Biospectroscopy最新文献

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Structure/activity studies of the anti-MUC1 monoclonal antibody C595 and synthetic MUC1 mucin-core-related peptides and glycopeptides 抗MUC1单克隆抗体C595的结构/活性研究及合成MUC1粘蛋白核心相关肽和糖肽类
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:2<79::AID-BSPY2>3.0.CO;2-%23
D. I. R. Spencer, S. Missailidis, G. Denton, A. Murray, K. Brady, C. I. D. Matteis, M. S. Searle, S. J. B. Tendler, M. R. Price
{"title":"Structure/activity studies of the anti-MUC1 monoclonal antibody C595 and synthetic MUC1 mucin-core-related peptides and glycopeptides","authors":"D. I. R. Spencer,&nbsp;S. Missailidis,&nbsp;G. Denton,&nbsp;A. Murray,&nbsp;K. Brady,&nbsp;C. I. D. Matteis,&nbsp;M. S. Searle,&nbsp;S. J. B. Tendler,&nbsp;M. R. Price","doi":"10.1002/(SICI)1520-6343(1999)5:2<79::AID-BSPY2>3.0.CO;2-%23","DOIUrl":"https://doi.org/10.1002/(SICI)1520-6343(1999)5:2<79::AID-BSPY2>3.0.CO;2-%23","url":null,"abstract":"<p>MUC1 mucin is a large complex glycoprotein expressed on normal epithelial cells in humans and overexpressed and under or aberrantly glycosylated on many malignant cancer cells which consequently allows recognition of the protein core by antibodies. In order to understand how glycosylation may modulate or regulate antibody binding of mucin protein core epitopes, we have analyzed the antibody C595 (epitope RPAP) for its structure, stability, and its binding to a series of synthetic peptides and glycopeptides by a number of spectroscopic methods. Thermal and pH denaturation studies followed by changes in the CD spectrum of the antibody indicate critical involvement of specific residues to the stability of the antibody. Fluorescence binding studies indicate that α-<i>N</i>-acetylgalactosamine (GalNAc) glycosylation of a MUC1 mucin synthetic peptide TAPPAHGVT<sub>9</sub>SAPDTRPAPGS<sub>20</sub>T<sub>21</sub>APPA at threonine residues 9 and 21 and serine residue 20 enhanced the binding of antibody. The structural effects of GalNAc glycosylation on the conformation of the MUC1 peptide were studied. CD of the peptides and glycopeptides in a cryogenic mixture cooled to approximately −97°C revealed that a left-handed polyproline II helix (PPII) is adopted by the peptides in solution, which appears to be further stabilized by addition of the GalNAc residues. Consistent with the PPII helical structure, which has no intra-amide hydrogen bonds, high-field NMR spectroscopy of the glycopeptide revealed no sequential d<sub>NN</sub>, medium-range, or long-range nuclear Overhauser effect (NOE) connectivities. These studies indicate that stabilization of the PPII helix by GalNAc glycosylation present the epitope of C595 antibody with a favorable conformation for binding. Furthermore, they illustrate that glycosylation of the MUC1 tumor marker protein with a simple O-linked saccharide expressed in many cancers, can enhance the binding of the clinically relevant C595 antibody. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 79–91, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 2","pages":"79-91"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"137816673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A study on the differences between oral squamous cell carcinomas and normal oral mucosas measured by Fourier transform infrared spectroscopy 傅里叶变换红外光谱测定口腔粘膜鳞状细胞癌与正常口腔粘膜差异的研究
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:2<117::AID-BSPY5>3.0.CO;2-K
Yoshikuni Fukuyama, Satoshi Yoshida, Shigetaka Yanagisawa, Masatsugu Shimizu
