system may be of general application for the expression of heterologous proteins in S. cerevisiae for surface display and secretion. © 2005 Wiley Periodicals, Inc.
Flow pattern visualization in a mimic anaerobic digester using CFD
Authors: Vesvikar Mehul S. , Al‐Dahhan Muthanna
Published: February 2005

Three‐dimensional steady‐state computational fluid dynamics (CFD) simulations were performed in mimic anaerobic digesters to visualize their flow pattern and obtain hydrodynamic parameters. The mixing in the digester was provided by sparging gas at three different flow rates. The gas phase was simulated with air and the liquid phase with water. The CFD results were first evaluated using experimental data obtained by computer automated radioactive particle tracking (CARPT). The simulation results in terms of overall flow pattern, location of circulation cells and stagnant regions, trends of liquid velocity profiles, and volume of dead zones agree reasonably well with the experimental data. CFD simulations were also performed on different digester configurations. The effects of changing draft tube size, clearance, and shape of the tank bottoms were calculated to evaluate the effect of digester design on its flow pattern. Changing the draft tube clearance and height had no influence on the flow pattern or dead regions volume. However, increasing the draft tube diameter or incorporating a conical bottom design helped in reducing the volume of the dead zones as compared to a flat‐bottom digester. The simulations showed that the gas flow rate sparged by a single point (0.5 cm diameter) sparger does not have an appreciable effect on the flow pattern of the digesters at the range of gas flow rates used. © 2005 Wiley Periodicals, Inc.
Column flow reactor using acetohydroxyacid synthase I from Escherichia coli as catalyst in continuous synthesis of R‐phenylacetyl carbinol
Authors: Engel Stanislav , Vyazmensky Maria , Berkovich Dvora , Barak Ze'ev , Merchuk Jose , Chipman David M.
Published: February 2005

We tested the possibility of utilizing acetohydroxyacid synthase I (AHAS I) from Escherichia coli in a continuous flow reactor for production of R‐phenylacetyl carbinol (R‐PAC). We constructed a fusion of the large, catalytic subunit of AHAS I with a cellulose binding domain (CBD). This allowed purification of the enzyme and its immobilization on cellulose in a single step. After immobilization, AHAS I is fully active and can be used as a catalyst in an R‐PAC production unit, operating either in batch or continuous mode. We propose a simplified mechanistic model that can predict the product output of the AHAS I‐catalyzed reaction. This model should be useful for optimization and scaling up of a R‐PAC production unit, as demonstrated by a column flow reactor. © 2005 Wiley Periodicals, Inc.
Restricted Rotation in Unbridged Sandwich Complexes: Rotational Behavior of closo‐[Co(η5‐NC4H4)(C2B9H11)] Derivatives
Authors: Viñas Clara , Llop Jordi , Teixidor Francesc , Kivekäs Raikko , Sillanpää Reijo
Published: February 2005

Rotation about the centroid/metal/centroid axis in ferrocene is facile; the activation energy is 1–5 kcal mol−1. The structurally similar sandwich complexes derived from closo‐[3‐Co(η5‐NC4H4)‐1,2‐C2B9H11] (1) have a different rotational habit. In 1, the cis rotamer in which the pyrrolyl nitrogen atom bisects the carboranyl cluster atoms is 3.5 kcal mol−1 more stable in energy than the rotamer that is second lowest in energy. This cis rotamer is wide, spanning 216°, and may be split into three rotamers of almost equal energy by substituting the N and the carboranyl carbon atoms adequately. To support this statement, closo‐[3‐Co(η5‐NC4H4)‐1,2‐(CH3)2‐1,2‐C2B9H9] (2), closo‐[3‐Co(η5‐NC4H4)‐1,2‐(μ‐CH2)3‐1,2‐C2B9H9] (3), 2→BF3, and 3→BF3 have been prepared. Two rotamers are found at low temperature for 2→BF3 and 3→BF3. Compounds 2, 3, and 1→BF3 behave similarly to 1. Rotational energy barriers and the relative populations of the different energy states are calculated from 1H DNMR spectroscopy (DNMR, dynamic NMR). These results agree with those of semiempirical calculations. Without exception, the cis rotamer is energetically the more stable. The fixed conformation of 1 assists in elucidating the rotational preferences of the [3,3′‐Co(1,2‐C2B9H11)2]− ion in the absence of steric hindrance; the [3,3′‐Co(1,2‐C2B9H11)2]− ion is commonly accepted to present a cisoid orientation. Complex 1 is electronically similar to the [3,3′‐Co(1,2‐C2B9H11)2]− ion. Both have heteroatoms in the π ligands, and they have the same electronegativity difference between the constituent atoms. This leads to a view of the [NC4H4]− as [7,8‐C2B9H11]2− ion, with no steric implications. Therefore the [3,3′‐Co(1,2‐C2B9H11)2]− ion should be considered to have a cisoid structure, and the different rotamers observed to be the result of steric factors and of the interaction of the counterion with either BH groups and/or ancillary ligands. The rotamer adopted is the one with the atoms holding the negative charges furthest apart.
Intramolecular Pauson–Khand Reactions of Methylenecyclopropane and Bicyclopropylidene Derivatives as an Approach to Spiro(cyclopropanebicyclo[n.3.0]alkenones)
Authors: de Meijere Armin , Becker Heike , Stolle Andreas , Kozhushkov Sergei I. , Bes M. Teresa , Salaün Jacques , Noltemeyer Mathias
Published: February 2005

