Hybridization of oligonucleotide-modified silver and gold nanoparticles in aqueous dispersions and on gold films

Functionalization of silver and gold nanoparticles by 12mer-thiolated homo-oligonucleotides, SA and ST (containing only adenine or thymine, respectively), and their hybridization and dehybridization in aqueous dispersions have been described. In addition, ST and SA were self-assembled onto gold films and hybridized with their complementary pairs, unlabeled or labeled by gold and silver nanoparticles. The base pairing between DNA strands and the types of oligonucleotides (adenine or thymine) attached to the nanoparticles was detected by Polarization Modulated Fourier Transform Infrared Reflection Absorption Spectroscopy (PM-FTIRRAS).     

Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.     

Grid-free DFT implementation of local and gradient-corrected XC functionals

Following an approach to density functional theory calculations based on the matrix representation of operators, we implemented a scheme as an alternative to traditional grid-based methods. These techniques allow integrals over exchange-correlation operators to be evaluated through matrix manipulations. Both local and gradient-corrected functionals can be treated in a similar way. After deriving all the required expressions, selected examples with various functionals are given. Received: 7 March 1998 / Accepted: 21 May 1998 / Published on line: 6 August 1998     

ToF-SIMS measurements with topographic information in combined images

In 2D and 3D time-of-flight secondary ion mass spectrometric (ToF-SIMS) analysis, accentuated structures on the sample surface induce distorted element distributions in the measurement. The origin of this effect is the 45° incidence angle of the analysis beam, recording planar images with distortion of the sample surface. For the generation of correct element distributions, these artifacts associated with the sample surface need to be eliminated by measuring the sample surface topography and applying suitable algorithms. For this purpose, the next generation of ToF-SIMS instruments will feature a scanning probe microscope directly implemented in the sample chamber which allows the performance of topography measurements in situ. This work presents the combination of 2D and 3D ToF-SIMS analysis with topographic measurements by ex situ techniques such as atomic force microscopy (AFM), confocal microscopy (CM), and digital holographic microscopy (DHM). The concept of the combination of topographic and ToF-SIMS measurements in a single representation was applied to organic and inorganic samples featuring surface structures in the nanometer and micrometer ranges. The correct representation of planar and distorted ToF-SIMS images was achieved by the combination of topographic data with images of 2D as well as 3D ToF-SIMS measurements, using either AFM, CM, or DHM for the recording of topographic data.     

Correspondence between de Saint-Venant and Boussinesq. 1: Birth of the Shallow–Water Equations

The Shallow–Water Equations (SWEs), also referred to as the de Saint-Venant equations, constitute the current governing mathematical tool for free-surface water flows. These include, e.g., flood flows in rivers and in urban zones, flows across hydraulic structures as dams or wastewater facilities, flows in the environmental fields, glaciology, or meteorology. Despite this attractiveness, the system of two partial differential equations has an exact mathematical solution only for a limited number of problems of practical relevance.This historical work on the SWEs is based on a correspondence between two 19th-century scientists, de Saint-Venant and Boussinesq. Their well-known papers are thus commented from the point of development of their theory; the input of both scientists is evidenced by their writings, and comments of both to each other that led to what is commonly known as the SWEs. Given the age difference of the two of 45 years, the experienced engineer de Saint-Venant, and the mathematician Boussinesq, two eminent researchers, met to discuss not only problems in hydraulics, but in physics generally. In addition, their correspondence embraced also questions in ethics, religion, history of sciences, and personal news.The results of the SWEs cease to hold if streamline curvature effects dominate; this includes breaking waves, solitary and cnoidal waves, or non-linear waves in general. In most other cases, however, the SWEs perfectly apply to typical flows in engineering practice; they are considered the fundamental system of equations describing open channel flows. This work thus provides a background to its birth, including lots of comments as to its improvement, physical meanings, methods of solution, and a discussion of the results. This paper also deals with the steady flow equations, gives a short account on the main persons mentioned in the Correspondence, and provides a summary of further developments of the SWEs until 1920.     