{"title":"A study on the differences between oral squamous cell carcinomas and normal oral mucosas measured by Fourier transform infrared spectroscopy","authors":"Yoshikuni Fukuyama,&nbsp;Satoshi Yoshida,&nbsp;Shigetaka Yanagisawa,&nbsp;Masatsugu Shimizu","doi":"10.1002/(SICI)1520-6343(1999)5:2<117::AID-BSPY5>3.0.CO;2-K","DOIUrl":"10.1002/(SICI)1520-6343(1999)5:2<117::AID-BSPY5>3.0.CO;2-K","url":null,"abstract":"<p>We investigated the differences of Fourier transform infrared (FTIR) spectra between oral squamous cell carcinoma (OSCC) and normal gingival epithelium (NGE) or normal subgingival tissue (NST). We used 15 specimens of OSCC which had not been treated before measurement and 10 of NGE or NST. We also used cultured oral squamous cell carcinoma (COSCC) and the tissue (MSCC) which massed for 3 months after the cultured oral squamous cell carcinoma was transplanted into the lower back of a rat. Those tissue spectra were compared with the purified human collagens and human keratin. One half of every tissue specimen was measured with FTIR and the other half was investigated histologically. The differences of FTIR spectra between OSCC and NGE were observed in the bands between 1431 and 1482 cm<sup>−1</sup> and between 1183 and 1274 cm<sup>−1</sup>. The shoulder at 1368 cm<sup>−1</sup> tended to disappear in OSCC, and the peaks at 1246 and 1083 cm<sup>−1</sup> found in NGE tended to shift to those at 1242 and 1086 cm<sup>−1</sup> in OSCC, respectively. The infrared spectrum of NST was noticed to be strongly influenced by the presence of collagen. Significant differences were also observed in the second derivative FTIR spectra between OSCC and NGE. Our data suggested that this infrared technique is applicable to clinical diagnostics. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 117–126, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 2","pages":"117-126"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:2<117::AID-BSPY5>3.0.CO;2-K","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"21087781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 70
Biodeterioration of granite monuments by Ochrolechia parella (L.) mass: An FT Raman spectroscopic study 花岗岩遗迹中斑蛭(ololechia parella (L.) mass的生物降解:FT拉曼光谱研究
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:1<53::AID-BSPY7>3.0.CO;2-%23
B. Prieto, M. R. D. Seaward, H. G. M. Edwards, T. Rivas, B. Silva
{"title":"Biodeterioration of granite monuments by Ochrolechia parella (L.) mass: An FT Raman spectroscopic study","authors":"B. Prieto,&nbsp;M. R. D. Seaward,&nbsp;H. G. M. Edwards,&nbsp;T. Rivas,&nbsp;B. Silva","doi":"10.1002/(SICI)1520-6343(1999)5:1<53::AID-BSPY7>3.0.CO;2-%23","DOIUrl":"https://doi.org/10.1002/(SICI)1520-6343(1999)5:1<53::AID-BSPY7>3.0.CO;2-%23","url":null,"abstract":"<p><i>Ochrolechia parella</i> is one of the most abundant lichens colonizing granite monuments in the region of Galicia (N.W. Spain). Its interaction with granite used in the construction of four ancient monuments was studied using FT Raman spectroscopy to evaluate the production of calcium oxalate by this lichen and the relationship of this production with different environmental conditions, particularly humidity. The results obtained showed that <i>Ochrolechia parella</i> is an aggressive colonizer, causing chemical disturbances to the granite through the formation of both calcium oxalate monohydrate and dihydrate. Apothecial development appears to be related to the production of calcium oxalate, and humidity determines the state of hydration of the calcium oxalate in the thallus. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 53–59, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 1","pages":"53-59"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:1<53::AID-BSPY7>3.0.CO;2-%23","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"137814050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Therese Cotton Therese棉花
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:1<1::AID-BSPY1>3.0.CO;2-6
W. E. Smith
