Quantification of brain lipids by FTIR spectroscopy and partial least squares regression

Brain tissue is characterized by high lipid content. Its content decreases and the lipid composition changes during transformation from normal brain tissue to tumors. Therefore, the analysis of brain lipids might complement the existing diagnostic tools to determine the tumor type and tumor grade. Objective of this work is to extract lipids from gray matter and white matter of porcine brain tissue, record infrared (IR) spectra of these extracts and develop a quantification model for the main lipids based on partial least squares (PLS) regression. IR spectra of the pure lipids cholesterol, cholesterol ester, phosphatidic acid, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, sphingomyelin, galactocerebroside and sulfatide were used as references. Two lipid mixtures were prepared for training and validation of the quantification model. The composition of lipid extracts that were predicted by the PLS regression of IR spectra was compared with lipid quantification by thin layer chromatography.     

Basic reactivity of CaO: investigating active sites under operating conditions

A set of CaO samples was prepared from thermal decomposition of several precursors, leading to very different surface properties. During storage, CaO samples rehydrated quickly but reversibly. Before characterization, the samples were pre-treated at 1023 K under nitrogen flow to obtain CaO as the active phase. Although this pre-treatment led to almost the same specific surface areas for all samples, their basic reactivity levels toward 2-methylbut-3-yn-2-ol conversion were different from one preparation to another. In contrast with the properties of MgO pre-treated at the same temperature, the basic reactivity of CaO correlates neither with the concentration of surface defects (exposing ions in low coordination) determined by photoluminescence nor with the deprotonation ability toward methanol. In order to identify the active sites on CaO pre-treated under nitrogen in the temperature range 673 K-1023 K, OH groups were quantified with (1)H NMR: the higher the surface density of OH groups, the higher the basic reactivity. Even after pre-treatment at 1023 K, after which only a few hydroxyls remain, the basic reactivity is governed by the remaining hydroxylation of the surface. The higher reactivity of OH groups of CaO compared to those of Ca(OH)(2) and MgO is discussed.     

Delimitation of squamous cell cervical carcinoma using infrared microspectroscopic imaging

Infrared (IR) spectroscopic imaging coupled with microscopy has been used to investigate thin sections of cervix uteri encompassing normal tissue, precancerous structures, and squamous cell carcinoma. Methods for unsupervised distinction of tissue types based on IR spectroscopy were developed. One-hundred and twenty-two images of cervical tissue were recorded by an FTIR spectrometer with a 64×64 focal plane array detector. The 499,712 IR spectra obtained were grouped by an approach which used fuzzy C-means clustering followed by hierarchical cluster analysis. The resulting false color maps were correlated with the morphological characteristics of an adjacent section of hematoxylin and eosin-stained tissue. In the first step, cervical stroma, epithelium, inflammation, blood vessels, and mucus could be distinguished in IR images by analysis of the spectral fingerprint region (950–1480 cm⁻¹). In the second step, analysis in the spectral window 1420–1480 cm⁻¹ enables, for the first time, IR spectroscopic distinction between the basal layer, dysplastic lesions and squamous cell carcinoma within a particular sample. The joint application of IR microspectroscopic imaging and multivariate spectral processing combines diffraction-limited lateral optical resolution on the single cell level with highly specific and sensitive spectral classification on the molecular level. Compared with previous reports our approach constitutes a significant progress in the development of optical molecular spectroscopic techniques toward an additional diagnostic tool for the early histopathological characterization of cervical cancer.     

Phosphorus. From elemental light to chemical element

Exactly 300 years ago in the city of Hamburg, a certain Hennig Brand, self-styled doctor medicinae, and chymist, discovered a strange substance in human urine, which was later called phosphorus (light bearer), a name then common to various luminous substances, and which created much excitement in the latter years of the 17th century on account of its properties. However, it was not Brand who profited from the discovery but others: Johann Daniel Krafft, Johann Kunckel, and Gottfried Wilhelm Leibniz, men who knew only too well how to exploit the weaknesses of the discoverer. “Cold fire”, Brand's own name for the new substance, was originally regarded as elemental light or fire, and it was not until the conception of the antiphlogistic theory by Antoine Laurent Lavoisier that the proper position of phosphorus among the chemical elements was recognized. In fact, the element played a decisive role in the overthrow of the phlogiston doctrine, a little over one hundred years after its discovery and almost two hundred years ago.     

