Angular Flow in Toroid Cavity Probes

NMR signals from samples that rotate uniformly about the central conductor of a TCD (toroid cavity detector) exhibit frequency shifts that are directly proportional to the sample's angular velocity. This newly observed effect is based on the unique radiofrequency field inside TCDs, which is variable in direction. If a liquid sample is pumped through a capillary tube wound about the central conductor, the frequency shift is proportional to the flow rate. A mathematical relationship between a volumetric flow rate and the frequency shift is established and experimentally verified to high precision. Additionally, two-dimensional flow-resolved NMR spectroscopy for discrimination between components with different flow velocities yet retaining chemical shift information for structural analysis is presented. The application of the two-dimensional method in chromatographic NMR is suggested. Furthermore, utilization of the frequency-shift effect for rheologic studies if combined with toroid-cavity rotating-frame imaging is proposed.     

Special phase mask and related data format for page-based holographic data storage systems

Random phase masks in object and reference beam of page-based holographic storage systems suppress the DC-peak and improve the overlap of both beams inside the storage material. Furthermore, they allow for a narrow shift-selectivity. In a holographic setup the phase mask has to be introduced at a conjugate image plane of the spatial light modulator (SLM), if it is not fixed directly on the SLM itself. A binary phase mask with cells generating 0 and π phase shifts has to be aligned very accurately with respect to the SLM pixels, otherwise image artifacts disturb the received data page. We present a phase mask, where the phase cells have the size of a data block which consists of a rectangular set of SLM pixels. Additionally, the corresponding data page has no data at the position of phase jumps and thus relaxes the alignment tolerance significantly.     

Effect of fluorination: gas-phase structures of N,N-dimethylvinylamine and perfluoro-N,N-dimethylvinylamine.

The gas-phase structures of N,N-dimethylvinylamine, (CH(3))(2)NC(H)=CH(2) (1), and perfluoro-N,N-dimethylvinylamine, (CF(3))(2)NC(F)=CF(2) (2), were determined by gas electron diffraction and quantum chemical methods (B3LYP and MP2 with 6-31G basis sets). The configuration around nitrogen is slightly pyramidal in both compounds, with the sum of the nitrogen bond angles 351.2(12) degrees and 354.8(6) degrees in 1 and 2, respectively. In the parent compound 1, the (CH(3))(2)N group lies nearly in the plane of the vinyl group, and the nitrogen lone pair (lp) is almost perpendicular to this plane (Phi(C=C-N-lp) = 98(6) degrees). In the perfluorinated species 2, however, the (CF(3))(2)N group is oriented perpendicular to the vinyl plane, and the lone pair is parallel to the C=C bond (Phi(C=C-N-lp) = 2(5) degrees). A natural bond orbital analysis provides a qualitative explanation for this conformational change upon fluorination. The sterically unfavorable in-plane orientation of the dimethylamino group in 1 is stabilized by conjugation between the nitrogen lone pair and the C=C pi-bond. The anomeric effect between the lone pair and the C(alpha)-F sigma-bond in addition to steric effects favors the perpendicular orientation of the (CF(3))(2)N group in 2. Both quantum chemical methods reproduce the experimental structures satisfactorily.     

Zur Existenz vollständiger Orthogonal-Systeme,welche kein multiplikativ-orthogonales Teilsystem enthalten

Ohne Zusammenfassung     

Hausdorff-summability of power series i

Let A be a regular summability method and P(w)=a_kw^k a power series with positive radius of convergence. A theorem of Okada states, that P(w) is summable (A) for w in the region, where M_P is the Mittag-Leffler-star of P and R _A is the largest star-shaped open region, such that w^k is uniformly summable (A) on each of its compact subsets. The question remains open, whether P(w) might be summable (A) when w is outside of the closure of G. In this paper the question is answered for the class of Hausdorff methods.     

Zur Konvergenz von Funktionenreihen

Ohne Zusammenfassung     

Biofunctionalization on alkylated silicon substrate surfaces via "click" chemistry

Biofunctionalization of silicon substrates is important to the development of silicon-based biosensors and devices. Compared to conventional organosiloxane films on silicon oxide intermediate layers, organic monolayers directly bound to the nonoxidized silicon substrates via Si-C bonds enhance the sensitivity of detection and the stability against hydrolytic cleavage. Such monolayers presenting a high density of terminal alkynyl groups for bioconjugation via copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC, a "click" reaction) were reported. However, yields of the CuAAC reactions on these monolayer platforms were low. Also, the nonspecific adsorption of proteins on the resultant surfaces remained a major obstacle for many potential biological applications. Herein, we report a new type of "clickable" monolayers grown by selective, photoactivated surface hydrosilylation of α,ω-alkenynes, where the alkynyl terminal is protected with a trimethylgermanyl (TMG) group, on hydrogen-terminated silicon substrates. The TMG groups on the film are readily removed in aqueous solutions in the presence of Cu(I). Significantly, the degermanylation and the subsequent CuAAC reaction with various azides could be combined into a single step in good yields. Thus, oligo(ethylene glycol) (OEG) with an azido tag was attached to the TMG-alkyne surfaces, leading to OEG-terminated surfaces that reduced the nonspecific adsorption of protein (fibrinogen) by >98%. The CuAAC reaction could be performed in microarray format to generate arrays of mannose and biotin with varied densities on the protein-resistant OEG background. We also demonstrated that the monolayer platform could be functionalized with mannose for highly specific capturing of living targets (Escherichia coli expressing fimbriae) onto the silicon substrates.     

Vibrational spectra and gas-phase structure of N-methyl-S,S-bis(trifluoromethyl)sulfimide, CH3N=S(CF3)2

The molecular structure of N-methyl-S,S-bis(trifluoromethyl)sulfimide, CH3N=S(CF3)2, was determined by gas electron diffraction and quantum chemical calculations [B3LYP and MP2 with 6-31+G(2df,p) basis sets]. Furthermore, vibrational spectra, IR (gas) and Raman (liquid), were recorded. These spectra were assigned by comparison with analogous molecules and with calculated frequencies and intensities (HF, B3LYP, and MP2 with 6-311G basis sets). All experimental data and computational methods result in a single conformer with syn orientation of the CH3 group relative to the bisector of the two CF3 groups. The molecule possesses C1 symmetry, slightly distorted from CS symmetry. The N=S bond length in this compound [1.522(10) A] is longer than that in imidosulfur difluorides RN=SF2 [1.476(4) A - 1.487(5) A].