{"title":"Therese Cotton","authors":"W. E. Smith","doi":"10.1002/(SICI)1520-6343(1999)5:1<1::AID-BSPY1>3.0.CO;2-6","DOIUrl":"https://doi.org/10.1002/(SICI)1520-6343(1999)5:1<1::AID-BSPY1>3.0.CO;2-6","url":null,"abstract":"","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 1","pages":"1-2"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:1<1::AID-BSPY1>3.0.CO;2-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"137814068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Lichen biodeterioration of the Convento de la Peregrina, Sahagún, Spain 修道院的地衣生物退化,Sahagún,西班牙
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:1<47::AID-BSPY6>3.0.CO;2-1
H. G. M. Edwards, F. Rull Perez
{"title":"Lichen biodeterioration of the Convento de la Peregrina, Sahagún, Spain","authors":"H. G. M. Edwards,&nbsp;F. Rull Perez","doi":"10.1002/(SICI)1520-6343(1999)5:1<47::AID-BSPY6>3.0.CO;2-1","DOIUrl":"10.1002/(SICI)1520-6343(1999)5:1<47::AID-BSPY6>3.0.CO;2-1","url":null,"abstract":"<p>Lichen encrustations from <i>Diploschistes scruposus</i> involved in the biodeterioration of the 13th Century Convento de la Peregrina in Sahagún Spain, have been analyzed using Raman spectroscopy. The vibrational spectra are characteristic of calcium oxalate monohydrate, β-carotene, chlorophyll, and <i>para</i>-depside phenolic acids such as atranorin, lecanoric acid, and diploschistesic acid. The destructive colonization of the monumental stonework is highlighted and evidence presented for deleterious lichen invasion of the wall paintings inside the Convent. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 47–52, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 1","pages":"47-52"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:1<47::AID-BSPY6>3.0.CO;2-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"21090721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 27
Polarizing microscopy of eyespot of Chlamydomonas: In situ observation of its location, orientation, and multiplication 衣藻眼斑的偏光显微镜:其位置、方向和繁殖的原位观察
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:2<93::AID-BSPY3>3.0.CO;2-X
Shi-Yuan Yang, Masamichi Tsuboi
{"title":"Polarizing microscopy of eyespot of Chlamydomonas: In situ observation of its location, orientation, and multiplication","authors":"Shi-Yuan Yang,&nbsp;Masamichi Tsuboi","doi":"10.1002/(SICI)1520-6343(1999)5:2<93::AID-BSPY3>3.0.CO;2-X","DOIUrl":"10.1002/(SICI)1520-6343(1999)5:2<93::AID-BSPY3>3.0.CO;2-X","url":null,"abstract":"<p>The eyespot in the cell of <i>Chlamydomonas reinhardtii</i> has been found to appear as a bright spot under the cross polar setting of a polarizing microscope. This was confirmed by isolating the eyespot from a homogenate of wall-deficient mutant cw-15, and by observing it under a polarizing microscope. Thus, the eyespot was proved to be a strongly birefringent body. Next, gametes (mt<sup>+</sup> and mt<sup>−</sup>) of 137c strain were prepared by cultivating it in a low-nitrogen (NH<sub>4</sub>Cl) medium. Here, every cell shows only one (and never more than one) birefringent spot. The birefringent eyespot was located always near the surface on the “equator,” that is, at the farthest point from the “meridional” cell-axis that is defined as the bisector of the two flagella projected out from the cell surface. It was shown, in addition, that the optic axis of this birefringent eyespot is oriented in the cell always along the parallel direction of the cell axis defined above. Thus, the polarizing microscopy has been shown to provide a powerful method for <i>in vivo</i>, <i>in situ</i> pursuit of the eyespot of <i>Chlamydomonas</i>. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 93–100, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 2","pages":"93-100"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:2<93::AID-BSPY3>3.0.CO;2-X","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"21087779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 14
Semiempirical and Raman spectroscopic studies of carotenoids 类胡萝卜素的半经验和拉曼光谱研究
Biospectroscopy Pub Date : 1999-04-09 DOI: 10.1002/(SICI)1520-6343(1999)5:1<19::AID-BSPY4>3.0.CO;2-E