连续波锁模P_r~（3＋）：YLF激光器

本文报导了采用氩离子激光器来泵浦Ｒｒ￣（３＋）：ＹＬＦ晶体，应用声光调制器实现了主动锁模；同时应用振动─高反射平面镜也实现了被动锁模，两种锁模均得到了ｐｓ光脉冲。据作者了解这是这种晶体材料的第一次锁模运转。     

Sample size planning for classification models

In biospectroscopy, suitably annotated and statistically independent samples (e.g. patients, batches, etc.) for classifier training and testing are scarce and costly. Learning curves show the model performance as function of the training sample size and can help to determine the sample size needed to train good classifiers. However, building a good model is actually not enough: the performance must also be proven. We discuss learning curves for typical small sample size situations with 5–25 independent samples per class. Although the classification models achieve acceptable performance, the learning curve can be completely masked by the random testing uncertainty due to the equally limited test sample size. In consequence, we determine test sample sizes necessary to achieve reasonable precision in the validation and find that 75–100 samples will usually be needed to test a good but not perfect classifier. Such a data set will then allow refined sample size planning on the basis of the achieved performance. We also demonstrate how to calculate necessary sample sizes in order to show the superiority of one classifier over another: this often requires hundreds of statistically independent test samples or is even theoretically impossible. We demonstrate our findings with a data set of ca. 2550 Raman spectra of single cells (five classes: erythrocytes, leukocytes and three tumour cell lines BT-20, MCF-7 and OCI-AML3) as well as by an extensive simulation that allows precise determination of the actual performance of the models in question.     

Functionalization of furans via phenacyl sulfides

A mild, efficient, photochemical method for the functionalization of furans via phenacyl sulfides is described.     

Small-Angle Scattering and Electron Microscopy Investigation of Nanotubules Made from a Perfluoroalkylated Glucophospholipid

Anionic glucophospholipids were recently reported as a new family of tubule-forming lipids. We report here investigations on the structure of nanotubules made from a glucophospholipid with a mixed fluorocarbon-hydrocarbon hydrophobe, using freeze fracture and cryo-transmission electron microscopy (TEM) and X-ray and neutron small angle scattering (SAXS, SANS). The hollow and regularly shaped tubules are very thin: they have an external radius of 140 ? and an internal radius of 35 ? on the average. Their 105 ?-thick wall appears to consist in three bilayers in which the glucophospholipid molecules are probably in a tilted and/or interdigitated configuration. Upon heating these nanotubes convert reversibly into vesicles; transformation is complete at 60 degrees C. Copyright 1999 Academic Press.     

Lise Meitner: Her Life and Times—On the Centenary of the Great Scientist's Birth

Cooperation between the three scientists Lise Meitner, Otto Hahn, and Fritz Strassmann in the study of the “transuranics” (1934—1938) prepared the way for the chemical identification of a first fission product of uranium by Otto Hahn and Fritz Strassmann at the end of 1938. Together with her nephew Otto Robert Frisch, she also gave the first theoretical interpretation of that experimental finding (barium instead of the expected radium) and suggested the inert gas krypton to be the second fission products, which Hahn and Strassmann subsequently identified (besides xenon) among the products. But she was kept from direct participation in the experiments conducted at the Kaiser Wilhelm Institute for Chemistry at Berlin—and therefore from the unrestricted claim to being co-discoverer of uranium fission—because she was an Austrian “Jewess”. Thus after the “annexation” of Austria by the German Reich, the Nazi racial laws also applied to her and precluded her continuing to work in Germany. She therefore emigrated illegally via Holland to Sweden in the middle of 1938. There she continued to work on problems of nuclear physics under less favorable conditions untill 1960. Work on radioactivity already started at Vienna had also brought her together with Hahn at Berlin in 1907, and she continued the work at the Kaiser Wilhelm Institute studying α-, β-, and γ-radiation and related nuclear processes. Not only because of her descent, but also because of her status of a woman in science, her fate was molded by the circumstances prevailing in Germany prior to World War II. On November 7, 1978 Lise Meitner would have celebrated her hundredth birthday, reason enough for recalling her lot as a woman scientist in Germany against the background of her times, which should stand as a warning to us. To that end contemporary documents could be quoted which till now were largely unknown.