Detection and identification of the designer benzodiazepine flubromazepam and preliminary data on its metabolism and pharmacokinetics

The appearance of pyrazolam in Internet shops selling ‘research chemicals’ in 2012 marked the beginning of designer benzodiazepines being sold as recreational drugs or ‘self medication’. With recent changes in national narcotics laws in many countries, where two uncontrolled benzodiazepines (phenazepam and etizolam), which were marketed by pharmaceutical companies in some countries, were scheduled, clandestine laboratories seem to turn to poorly characterized research drug candidates as legal substitutes. Following the appearance of pyrazolam, it comes with no surprise that recently, flubromazepam (7‐bromo‐5‐(2‐fluorophenyl)‐1,3‐dihydro‐2H‐1,4‐benzodiazepin‐2‐one), a second designer benzodiazepine, was offered on the market. In this article, this new compound was characterized using nuclear magnetic resonance, gas chromatography‐mass spectrometry (GC–MS), liquid chromatography–mass spectrometry (LC–MS/MS) and liquid chromatography quadrupole time‐of‐flight MS (LC–Q–ToF–MS). Additionally, a study was carried out, in which one of the authors consumed 4 mg of flubromazepam to gain preliminary data on the pharmacokinetic properties and the metabolism of this compound. For this purpose, serum as well as urine samples were collected for up to 31 days post‐ingestion and analyzed applying LC–MS/MS and LC–Q‐ToF‐MS techniques. On the basis of this study, flubromazepam appears to have an extremely long elimination half‐life of more than 100 h. One monohydroxylated compound and the debrominated compound could be identified as the predominant metabolites, the first allowing a detection of a consumption for up to 28 days post‐ingestion when analyzing urine samples in our case. Additionally, various immunochemical assays were evaluated, showing that the cross‐reactivity of the used assay seems not to be sufficient for safe detection of the applied dose in urine samples, bearing the risk that it could be misused in drug‐withdrawal settings or in other circumstances requiring regular drug testing. Furthermore, it may be used in drug‐facilitated crimes without being detected. Copyright © 2013 John Wiley & Sons, Ltd.     

Batch tautomer generation with MolTPC

Besides all their conformational degrees of freedom, drug‐like molecules and natural products often also undergo tautomeric interconversions. Compared to the huge efforts made in experimental investigation of tautomerism, open and free algorithmic solutions for prototropic tautomer generation are surprisingly rare. The few freely available software packages limit their output to a subset of the possible configurational space by sometimes unwanted prior assumptions and complete neglection of ring‐chain tautomerism. Here, we describe an adjustable fully automatic tautomer enumeration approach, which is freely available and also incorporates the detection of ring‐chain variants. The algorithm is implemented in the MolTPC framework and accessible on SourceForge. © 2013 Wiley Periodicals, Inc.     

Important aspects in the formulation of solid–fluid debris-flow models. Part II. Constitutive modelling

This article points at some critical issues which are connected with the theoretical formulation of the thermodynamics of solid–fluid mixtures of frictional materials. It is our view that a complete thermodynamic exploitation of the second law of thermodynamics is necessary to obtain the proper parameterizations of the constitutive quantities in such theories. These issues are explained in detail in a recently published book by Schneider and Hutter (Solid–Fluid Mixtures of Frictional Materials in Geophysical and Geotechnical Context, 2009), which we wish to advertize with these notes. The model is a saturated mixture of an arbitrary number of solid and fluid constituents which may be compressible or density preserving, which exhibit visco-frictional (visco-hypoplastic) behavior, but are all subject to the same temperature. Mass exchange between the constituents may account for particle size separation and phase changes due to fragmentation and abrasion. Destabilization of a saturated soil mass from the pre- and the post-critical phases of a catastrophic motion from initiation to deposition is modeled by symmetric tensorial variables which are related to the rate independent parts of the constituent stress tensors.