R. J. Weesie, J. C. Merlin, J. Lugtenburg, G. Britton, F. J. H. M. Jansen, J. P. Cornard
{"title":"Semiempirical and Raman spectroscopic studies of carotenoids","authors":"R. J. Weesie,&nbsp;J. C. Merlin,&nbsp;J. Lugtenburg,&nbsp;G. Britton,&nbsp;F. J. H. M. Jansen,&nbsp;J. P. Cornard","doi":"10.1002/(SICI)1520-6343(1999)5:1<19::AID-BSPY4>3.0.CO;2-E","DOIUrl":"10.1002/(SICI)1520-6343(1999)5:1<19::AID-BSPY4>3.0.CO;2-E","url":null,"abstract":"<p>Semiempirical AM1 calculations have been carried out for β-carotene and the three xanthophylls (zeaxanthin, canthaxanthin, and astaxanthin) containing oxygen functions (hydroxy/keto groups) found in the majority of natural pigment. The fully optimized geometries correspond well with the X-ray structures of β-carotene and canthaxanthin and indicate that substitutions on the terminal rings have a minimal effect on the conformation of the chromophore. Twisting along the polyenic chain results from steric interaction involving methyl substituents, and a <i>C<sub>i</sub></i> point group can be proposed for the four investigated carotenoids. AM1 calculated excitation energies for the strongly allowed excited states can be compared to with the experimental absorption band in the visible region, considering solvent effect. Resonance Raman (RR) and Fourier transform (FT) Raman spectra of natural astaxanthin as well as astaxanthins specifically <sup>13</sup>C labeled at the positions 12,12′; 13,13′; 14,14′; 15,15′; 15, and 20,20′ were recorded. Furthermore the RR and FT Raman spectra of the asymmetric carotenoid 20-norastaxanthin are presented. The data reveal a substantial amount of information about the coupling between the different vibrations, and enabled an extensive experimental verification of the theoretical normal-coordinate analysis previously performed on polyenic molecules [J Raman Spectrosc 1983, 14, 310–321; <i>Advances in Infrared and Raman Spectroscopy</i>, Vol. 12, 1985, pp. 115–178; Spectrochim Acta 1996, 53, 381–392; Biochim Biophys Acta 1994, 1185, 188–196]. The results make up a very interesting dataset which allowed the interpretation and/or observation of several, hitherto never observed or not well understood, effects in the Raman spectra of the differently labeled astaxanthins. © 1999 John Wiley &amp; Sons, Inc. Biospectroscopy 5: 19–33, 1999</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"5 1","pages":"19-33"},"PeriodicalIF":0.0,"publicationDate":"1999-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1999)5:1<19::AID-BSPY4>3.0.CO;2-E","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"21090719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 72
Conformation and interactions of the packaged double-stranded DNA genome of bacteriophage T7 噬菌体T7包装双链DNA基因组的构象和相互作用
Biospectroscopy Pub Date : 1999-01-06 DOI: 10.1002/(SICI)1520-6343(1998)4:5+<S47::AID-BSPY6>3.0.CO;2-7
Stacy A. Overman, Kelly L. Aubrey, Kim E. Reilly, Olivia Osman, Shirley J. Hayes, Philip Serwer, George J. Thomas Jr.
{"title":"Conformation and interactions of the packaged double-stranded DNA genome of bacteriophage T7","authors":"Stacy A. Overman,&nbsp;Kelly L. Aubrey,&nbsp;Kim E. Reilly,&nbsp;Olivia Osman,&nbsp;Shirley J. Hayes,&nbsp;Philip Serwer,&nbsp;George J. Thomas Jr.","doi":"10.1002/(SICI)1520-6343(1998)4:5+<S47::AID-BSPY6>3.0.CO;2-7","DOIUrl":"10.1002/(SICI)1520-6343(1998)4:5+<S47::AID-BSPY6>3.0.CO;2-7","url":null,"abstract":"<p>The structure of the packaged double-stranded DNA genome of bacteriophage T7 was compared to that of unpackaged T7 DNA using digital difference Raman spectroscopy. Spectral data were obtained at 25°C from native T7 virus (100 mg/mL), empty T7 capsids (50 mg/mL), and purified T7 DNA (40 mg/mL) in buffer containing 200 m<i>M</i> NaCl, 10 m<i>M</i> MgCl<sub>2</sub>, and 10 m<i>M</i> Tris at pH 7.5. At these conditions, the local conformation of T7 DNA was not affected by