The trimethylsilyl‐protected enynes 9 a–c and 14 a, b with alkynyl substituents on the three‐membered ring or on the double bond of a methylenecyclopropane or a bicyclopropylidene moiety were prepared in two steps from the alcohols 6 a–c and 12 a, b, respectively, by conversion to the iodides and their coupling with lithium (trimethylsilyl)acetylide (8) in 38–73 % overall yields. The bicyclopropylidene derivative 9 d was synthesized in 49 % yield directly from bicyclopropylidene (3) by lithiation followed by coupling with (5‐iodopent‐1‐ynyl)trimethylsilane (11). Enynes 9 b–d were protiodesilylated by treatment with K2CO3 in methanol to give the corresponding unprotected enynes 10 b–d in 53, 74 and 94 % yield, respectively. Enynes 17 a–c with a carbonyl group adjacent to the acetylenic moiety were synthesized from oxo derivatives 15 a–c by Wittig olefination followed by coupling with 8 in 47, 18 and 12 % overall yield, respectively. Pauson–Khand reactions of the methylenecyclopropane derivatives with a substituent on the ring (9 a,b and 10 a) as well as on the double bond (14 a,b and their in situ prepared protiodesilylated analogues) proceeded smoothly by stirring of the corresponding enyne with [Co2(CO)8] in dichloromethane at ambient temperature followed by treatment of the formed complexes with trimethylamine N‐oxide under an oxygen atmosphere at −78 °C to give tricyclic or spirocyclopropanated bicyclic enones 18 a, b, 19 a, 20 a, b, 21 a, b in good yields. Alkynylbicyclopropylidene derivatives 9 c, d and 10 c, d formed the corresponding cobalt complexes at −78 to −20 °C. Treatment of the latter with N‐methylmorpholine N‐oxide under an argon atmosphere at −20 °C gave the spirocyclopropanated tricyclic enones 18 c, 19 c and 18 d in 31–45 % yields. The structure of 19 c was proved by X‐ray crystal structure analysis. The cyclization of enynones 17 a–c in MeCN at 80 °C gave the spirocyclopropanated bicyclic diketones 22 a–c in 38–65 % yields. Intramolecular PKRs of the enynes 25 a, d with a chiral auxiliary adjacent to the triple bond gave the corresponding products 26 a, d in 70 and 79 % yield, respectively, as 5:1 and 8:1 mixtures of diastereomers, respectively. Addition of lithium dimethylcuprate or higher order cuprates to the double bond of the former furnished bridgehead‐substituted bicyclo[3.3.0]octanones 27 a–c in 57–86% yields. Protiodesilylation of 27 a followed by acetal cleavage gave the enantiomerically pure spirocyclopropanated bicyclo[3.3.0]octanedione (1R,5R)‐ 29 a with [α]${{{20\hfill \atop {\rm D}\hfill}}}$=−148 (c=1.0 in CHCl3) in 55 % overall yield.
High‐Content Photochromic Polymers Based on Dithienylethenes
Authors: Wigglesworth Tony J. , Myles Andrew J. , Branda Neil R.
Published: February 2005

Dithienylethenes (DTEs) are one of the most promising classes of photochromic compounds for use in optoelectronic devices such as waveguides, memory media and sensors. The development of DTE based polymers that contain a high mass‐content of the photoactive DTE component, that maintain their photochromic activity in the solid‐state and that are easily processed into thin‐films under a variety of conditions is critical for the implementation of the materials into useful applications. This Microreview provides an overview of the current approaches for preparing DTE‐based polymers and discusses some of the problems associated with the resulting materials such as poor solubility, low DTE content and poor photochromic activity. We present specific examples from our own research, which highlight our research group’s contributions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Essential oil composition of six Hypericum species from southern Brazil
Authors: Ferraz A. B. F. , Limberger R. P. , Bordignon S. A. L. , von Poser G. L. , Henriques A. T.
Published: February 2005

The essential oil of six Brazilian Hypericum species (Family Guttiferae) has been obtained by hydrodistillation: H. caprifoliatum Cham. & Schlecht. (0.2%), H. carinatum Griseb. (0.2%), H. connatum Lam. (0.1%), H. myrianthum Cham. & Schlecht. (0.5%), H. polyanthemum Klotzsch ex Reichardt. (0.2%) and H. ternum A. St. Hil. (0.1%). The composition of the oils was determined by GC and GC–MS and 84 compounds in total have been characterized. The principal constituents of each oil are: nonane (56%) in H. caprifoliatum, undecane (21%) in H. myrianthum, β‐caryophyllene (21%) in H. carinatum, caryophyllene oxide (40%) in H. connatum, β‐caryophyllene (12%) in H. ternum and the benzopyran HP1 (6‐isobutyryl‐5,7‐dimethoxy‐2,2‐dimethyl‐benzopyran) (27%) in H. polyanthemum. Copyright © 2005 John Wiley & Sons, Ltd.
The essential oil composition of Phlomis bruguieri Desf. from Iran
Authors: Morteza‐Semnani Katayoun , Saeedi Madjid
Published: February 2005

