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Rationale: Mass spectrometry imaging (MSI) is a powerful tool for mapping the surface of a sample. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) offer complementary capabilities. Here, we present a workflow to apply both techniques to a single tissue section and combine the resulting data for the example of human colon cancer tissue. Methods: Following cryo-sectioning, images were acquired using the high spatial resolution (1 μm pixel size) provided by TOF-SIMS. The same section was then coated with a para-nitroaniline matrix and images were acquired using AP-MALDI coupled to an Orbitrap mass spectrometer, offering high mass resolution, high mass accuracy and tandem mass spectrometry (MS/MS) capabilities. Datasets provided by both mass spectrometers were converted into the open and vendor-independent imzML file format and processed with the open-source software MSiReader. Results: The TOF-SIMS and AP-MALDI mass spectra show strong signals of fatty acids, cholesterol, phosphatidylcholine and sphingomyelin. We showed a high correlation between the fatty acid ions detected with TOF-SIMS in negative ion mode and the phosphatidylcholine ions detected with AP-MALDI in positive ion mode using a similar setting for visualization. Histological staining on the same section allowed the identification of the anatomical structures and their correlation with the ion images. Conclusions: This multimodal approach using two MSI platforms shows an excellent complementarity for the localization and identification of lipids. The spatial resolution of both systems is at or close to cellular dimensions, and thus spatial correlation can only be obtained if the same tissue section is analyzed sequentially. Data processing based on imzML allows a real correlation of the imaging datasets provided by these two technologies and opens the way for a more complete molecular view of the anatomical structures of biological tissues. [ABSTRACT FROM AUTHOR]

A new method is presented using an optical particle counter and the compact mobile laser mass spectrometer LAMPAS 3 for in situ analysis of single particles generated by electrosurgical dissection of biological tissues. The instrumental performance is demonstrated for analysing aerosol particles formed during rapid thermal evaporation of porcine liver and porcine kidney tissues. Particle number concentrations of up to 5,000 particles per cubic centimetre were detected during surgical dissection. Chemical analysis of tissue particles was performed by bipolar time-of-flight mass spectrometry. The application of an online mass spectrometric particle analysis for surgical aerosols is reported here for the first time. [ABSTRACT FROM AUTHOR]

An important fraction of secondary organic aerosol (SOA) formed by atmospheric oxidation of diverse volatile organic compounds (VOC) has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006), we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI) formed during the ozonolysis reaction, which were CH2O2 (mass 46) for alkyl vinyl ethers (AVE) and C2H4O2 (mass 60) for ethyl propenyl ether (EPE). In the present work, we extend our previous study to another enol ether (ethyl butenyl ether EBE) and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3- dimethyl-2-butene). Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS). SOA filter samples were collected and chemically characterized off-line by ESI(+)/TOF MS and ESI(+)/TOF MS/MS, and elemental compositions were determined by ESI(+)/FTICR MS and ESI(+)/FTICR MS/MS. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI) formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74) for ethyl butenyl ether (EBE), trans-3-hexene, and 2,3-dimethyl- 2-butene, and C4H8O2 (mass 88) for trans-4-octene. Analogous fragmentation pathways among the oligomers formed by gas-phase ozonolysis of he different alkenes and enol ethers in our present and previous study, characterized by successive losses of the respective CI-like chain unit as a neutral fragment, indicate a similar principal structure. In this work, we confirm the basic structure of a linear oligoperoxide - [CH(R)-O-O]n - for all detected oligomers, with the repeated chain unit CH(R)OO corresponding to the respective major CI. The elemental compositions of parent ions, fragment ions and fragmented neutrals determined by accurate mass measurements with the FTICR technique allow us to assign a complete structure to the oligomer molecules. We suggest that the formation of the oligoperoxidic chain units occurs through a new gas-phase reaction mechanism observed for the first time in our present work, which involves the addition of stabilized CI to organic peroxy radicals. Furthermore, copolymerization of CI simultaneously formed in the gas phase from two different unsaturated compounds is shown to occur during the ozonolysis of a mixture of trans-3-hexene and ethyl vinyl ether (EVE), leading to formation of oligomers with mixed chain units C3H6O2 (mass 74) and CH2O2 (mass 46). We therefore suggest oligoperoxide formation by repeated peroxy radical-stabilized CI addition to be a general reaction pathway of small stabilized CI in the gas phase, which represents an alternative way to highmolecular products and thus contributes to SOA formation. [ABSTRACT FROM AUTHOR]

An important fraction of secondary organic aerosol (SOA) formed by atmospheric oxidation of diverse volatile organic compounds (VOC) has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006), we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI) formed during the ozonolysis reaction, which were CH2O2 (mass 46) for alkyl vinyl ethers (AVE) and C2H4O2 (mass 60) for ethyl propenyl ether (EPE). In the present work, we extend our previous study (Sadezky et al., 2006) to another enol ether (ethyl butenyl ether EBE) and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene). Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS). SOA filter samples were collected and chemically characterized off-line by ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF, and elemental compositions were confirmed by ESI(+)/MS/MS-FTICR. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study (Sadezky et al., 2006). Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI) formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74) for ethyl butenyl ether (EBE), trans-3-hexene, and 2,3-dimethyl-2-butene, and C4H8O2 (mass 88) for trans-4-octene. Analogous fragmentation pathways among the oligomers formed by gas-phase ozonolysis of the different alkenes and enol ethers in our present and previous study (Sadezky et al., 2006), characterized by successive losses of the respective CI-like chain unit as a neutral fragment, indicate a similar principal structure. As in our previous work (Sadezky et al., 2006), we suggest the basic structure of a linear oligoperoxide --[CH(R)-O-O]n-- for all detected oligomers, with the repeated chain unit CH(R)OO corresponding to the respective major CI. Furthermore, copolymerization of CI simultaneously formed in the gas phase from two different unsaturated compounds is shown to occur during the ozonolysis of a mixture of trans-3-hexene and ethyl vinyl ether (EVE), leading to formation of oligomers with mixed chain units C3H6O2 (mass 74) and CH2O2 (mass 46). We therefore suggest oligoperoxide formation to be a general, so far unknown reaction pathway of small stabilized CI in the gas phase, which represents an alternative way to high-molecular products and thus contributes to SOA formation. [ABSTRACT FROM AUTHOR]