packaging. Specifically, the local <i>B</i>-form secondary structure of unpackaged T7 DNA, including furanose C2′-<i>endo</i> pucker, <i>anti</i> glycosyl torsion, Watson-Crick base pairing, and base stacking, were essentially fully (&gt;98%) retained when the genome was condensed within the viral capsid. However, the average electrostatic environment of T7 DNA phosphates was altered dramatically by packaging as revealed by large perturbations in the Raman bands associated with localized vibrations of the DNA phosphate groups. The change in the phosphate environment was attributed to Mg<sup>2+</sup> ions that were packaged with the genomic DNA, and the observed Raman perturbations of genomic DNA were equivalent to those generated by a 50–100-fold increase in Mg<sup>2+</sup> concentration in aqueous phosphodiester model compounds. The T7 data were qualitatively and quantitatively similar to those observed previously for packaged DNA of bacteriophage P22 and imply that genomic DNAs of T7 and P22 are both organized in a similar fashion within their respective capsids. The results show that the condensed genome does not contain kinks or folds that would disrupt the local <i>B</i> conformation by more than 2%. The present findings are discussed in relation to previously proposed models for condensation and organization of double-stranded and single-stranded viral DNA. © 1998 John Wiley &amp; Sons, Inc. Biospectroscopy 4: S47–S56, 1998</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"4 S5","pages":"S47-S56"},"PeriodicalIF":0.0,"publicationDate":"1999-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1998)4:5+<S47::AID-BSPY6>3.0.CO;2-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"20701092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 39
Insight into externally bound 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrinatopalladium(II), PdP(2), with B-form DNA duplexes poly(G-C)2, poly(A-T)2, and CT DNA by using combined MCD, CD, and optical data 通过结合MCD, CD和光学数据,深入了解外部结合的5,10,15,20-tetrakis(2- n -methylpyridyl)卟啉atopalladium(II), PdP(2),具有b型DNA双链poly(G-C)2, poly(A-T)2和CT DNA
Biospectroscopy Pub Date : 1999-01-06 DOI: 10.1002/(SICI)1520-6343(1998)4:5<341::AID-BSPY5>3.0.CO;2-E
N. Randy Barnes, Anton F. Schreiner, Michael G. Finnegan, Michael K. Johnson
{"title":"Insight into externally bound 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrinatopalladium(II), PdP(2), with B-form DNA duplexes poly(G-C)2, poly(A-T)2, and CT DNA by using combined MCD, CD, and optical data","authors":"N. Randy Barnes,&nbsp;Anton F. Schreiner,&nbsp;Michael G. Finnegan,&nbsp;Michael K. Johnson","doi":"10.1002/(SICI)1520-6343(1998)4:5<341::AID-BSPY5>3.0.CO;2-E","DOIUrl":"10.1002/(SICI)1520-6343(1998)4:5<341::AID-BSPY5>3.0.CO;2-E","url":null,"abstract":"<p>The Soret (<i>B</i><sub>0</sub>) region of free and externally DNA-bound 5,10,15,20-tetrakis(2-<i>N</i>-methylpyridyl)porphyrinatopalladium(II), <b>PdP(2)</b>, was investigated by electronic magnetic circular dichroism (MCD), natural circular dichroism (CD), and optical (UV-visible) absorption spectroscopies. We conclude that four-coordinate, “thick” <b>PdP(2)</b> binds to the exterior of each of poly(A-T)<sub>2</sub> and calf thymus DNA (CT DNA) by two distinctly different AT-specific minor and major groove modes, with site 5′TA3′ being favored for both modes. The minor groove mode involves an edge-on orientation of <b>PdP(2)</b>, for which porphyrin electric dipole transition moments (edtms) μ<sub><i>x</i></sub> (most perturbed direction of the bound porphyrin) and μ<sub><i>y</i></sub> (least perturbed direction) have approximate orientation angles of α/β/β′ = ∼ 90°/0°/0° and ∼ 45°/0°/90°, respectively. Major groove binding is by a face-on mode, which results in the porphyrin plane being approximately parallel to the helix axis, such that ν<sub><i>x</i></sub> (most perturbed direction) and