The composition of the essential oil obtained from the dried flowering aerial parts of Phlomis bruguieri Desf. (Labiatae) was analysed by GC and GC–MS for the first time; 99 components were identified. The major constituents of the essential oil were germacrene D (23.6%), 4‐hydroxy‐4‐methyl‐2‐pentanone (15.0%), α‐pinene (6.8%) and β‐caryophyllene (6.7%). Copyright © 2005 John Wiley & Sons, Ltd.
The duties of a receiver/manager in Nigeria and Ghana
Authors: Nwauche E. S.
Published: February 2005

This paper critically examines the duties of receiver/managers in Nigeria and Ghana with a view to determining their adequacy or otherwise. The paper distinguishes between a receiver/manager appointed pursuant to ownership or management dispute and a receiver/manager appointed pursuant to the realization of security. With respect to the former the paper concludes that the persons appointed thereby are better described as managers and suggests a more detailed elaboration of their duties. To determine the duties of receiver/managers appointed to realize security the paper examines the meaning of the receiver/managers; the capacity to be appointed to that office and the duties of a receiver/manager appointed by the court as well as those appointed out of court by the security holders. The paper also considers the consequences of a breach of duty and concludes that the law on receivership is largely the same in Nigeria and Ghana even though there is more litigation in Nigeria. Furthermore the paper suggests the importance of appointing professionals as receiver/managers; the need for the clarity of rules to enable the receiver/managers effectively discharge their duties to enable an assessment of the adequacy of the duties. In this regard the paper recommends a comprehensive reform of insolvency law in Nigeria and Ghana. Copyright © 2005 John Wiley & Sons, Ltd.
Co‐expression of alternatively spliced forms of PAX3, PAX7, PAX3‐FKHR and PAX7‐FKHR with distinct DNA binding and transactivation properties in rhabdomyosarcoma
Authors: Du Shouying , Lawrence Eric J. , Strzelecki Donna , Rajput Prerna , Xia Shujuan J. , Gottesman Dina M. , Barr Frederic G.
Published: February 2005

PAX3 and PAX7 encode transcription factors implicated in the pathogenesis of rhabdomyosarcoma (RMS), including alveolar RMS in which chromosomal translocations generate PAX3‐FKHR and PAX7‐FKHR fusions. Previous studies of wild‐type PAX3 and PAX7 identified alternative splicing events that modify the paired box and generate 2 isoforms of PAX3 (Q+ and Q−) and 4 isoforms of PAX7 (Q+GL+, Q+GL−, Q−GL+, Q−GL−). In our study, we investigated alternative splicing of the wild‐type and fusion forms of PAX3 and PAX7 in alveolar and embryonal RMS and assessed the functional implications. For PAX3 and PAX3‐FKHR, the Q+ and Q− isoforms were consistently co‐expressed in RMS tumors with slightly higher levels of the Q+ isoform. For PAX7 and PAX7‐FKHR, there was a consistent pattern of co‐expression of the 4 isoforms in RMS tumors: Q+GL− > Q+GL+ ≥ Q−GL− > Q−GL+. DNA binding analysis demonstrated that PAX3 and PAX3‐FKHR Q− isoforms exhibit higher affinity than corresponding Q+ isoforms for class I sites and no difference for class II sites. For PAX7 and PAX7‐FKHR, the relative affinity was Q−GL− > Q+GL− > Q−GL+ ≥ Q+GL+ for class I sites and Q−GL−, Q+GL− > Q−GL+, Q+GL+ for class II sites. Finally, the transcriptional activities of the PAX3‐FKHR and PAX7‐FKHR isoforms on reporter plasmids varied over a 5‐fold and 50‐fold range, respectively, in accord with the differences in DNA binding activity. In conclusion, these studies reveal that PAX3, PAX7 and their fusions with FKHR are each expressed in RMS tumors as a consistent mixture of functionally distinct isoforms. © 2005 Wiley‐Liss, Inc.
Transgenic expression of CCK2 receptors sensitizes murine pancreatic acinar cells to carcinogen‐induced preneoplastic lesions formation
Authors: Mathieu Anne , Clerc Pascal , Portolan Ghislaine , Bierkamp Christiane , Lulka Hubert , Pradayrol Lucien , Seva Catherine , Fourmy Daniel , Dufresne Marlène
Published: February 2005