In human neuroblastoma tumors, amplification of the N-myc proto-oncogene and loss of all or part of the short arm of chromosome #1 are both associated with a poor prognosis. Accruing evidence indicates that it is the absence of one allele of the HuD (ELAVL4) gene, encoding the neuronal-specific RNA-binding protein HuD and localized to 1p34, that is linked to amplification. In 12 human neuroblastoma cell lines, N-myc amplification correlates with loss of one HuD allele and decreased HuD expression. Transfection experiments demonstrate that modulating HuD expression affects N-myc gene copy number as well as expression. Introduction of a sense HuD construct into two N-myc amplified cell lines considerably increases N-myc expression whereas gene copy number decreases. Conversely, expression of antisense HuD in N-myc nonamplified SH-SY5Y cells reduces HuD and N-myc mRNA levels even as cells show amplification of the N-myc gene. Thus, N-myc gene copy number is modulated by alteration of HuD expression. We propose that haploinsufficiency of HuD due to chromosome #1p deletion in neuroblastoma selects for cells that amplify N-myc genes. Application of these findings could lead to more effective therapies in the treatment of those patients with the worst prognosis.Oncogene (2006) 25, 706–712. doi:10.1038/sj.onc.1209095; published online 7 November 2005 [ABSTRACT FROM AUTHOR]

A special arrangement of combined sewer overflow tanks is the in-line storage sewer with downstream discharge (ISS-down). This layout has the advantage that, besides the sewer system, no other structures are required for stormwater treatment. The verification of the efficiency with respect to the processes of sedimentation and remobilization of sediment within the in-line storage sewer with downstream discharge is carried out in a combination of a field and a pilot plant study. The model study was carried out using a pilot plant model scaled 1:13. The following is intended to present some results of the pilot plant study and the mathematical empirical modelling of the sedimentation and remobilization process. [ABSTRACT FROM AUTHOR]

A special structure of combined sewer overflow tanks is the inline storage sewer with downstream discharge (SKU). This layout has the advantage that besides the sewer system, no other structures are required for storm water treatment. Consequently only very little space is required and compared to combined sewer overflow tanks, there is an enormous potential in reducing costs during construction. To investigate the efficiency of an inline storage sewer, a monitoring station was established in Dortmund-Scharnhorst, Germany. The monitoring station was in operation for a period of 2.5 years. Within this period water samples were taken during a total of 20 discharge events. Besides the complete hydraulic data collection, seven water samplers took more than 5,000 water samples during dry and wet weather. This adds up to a total of more than 20,000 individual lab analyses. The average of the total efficiency for the SKU-West is 86%. 29% of this efficiency can be attributed to the throttle flow. The remaining 57% can be divided into a part of 48% that can be attributed to the process storage and 9% that can be attributed to sedimentation and erosion process. [ABSTRACT FROM AUTHOR]

A new mobile mass spectrometrical acquisition and evaluation system for on-line analysis of single airborne particles and for characterization of particle populations (aerosols), ''LAMPAS 2,'' is described. The modular aerosol inlet system of the instrument can be quickly exchanged with an alternate unit, providing for quasi-continuous long-term operation. The technical design allows for field operation with only a 9 A single phase power supply. Statistical evaluation of large numbers of single particle spectra is performed immediately after acquisition, resulting in a time course resolution for aerosol characterization of about 1 hr. The instrument was first employed in a joint field experiment ''LACE 98'' in July and August 1998, providing for chemical and physical characterization within the framework of other state-of-the-art technologies of characterizing the atmospheric aerosol. [ABSTRACT FROM AUTHOR]

A special structure of combined sewer overflow tanks is the inline storage sewer with downstream discharge (SKU). This layout has the advantage that besides the sewer system, no other structures are required for storm water treatment. Consequently only very little space is required and compared to combined sewer overflow tanks, there is an enormous potential in reducing costs during construction. To investigate the efficiency of an inline storage sewer, a monitoring station was established in Dortmund-Scharnhorst, Germany. The monitoring station was in operation for a period of 2.5 years. Within this period water samples were taken during a total of 20 discharge events. Besides the complete hydraulic data collection, seven water samplers took more than 5,000 water samples during dry and wet weather. This adds up to a total of more than 20,000 individual lab analyses. The average of the total efficiency for the SKU-West is 86%. 29% of this efficiency can be attributed to the throttle flow. The remaining 57% can be divided into a part of 48% that can be attributed to the process storage and 9% that can be attributed to sedimentation and erosion process. [ABSTRACT FROM AUTHOR]

The aim of our investigation was to develop carrier systems for an application of inert drugs in photodynamic cancer therapy. β-Cyclodextrin dimers linked at their primary and secondary faces by spacers of varying lengths were synthesized as carrier systems. The binding constants of the inclusion complexes of these cyclodextrin dimers and porphyrinoid photosensitizers were determined by competitive spectrofluorometry. Particularly the secondary face linked dimers exhibited extremely high binding constants with values of 106-107 L/mol. Theoretical studies were carried out on these inclusion complexes to confirm the influence of spacer length and connecting side on complex stability. [ABSTRACT FROM AUTHOR]