μ<sub><i>y</i></sub> (least perturbed direction) have approximate orientation angles of α/β/β′ = ∼ 45°/180°/90° and ∼ 45°/180°/270°, respectively. The Soret MCD and optical band alterations upon binding (i.e., sign retention of the tetragonal, genuine MCD (+) <i>A</i>-term on becoming the (+) pseudo-<i>A</i>-term of similar amplitude and small DNA-induced optical red (Δλ) and hypochromic (H) shifts) are all consistent with exterior binding perturbations of the porphyrin's pπ MOs (1<i>a</i><sub>1<i>u</i></sub>3<i>a</i><sub>2<i>u</i></sub> 4<i>e</i><sub><i>g</i></sub>) by the A and T bases of each polymer being weaker than caused by intercalation. Furthermore, that the (+) <i>A</i>-term of <b>PdP(2)</b> retains the (+) sign upon binding informs that the 4<i>e</i><sub><i>g</i></sub> splitting, or ΔLUMO, is less than the energy separation |1<i>a</i><sub>1<i>u</i></sub>-3<i>a</i><sub>2<i>u</i></sub>|, or ΔHOMO. For the third system, <b>PdP(2)</b>/poly(G-C)<sub>2</sub>, the <i>B</i><sub>0</sub> CD spectrum has two extremely weak (+) and (−) CD bands at higher and lower energy, respectively, indicating that weak outside binding (wob) interactions are taking place between the cationic porphyrin and the electron-rich phosphate backbone of this rigid polymer. The composite of our CD, MCD, and optical data are suggestive of a face-on mode at the GC major groove. Band parameter extraction is performed on the Soret CD and MCD bands of each of the three bound systems, and it is determined that (1) very little spatial rotation of molecular charge is induced during CD excitation and (2) the excited state angular momentum, 〈<i>L</i><sub><i>j</i></sub>〉, changes very little upon binding of <b>PdP(2)</b> to each duplex. These findings are also consistent with each <b>PdP(2)</b>/B-DNA interaction not being very strong. © 1998 John Wiley &amp; Sons, Inc. Biospectroscopy 4: 341","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"4 5","pages":"341-352"},"PeriodicalIF":0.0,"publicationDate":"1999-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1998)4:5<341::AID-BSPY5>3.0.CO;2-E","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75040059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 7
Applications of Raman spectroscopy to ophthalmology: Spectroscopic characterization of disposable soft contact lenses 拉曼光谱在眼科的应用:一次性软性隐形眼镜的光谱表征
Biospectroscopy Pub Date : 1999-01-06 DOI: 10.1002/(SICI)1520-6343(1998)4:6<413::AID-BSPY6>3.0.CO;2-G
P. Monti, R. Simoni, R. Caramazza, A. Bertoluzza
{"title":"Applications of Raman spectroscopy to ophthalmology: Spectroscopic characterization of disposable soft contact lenses","authors":"P. Monti,&nbsp;R. Simoni,&nbsp;R. Caramazza,&nbsp;A. Bertoluzza","doi":"10.1002/(SICI)1520-6343(1998)4:6<413::AID-BSPY6>3.0.CO;2-G","DOIUrl":"10.1002/(SICI)1520-6343(1998)4:6<413::AID-BSPY6>3.0.CO;2-G","url":null,"abstract":"<p>Disposable soft contact lenses based on HEMA–MAA hydrogels are examined using Raman and ATR/FTIR vibrational spectroscopies and thermal analysis. The main factors dealing with physical, chemical, and biological biocompatibility are evaluated in relation to those of long-wear soft contact lenses with the aim of individuating the most biocompatible lens. The Raman spectra of HEMA–MAA lenses show that some biocompatibility factors are affected by environmental conditions and, in particular, by changes in pH and ionic strength values. © 1998 John Wiley &amp; Sons, Inc. Biospectroscopy 4: 413–419, 1998</p>","PeriodicalId":9037,"journal":{"name":"Biospectroscopy","volume":"4 6","pages":"413-419"},"PeriodicalIF":0.0,"publicationDate":"1999-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/(SICI)1520-6343(1998)4:6<413::AID-BSPY6>3.0.CO;2-G","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75908218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 7
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