In humans, initial events of pancreatic carcinogenesis remain unknown, and the question of whether this cancer, which has a ductal phenotype, exclusively arises from duct cells has been raised. Previous studies have demonstrated that transgenic expression of the CCK2 receptor in acinar cells of ElasCCK2 mice plays a role in the development of pancreatic neoplasia. The aim of our study was to examine initial steps of carcinogenesis in ElasCCK2 mice, adding a supplementary defect by using a chemical carcinogen, azaserine. Results of posttreatment sequential immunohistochemical examinations and quantifications demonstrate that mice responded to azaserine. Transition of acinar cells into duct‐like cells expressing Pdx1 and gastrin, as well as proliferation of acinar cells, were transiently observed in both transgenic and control mice. The carcinogen also induced formation of preneoplastic lesions, adenomas, exhibiting properties of autonomous growth. Importantly, expression of the CCK2 receptor increased the susceptibility of pancreas to azaserine. Indeed, treated ElasCCK2 mice exhibited larger areas of pancreatic acinar‐ductal transition, increased cellular proliferation as well as larger adenomas areas vs. control mice. These amplified responses may be related to auto/paracrine stimulation of CCK2 receptor by gastrin expressed in newly formed duct‐like cells. Our results demonstrate that activation of CCK2 receptor and azaserine result in cumulative effects to favor the emergence of a risk situation that is a potential site for initiation of carcinogenesis. © 2005 Wiley‐Liss, Inc.
Suppression of oncogenic NRAS by RNA interference induces apoptosis of human melanoma cells
Authors: Eskandarpour Malihe , Kiaii Shahryar , Zhu Chaoyong , Castro Juan , Sakko Andrew J. , Hansson Johan
Published: February 2005

The majority of human melanomas harbor activating mutations in either the BRAF or NRAS gene. To date, the role of oncogenic NRAS in melanoma remains poorly defined and no current therapies are directed at specifically suppressing oncogenic NRAS in human melanoma tumors. The aim of our study, therefore, was to investigate the effects of suppressing oncogenic NRAS in human melanoma cell lines in vitro. Using both small interfering RNA‐ and plasmid based‐RNA interference techniques, oncogenic NRAS was specifically suppressed in 2 human melanoma cell lines, 224 and BL, which harbor a codon 61 CAA (glutamine) to CGA (arginine) NRAS mutation. Suppression of oncogenic NRAS in these cell lines resulted in increased apoptosis. Furthermore, in 224 cells we demonstrated decreased phosphorylation of extracellular signal‐regulated kinase (ERK) and Akt, and reduced expression of NF‐κB and cyclin D1 in the N‐Ras signaling pathway. In contrast, RNA interference directed at wild‐type (WT) NRAS had no significant effect on apoptosis of 224 cells or 2 human melanoma cell lines (A375 and 397) containing WT NRAS but a codon 600 GTG (valine) to GAG (glutamate) mutation in BRAF. These data suggest that oncogenic NRAS is important for avoidance of apoptosis in melanomas that harbor the codon 61 NRAS mutation and emphasizes oncogenic NRAS as a therapeutic target in patients with tumors that harbor this mutation. © 2005 Wiley‐Liss, Inc.
Evidence for inactivation of distinct telomerase repressor genes in different types of human cancers
Authors: Tanaka Hiromi , Horikawa Izumi , Barrett J. Carl , Oshimura Mitsuo
Published: February 2005

Telomerase activation, a critical event in human carcinogenesis, may result from defects in telomerase‐repressing mechanisms. Data from microcell‐mediated chromosome transfer (MMCT) suggests the presence of telomerase repressor genes that become inactivated during carcinogenic processes. The transfer of a normal human chromosome 3 represses telomerase activity of both human renal cell carcinoma (RCC) and breast carcinoma (BC) cells. For a genetic complementation analysis of telomerase repression, 2 RCC cell lines (KC12 and RCC23) and a BC cell line (21NT) were used to make somatic cell hybrids. All of the self‐hybrids (KC12×KC12 and 21NT×21NT) and hybrids from 2 RCC cell lines (KC12×RCC23) expressed the telomerase activity similarly to their parental cells, excluding the possibility of a ploidy‐associated change in telomerase activity and suggesting the same genetic defect shared by the 2 RCC cell lines. In contrast, the fusion of BC and RCC cells (21NT×KC12 and 21NT×RCC23) produced a significant number of telomerase‐negative hybrids, suggesting that the RCC and BC cells have different defects in the telomerase repression, which are functionally corrected through genetic complementation in the hybrids. This notion was supported by the mapping of the RCC telomerase repressor gene to a 5.7‐Mb region on 3p21, which is different from the candidate region for the BC telomerase repressor gene on the same chromosomal band. These findings provide direct evidence for inactivation of distinct telomerase repressor genes in different types of human cancers and may have implications in the tissue‐specific regulation of telomerase during human development and carcinogenesis. © 2005 Wiley‐Liss, Inc.
Cancer risk to the gastric corpus in Japanese, its correlation withinterleukin‐1βgene polymorphism (+3953*T) and Epstein‐Barr virus infection
Authors: Sakuma Kazuya , Uozaki Hiroshi , Chong Ja‐Mun , Hironaka Mitsugu , Sudo Makoto , Ushiku Tetsuo , Nagai Hideo , Fukayama Masashi
Published: February 2005

