Multivariate determination of 13CO2/12CO2 ratios in exhaled mouse breath with mid-infrared hollow waveguide gas sensors

The ¹²CO₂/¹³CO₂ isotope ratio is a well-known marker in breath for a variety of biochemical processes and enables monitoring, e.g., of the glucose metabolism during sepsis. Using animal models—here, at a mouse intensive care unit—the simultaneous determination of ¹²CO₂ and ¹³CO₂ within small volumes of mouse breath was enabled by coupling a novel low-volume hollow waveguide gas cell to a compact Fourier transform infrared spectrometer combined with multivariate data evaluation based on partial least squares regression along with optimized data preprocessing routines.     

Radical Protection by Differently Composed Creams in the UV/VIS and IR Spectral Ranges

Modern sunscreens are well suited to provide sufficient protection in the UV range because the filter substances absorb or scatter UV radiation. Although up to 50% of radicals are formed in the visible and infrared spectral range during solar radiation protection strategies are not provided in this range. Previous investigations of commercially available products have shown that in addition to physical filters, antioxidants (AO) are necessary to provide protective effects in the infrared range by neutralizing already formed radicals. In this study, the efficacy of filter substances and AO to reduce radical formation in both spectral ranges was investigated after UV/VIS or IR irradiation. Optical properties and radical protection were determined for the investigated creams. It was found that organic UV filters lower radical formation in the UV/VIS range to 35% compared to untreated skin, independent of the presence of AO. Further reduction to 14% was reached by addition of 2% physical filters, whereas physical filters alone were ineffective in the UV/VIS range due to the low concentration. In contrast, this filter type reduced radical formation in the IR range significantly to 65%; similar effects were aroused after application of AO. Sunscreens which contain organic UV filters, physical filters and AO ensure protection in the complete solar spectrum.     

A New Clathrate Featuring a Spiro-Type Ammonium Host. X-Ray Structure of the Inclusion Compound with Chloroform

A new onium salt host molecule 1 featuring a spiro-type ammonium backbone was synthesized and shown to form a crystalline inclusion compound with chloroform, 1 · chloroform (1:2), the crystal structure of which is reported. The host molecular interactions including C–H···Br, Cl···Cl and aromatic stacking contacts are typical of the packing structure.     

Bivariate hypergeometric D-modules

We undertake the study of bivariate Horn systems for generic parameters. We prove that these hypergeometric systems are holonomic, and we provide an explicit formula for their holonomic rank as well as bases of their spaces of complex holomorphic solutions. We also obtain analogous results for the generalized hypergeometric systems arising from lattices of any rank.     

Surface-enhanced Raman spectroscopy of DNA

We report a method for obtaining highly reproducible surface-enhanced Raman spectroscopy (SERS) of single and double-stranded thiolated DNA oligomers. Following a protocol that relaxes the DNA into an extended conformation, SERS spectra of DNA oligonucleotides are found to be extremely similar, strongly dominated by the Stokes modes of adenine. A spectral correlation function analysis useful for assessing reproducibility and for quantifying the highly complex changes corresponding to modifications in molecular conformation of the adsorbate molecules is introduced. This approach is used to monitor the interaction of DNA with cisplatin, a chemotherapy agent in widespread use.     

Spectroscopic investigations and crystal structure from synchrotron powder data of the inclusion complex of beta-cyclodextrin with atenolol

Inclusion complexes of atenolol with beta-cyclodextrin (beta-CD) in aqueous solution have been investigated with (1)H NMR and UV-vis spectroscopy. The stoichiometry of this inclusion complex was established to be equimolar (1:1) and its stability constant was determined by UV-vis spectroscopy. The crystal structure of the beta-CD-atenolol (1:1) inclusion compound has been solved from synchrotron powder diffraction data using direct-space search techniques. The crystal structure model and (1)H NMR data are in good agreement and, with support of Hyperchem MM+ molecular dynamics results, suggest which protons are likely to be involved in the inclusion process that leads to the supramolecular architecture of this guest-host complex.     

Assessment of hand-held Raman instrumentation for in situ screening for potentially counterfeit artesunate antimalarial tablets by FT-Raman spectroscopy and direct ionization mass spectrometry

Pharmaceutical counterfeiting has become a significant public health problem worldwide and new, rapid, user-friendly, reliable and inexpensive methods for drug quality screening are needed. This work illustrates the chemical characterization of genuine and fake artesunate antimalarial tablets by portable Raman spectroscopy and validation by FT-Raman spectroscopy and ambient mass spectrometry. The applicability of a compact and robust portable Raman spectrometer (TruScan™) for the in situ chemical identification of counterfeit tablets is reported.     

Comparison of two methods for 14C analysis from essential oils using LSC

Natural essential oil sample obtained from basil (Ocinum basilicum), and ethanol sample obtained from wine were measured to determine ¹⁴C specific activity, using two different sample preparation methods, and liquid scintillation counting method. The paper describes the use of two preparation methods, direct measurement method and CO₂ absorption method, and the results obtained for this comparative study. Depending on carbon content of the sample and bubbling time, different correction factors of carbon mass trapped in liquid scintillation cocktail were established for CO₂ absorption method.

     

Arbitrary rank jumps for A-hypergeometric systems through Laurent polynomials

We investigate the solution space of hypergeometric systemsof differential equations in the sense of Gel’fand, Graev,Kapranov and Zelevinski. For any integer d 2, we constructa matrix A_(d) ^{d x 2d} and a parameter vector ß_(d)such that the holonomic rank of the A-hypergeometric systemH_A(d)(ß_(d)) exceeds the simplicial volume vol(A_(d))by at least d – 1. The largest previously known gap betweenrank and volume was 2. Our construction gives evidence to the general observation thatrank jumps seem to go hand in hand with the existence of multipleLaurent (or Puiseux) polynomial solutions.     

Identification and synthesis of novel biomaterials based on spider structural silk fibers

The diversity in function and mechanical behavior of spider silks, and the ability to produce these silks recombinantly, have tremendous potential in creating a new class of biomimetic materials. Here we investigate the structural and mechanical properties of pyriform silks from the golden orb-weaver, Nephila clavipes. Nanoscale indentation measurements using atomic force microscopy on natural pyriform silk suggests that this biomaterial has high toughness that may be suitable for dissipating high amounts of mechanical energy. We also observed the occurrence of highly organized nanocrystals within the pyriform silk fibers that may contribute to the remarkable energy dissipation capability of these silks. It has been demonstrated that poly-(Gly–Ala) and poly-Ala stretches within the internal block repeat modules of dragline silk fibroins form nanocrystals, and these nanocrystalline structures may be responsible for the high extensibility of the dragline silks. In contrast, amino acid sequence analysis shows that PySp2 does not contain the same motifs. In the absence of poly-(Gly–Ala) and poly-Ala repeats, we hypothesized that PySp2 contains new protein motifs sufficient to polymerize into functional structures. To investigate the functional contributions of these novel motifs during pyriform fiber formation, we expressed different recombinant PySp2 fibroins with various segments spanning its block repeat units. We demonstrate that PySp2 recombinant proteins with the Pro-rich sub-block domain (PXP motifs, where X= sub-set of the amino acids A, L, or R) and/or the Ser + Gln + Ala-rich sub-block domain (QQSSVAQS motifs) are sufficient for artificial fiber formation. Moreover, we show that recombinant PySp2 proteins that contain a single block repeat unit can self-assemble into foam-like nanostructures. Collectively, our findings support the use of PySp2 recombinant proteins for a wide range of biomimetic materials with morphologies ranging from fibers to porous structures.