Polymorphisms ofinterleukin‐1 (IL‐1)genes have been reported to modify the risk of gastric carcinoma (GC) in Caucasians. The significance ofIL‐1βgene polymorphisms was evaluated in Japanese GC patients with or without infection ofHelicobacter pyloriand Epstein Barr virus (EBV) with special reference to the topographic features of GC.IL‐1βgene polymorphisms at positions ‐511 and +3953 were evaluated by PCR‐RFLP and a penta‐allelic polymorphism ofIL‐1RAby PCR in healthy controls (n= 103) and GC (n=140; corpus 95, antrum 45). EBV‐infection was determined in the neoplastic tissues byEBER1 in situhybridization, andH. pyloriinfection in nonneoplastic gastric mucosa by PCR targeting of theH. pylori urease Agene. GC consisted of EBV‐associated (n= 24) and EBV‐negative (n= 116) patients, whereasH. pyloriinfection was positive in 130 cases. AmongIL‐1βgene polymorphisms, genotypeIL‐1β+3953 C/T was more frequent in the EBV‐negative (21%) and corpus GC (23%) patients, compared to the controls (10%), respectively, although there was no genotypeIL‐1β+3953 T/T in either group. Thus, the effect ofIL‐1β+3953 T was statistically significant in logistic regression models adjusted for age in EBV negativity (odds ratio [OR] 2.27, 95% confidence interval [CI] 1.02–5.05) and in the corpus GC (2.70, 1.19–6.12) with highest OR 3.55 (1.54–8.23) in EBV‐negative corpus GC. There was no significant influence ofIL‐1gene polymorphism in EBV‐associated GC, but it occurred predominantly in the corpus (24/24) compared to EBV‐negative GC (71/116) (p= 0.00002). There was no correlation betweenH. pyloriinfection andIL‐1gene polymorphism in GC. The cancer risk of the gastric corpus in Japanese is influenced byIL‐1β+3953 polymorphisms. On the other hand, the risk of EBV‐associated GC, which occurs predominantly in the corpus, is not influenced by this pro‐inflammatory polymorphism. © 2005 Wiley‐Liss, Inc.
Virus target cell conditioning model to explain some epidemiologic characteristics of childhood leukemias and lymphomas
Authors: zur Hausen Harald , de Villiers Ethel‐Michele
Published: February 2005

Frequent infections in early childhood, whole‐day care and a socially unprivileged environment have been reported as protective factors for childhood leukemias and lymphomas. Conversely, a protected social environment, higher level of education and growing up in families with a low number of children are considered as risk factors. Additional risk factors involve agricultural occupation of the parents and exposure to several other occupational factors. These data led to a number of hypotheses that attempted to explain the epidemiologic observations; however, a number of questions are still open. Here we propose a new concept that could explain most of the epidemiologic characteristics. This concept is based on the assumption that persistent infections with TT virus‐like agents increase the risk for specific chromosomal translocations. This risk should correlate with the viral load. Interferon induction by intermittent infections should reduce the viral load and thus decrease the risk for chromosomal modifications. Some virologic observations in support of this model are presented. © 2005 Wiley‐Liss, Inc.
Structures and electron affinities of the di‐arsenic fluorides As2Fn/As2F (n = 1–8)
Authors: Kasalová Veronika , Schaefer Henry F.
Published: February 2005

Developments in the preparation of new materials for microelectronics are focusing new attention on molecular systems incorporating several arsenic atoms. A systematic investigation of the As2Fn/As2F systems was carried out using Density Functional Theory methods and a DZP++ quality basis set. Global and low‐lying local geometric minima and relative energies are discussed and compared. The three types of neutral‐anion separations reported in this work are: the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Harmonic vibrational frequencies pertaining to the global minimum for each compound are reported. From the first four studied species (As2Fn, n = 1–4), all neutral molecules and their anions are shown to be stable with respect to AsAs bond breaking. The neutral As2F molecule and its anion are predicted to have Cs symmetry. We find the trans FAsAsF isomer of C2h symmetry and a pyramidalized vinylidene‐like AsAsF isomer of Cs symmetry to be the global minima for the As2F2 and As2F species, respectively. The lowest lying minima of As2F3 and As2F are vinyl radical‐like structures FAsAsF2 of Cs symmetry. The neutral As2F4 global minimum is a trans‐bent (like Si2H4) F2AsAsF2 isomer of C2 symmetry, while its anion is predicted to have an unusual fluorine‐bridged (C1) structure. The global minima of the neutral As2Fn species, n = 5–8, are weakly bound complexes, held together by dipole–dipole interactions. All such structures have the AsFmAsFn form, where (m,n) is (2,3) for As2F5, (3,3) for As2F6, (4,3) for As2F7, and (5,3) for As2F8. For As2F8 the beautiful pentavalent F4AsAsF4 structure (analogous to the stable AsF5 molecule) lies about 30 kcal/mol above the AsF3 · · · AsF5 complex. The stability of AsF5 depends crucially on the strong AsF bonds, and replacing one of these with an AsAs bond (in F4AsAsF4) has a very negative impact on the molecule's stability. The anions As2F, n = 5–8, are shown to be stable with respect to the AsAs bond breaking, and we predict that all of them have fluorine‐bridged or fluorine‐linked structures. The zero‐point vibrational energy corrected adiabatic electron affinities are predicted to be 2.28 eV (As2F), 1.95 eV (As2F2), 2.39 eV (As2F3), 1.71 eV (As2F4), 2.72 eV (As2F5), 1.79 eV (As2F6), 5.26 eV (As2F7), and 3.40 eV (As2F8) from the BHLYP method. Vertical detachment energies are rather large, especially for species with fluorine‐bridged global minima, having values up to 6.45 eV (As2F7, BHLYP). © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 411–435, 2005
A comparative study of various computational approaches in calculating the structure of pyridoxal 5′‐phosphate (PLP)‐dependent β‐lyase protein. The importance of protein environment
Authors: Prabhakar Rajeev , Morokuma Keiji , Musaev Djamaladdin G.
Published: February 2005

Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the “active site‐only” approach (including only active site atoms) has been found to give the largest root‐mean‐square (RMS) deviation from the X‐ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X‐ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two‐layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active‐site interaction on the active‐site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 443–446, 2005
Isolation and characterization of collagen from bigeye snapper (Priacanthus macracanthus) skin
Authors: Jongjareonrak Akkasit , Benjakul Soottawat , Visessanguan Wonnop , Tanaka Munehiko
Published: February 2005

Acid‐solubilized collagen (ASC) and pepsin‐solubilized collagen (PSC) were isolated from the skin of bigeye snapper (Priacanthus macracanthus) with yields of 64 and 11 g kg−1 wet weight, respectively. Both ASC and PSC were characterized as type I collagens with no disulfide bonds. Peptide maps of ASC and PSC digested by V8 protease and lysyl endopeptidase showed some differences in peptide patterns and were totally different from those of calf skin collagen. The maximum solubility was observed at pH 4 and 5 for ASC and PSC, respectively. A sharp decrease in solubility of both collagens in acetic acid was found with NaCl concentration above 30 g l−1. Thermal transitions of ASC and PSC in deionized water were observed with Tmax of 30.37 and 30.87 °C, respectively, and were lowered in the presence of acetic acid (0.05 mol kg−1 solution). Therefore, ASC was a major fraction in bigeye snapper skin and it exhibited some different characteristics to PSC. Copyright © 2005 Society of Chemical Industry
Quantification of lycopene in tomato products: comparing the performances of a newly proposed direct photothermal method and high‐performance liquid chromatography
Authors: Bicanic Dane , Fogliano Vincenzo , Luterotti Svjetlana , Swarts Jan , Piani Giovanni , Graziani Giulia
Published: February 2005

A new photothermal method suitable for direct, accurate and highly reproducible quantitative measurements of lycopene in tomato products has been introduced. The intrinsic precision of the method is typically better than 0.2%; the repeatability of determination is comparable to that of high‐performance liquid chromatography, with 0.86% least overall error. Copyright © 2005 Society of Chemical Industry
Analyses of tomato peel and seed byproducts and their use as a source of carotenoids
Authors: Knoblich Monika , Anderson Brandi , Latshaw David
Published: February 2005

Commercial tomato canning yields two different byproducts. One is the material that results from peeling tomatoes, while the other results from removing the seeds. The peel byproduct contained 100.8 g protein, 256.4 g ash and 299.4 g acid detergent fiber kg−1. Ash content was high because the peel byproduct contained 83.8 g kg−1 sodium as a result of using a sodium hydroxide solution to peel the tomatoes. The seed byproduct contained 202.3 g protein, 51.8 g ash, and 537.9 g acid detergent fiber kg−1. An amino acid analysis of seeds indicated that approximately 60% of the protein results from amino acids. Both byproducts were analyzed for carotenoid content. The lycopene content of peel byproduct was 734 µg g−1 of dry material. Significant amounts of lutein, β‐carotene, and cis‐β‐carotene were also present. Seed byproduct contained 130 µg lycopene kg−1 of dry matter. The content of other carotenoids was approximately half of that present in the peels. Peel and seed byproducts were included at 75 g kg−1 in hen diets to determine the transfer of carotenoids to the yolk. When fed at this concentration, the lycopene content of dry egg yolk was approximately 0.9 µg g−1. Approximately 0.1% of the lycopene in peel byproduct and approximately 0.7% of the lycopene in the seed byproduct was transferred from the feed to the yolk. Lycopene appears more similar to carotene than to oxycarotenoids in its transfer to the yolk. Copyright © 2005 Society of Chemical Industry
The oxidative degradation of the lipid fraction of ripened sausages as influenced by the raw material
Authors: Summo Carmine , Caponio Francesco , Bilancia Maria Teresa
Published: February 2005

An experimental investigation was conducted to assess the actual degree of oxidative degradation of the lipid fraction of 30‐day‐ripened sausages using both commonly used investigations and non‐conventional means, such as the high‐performance size‐exclusion chromatography analysis of polar compounds. Sausages made from pork shoulders from extensive and intensive pig rearing were considered. The obtained results showed a high degree of primary oxidative degradation of the sausage lipid fraction, as evidenced by oxidized triacylglyrerol and peroxide values, while a low secondary oxidation of fats was found, as evidenced by triacylglycerol oligopolymers and 2‐tiobarbituric acid test values. Moreover, the degree of oxidative degradation did not show any significant difference between the two types of sausage, although the samples prepared from extensively reared pigs, as compared with those from intensively reared pigs, showed significantly (p < 0.001) higher contents of polyunsaturated fatty acids and significantly (p < 0.01) lower amounts of saturated fatty acids. Copyright © 2005 Society of Chemical Industry
Influence of ripening stage on volatiles composition, physicochemical indexes and sensory evaluation in two varieties of muskmelon (Cucumis melo L var reticulatus Naud)
Authors: Senesi Emilio , Di Cesare Luigi F , Prinzivalli Caterina , Scalzo Roberto Lo
Published: February 2005

The quality parameters of muskmelon (Cucumis melo L var reticulatus Naud) are often related to sugar content and aroma composition. A study of aroma composition using two different extraction techniques (GC‐HS and GC‐MS extraction concentration) was performed in order to find correlations with sensory descriptors, other quality indices and ripening stage. Two muskmelon varieties (Calypso and Pamir) were assayed at three different ripening stages (unripe, ripe, overripe). Chemical, physical and sensory analyses were performed on the muskmelon samples just after harvest and after 7 days of cold storage. Solid soluble content (SSC) changed from about 10°Bx in unripe samples to about 15°Bx in ripe and overripe samples. Different aroma composition and sensory evaluation were found depending on the ripening stages. The main flavour components detected were esters which increased 10–15‐fold from unripe to ripe and overripe stages. The acceptance judgements by panellists were strongly correlated with the sensory descriptor flavour. High statistical correlations were also found between sensory descriptor flavour and some classes of aroma compounds, mainly with total esters (about 0.66–0.69), formates (0.70) and acetates (0.64 and 0.72). The paper demonstrates that some classes of esters are very important to assess the sensory flavour and overall eating quality of muskmelons. Copyright © 2005 Society of Chemical Industry
Improving the quality of sorghum injera by decortication and compositing with tef
Authors: Yetneberk Senayit , Rooney Lloyd W , Taylor John RN
Published: February 2005

Injera is an Ethiopian fermented pancake‐like bread made from cereals, with tef being preferred. Decortication and compositing with tef were evaluated as methods to improve the injera‐making quality of red tannin‐free and tannin‐containing sorghums. Both decortication and compositing improved sorghum injera quality. Concerning decortication, mechanical abrasion was found to be more effective than hand pounding because acceptable injera was obtained with lower milling loss. Good quality injera was produced at an extraction rate of 540 g kg−1 for tannin‐containing and 830 g kg−1 for tannin‐free sorghum. With compositing, good quality injera was produced with a 50:50 (w/w) composite of whole tannin‐containing sorghum and tef. Both processes reduced the tannin content of the flours, which appeared to relieve the inhibiting effects of tannins on the fermentation. Decortication also seemed to improve sorghum flour injera‐making quality by improving flour pasting as a result of reducing the level of interfering substances such as lipids and proteins. In contrast, the improvement brought about by compositing with tef seemed to be due to inherent differences between tef and sorghum starch granules and an increase in the water solubility index of the flour. Compositing seems to be a more useful method of improving sorghum injera quality than decorticating as it avoids the grain loss associated with decortication. Copyright © 2005 Society of Chemical Industry
Water distribution and mobility in herring muscle in relation to lipid content, season, fishing ground and biological parameters
Authors: Jensen Kristina Nedenskov , Jørgensen Bo M , Nielsen Henrik H , Nielsen Jette
Published: February 2005

Low‐field 1H nuclear magnetic resonance transverse relaxation profiles were measured on muscle samples from herring differing in catch season (summer or winter), fishing ground (Baltic Sea, North Sea, Skagerrak or Kattegat), biological parameters (maturity status, sex and spawning type), lipid and water content, and catching vessel (the institute's research vessel Dana or commercial fishing vessels). Water mobility and distribution in herring muscle samples were calculated from the NMR signals by the use of multi‐way analysis. The distribution and mobility of water in samples from herring caught by Dana differed according to season, samples from summer herring having two water pools (with T2‐values of 37 and 75 ms) and samples from winter herring having three water pools (with T2‐values of 41, 58 and 102 ms). This difference in number of water pools was also found in samples from herring caught by commercial vessels. It is suggested that samples from herring caught during winter contain an extra pool of inter‐myofibrillar water not present in the samples from herring caught during the summer due to their higher lipid content. The water and lipid content significantly affected the water distribution in both summer and winter herring. The differences in water pools were also reflected in the sensory quality of a marinated herring product. The leaner winter herring corresponding to samples with three water pools were more firm and had less fatty mouth feel than the more fatty summer herring, corresponding to samples with only two water pools. Copyright © 2005 Society of Chemical Industry
Optimization of solid‐phase microextraction methods for GC‐MS determination of terpenes in wine
Authors: Peña Rosa M , Barciela Julia , Herrero Carlos , García‐Martín Sagrario
Published: February 2005

Solid‐phase microextraction using a 100 µm poly(dimethylsiloxane) fiber, followed by gas chromatography–mass spectrometry determination, has been optimized for the analysis of some terpenes in wine samples. The best results were obtained by direct immersion of the fiber using a sampling period of 15 min with constant magnetic stirring (1100 rpm) and an extraction temperature of 20 °C. The sample volume was 7 ml with 25% NaCl, in a 15 ml capped vial. Desorption was performed directly in the gas chromatograph injector port over 5 min at 250 °C using the splitless mode. The method is sensitive, with detection limits between 11 and 25 µg l−1, precise, with variation coefficients in the range 1.28–3.71%, and linear over more than one order of magnitude. The related conditions were used for wine sample analyses with recoveries between 71.8 and 90.9%. Solid‐phase microextraction remains an attractive alternative technique due to its rapidity and because it is a solvent‐free extraction. Copyright © 2005 Society of Chemical Industry
Generation and interrogation of a pure nuclear spin state by parahydrogen‐enhanced NMR spectroscopy: a defined initial state for quantum computation
Authors: Blazina D. , Duckett S. B. , Halstead T. K. , Kozak C. M. , Taylor R. J. K. , Anwar M. S. , Jones J. A. , Carteret H. A.
Published: February 2005

We describe a number of studies used to establish that parahydrogen can be used to prepare a two‐spin system in a pure state, which is suitable for implementing NMR quantum computation. States are generated by pulsed and continuous‐wave (CW) UV laser initiation of a chemical reaction between Ru(CO)3(L2) [where L2 = dppe = 1,2‐bis(diphenylphosphino)ethane or L2 = dpae = 1,2‐bis(diphenylarsino)ethane] with pure parahydrogen (generated at 18 K). This process forms Ru(CO)2(dppe)(H)2 and Ru(CO)2(dpae)(H)2 on a sub‐microsecond time‐scale. With the pulsed laser, the spin state of the hydride nuclei in Ru(CO)2(dppe)(H)2 has a purity of 89.8 ± 2.6% (from 12 measurements). To achieve comparable results by cooling would require a temperature of 6.6 mK, which is unmanageable in the liquid state, or an impractical magnetic field of 0.44 MT at room temperature. In the case of CW initiation, reduced state purities are observed due to natural signal relaxation even when a spin‐lock is used to prevent dephasing. When Ru(CO)3(dpae) and pulsed laser excitation are utilized, the corresponding dihydride product spin state purity was determined as 106 ± 4% of the theoretical maximum. In other words, the state prepared using Ru(CO)3(dpae) as the precursor is indistinguishable from a pure state. Copyright © 2004 John Wiley & Sons, Ltd.
The size of the alpha‐effects in methyl transfers correlate with Koopmans' theorem ionization potentials
Authors: Fountain K. R.
Published: February 2005

The size of the alpha‐effects in methyl transfers to the alpha‐nucleophile's peroxide anion and two N‐methylbenzohydroxamate anions correlate strongly with the Koopmans' theorem ionization potentials of the leaving groups. This correlation supports the Shaik and Pross valence bond configuration mixing theory for the SN2 reaction. The Koopmans' theorem ionization potentials of the alpha‐nucleophiles relate to the slopes of the regression plots inversely, indicating that the size of the alpha‐effect depends on a balance between the ability of the alpha‐nucleophile and the leaving group to donate single electron character to the methyl group. Copyright © 2005 John Wiley & Sons, Ltd.
Multiple‐substituent effects on the isomerization of unsymmetrical cis‐1,3‐diphenyltriazenes
Authors: Zhang Huaibin , Barra Mónica
Published: February 2005

Trans‐to‐cis photoisomerization of unsymmetrical 4,4′‐disubstituted trans‐1,3‐diphenyltriazenes renders a non‐equilibrium mixture of two isomeric cis pairs which, as in the case of symmetrical 1,3‐diphenyltriazenes, undergo thermal cis‐to‐trans isomerization by means of 1,3‐prototropic rearrangements catalyzed by general acids and general bases. A quantitative analysis, by means of a multiple‐substituent Hammett equation, of the rate constants for restricted rotation around the N‐2—N‐3 bond in cis‐1,3‐diphenyltriazenes renders ρ values of −1.93±0.08 and 0.82±0.08 for N‐1 and N‐3, respectively. Copyright © 2005 John Wiley & Sons, Ltd.