Optical spectroscopic methods for intraoperative diagnosis

Molecular analytical methods are increasingly needed for a quick and reliable analysis of tissue in an operating room to provide more information during operations. In this Trends article, we highlight the current state and the developments of optical spectroscopic methods as intra operative tools. The clinical problem and challenges are illustrated on the example of brain tumor surgery. While fluorescence microscopy is already used, vibrational spectroscopy techniques will complement the standard method for brain tissue diagnostics. New portable instruments are currently available and can be stationed in the operating room for quick evaluation of tissue. The promise and limitations of fluorescence and vibrational spectroscopy as intraoperative tools are surveyed in this report.     

Simultaneous Raman and fluorescence spectroscopy of single conjugated polymer chains

Simultaneous surface enhanced Raman scattering (SERS) and fluorescence is demonstrated from single conjugated polymer chains. As resonance enhancement of SERS depends on the spectral overlap of the polymer's absorption and the incident laser, resonance Raman and fluorescence effectively probe the absorbing and emitting part of the polymer, respectively. The optical phonon energies change along the polymer chain, providing a window to spatially track excited state relaxation. Whereas a mean spatial redistribution of the excitation is witnessed by a change in vibronic fingerprint following interchromophoric energy transfer, intrachromophoric exciton self-trapping leaves the vibrations unchanged.     

Subcentimeter depth resolution using a single-photon counting time-of-flight laser ranging system at 1550 nm wavelength

We demonstrate subcentimeter depth profiling at a stand off distance of 330 m using a time-of-flight approach based on time-correlated single-photon counting. For the first time to our knowledge, the photon-counting time-of-flight technique was demonstrated at a wavelength of 1550 nm using a superconducting nanowire single-photon detector. The performance achieved suggests that a system using superconducting detectors has the potential for low-light-level and eye-safe operation. The system's instrumental response was 70 ps full width at half-maximum, which meant that 1 cm surface-to-surface resolution could be achieved by locating the centroids of each return signal. A depth resolution of 4 mm was achieved by employing an optimized signal-processing algorithm based on a reversible jump Markov chain Monte Carlo method.     

The Berkeley Center for Structural Biology at the Advanced Light Source

The Berkeley Center for Structural Biology (BCSB) operates and develops a suite of protein crystallography beamlines at the Advanced Light Source (ALS) located at Lawrence Berkeley National Laboratory (LBNL). Although the ALS was conceived as a low-energy (1.9-GeV), third-generation synchrotron source of vacuum ultraviolet (VUV) and soft X-ray radiation, it was realized during the development of the facility in the mid-1990s that a multipole wiggler coupled with brightness-preserving optics would result in a beamline whose performance in the energy range of 5 to 15 keV would be sufficient for most protein crystallographic experiments. Later, the hard X-ray capabilities of the ALS were expanded by the addition of three superconducting bending magnets, resulting in additional protein crystallography facilities at the ALS [1 A.A. MacDowell, J Synchrotron Radiation 11(6), 447–55 (2004).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]].     

The Electronic Ground State of [Fe(CO)3(NO)]−: A Spectroscopic and Theoretical Study

During the past 10 years iron‐catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion [Fe(CO)₃(NO)]^?, which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with [Fe(CO)₄]^2?, which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate [Fe(CO)₃(NO)]^? cannot be regarded as a Fe^?II species, but rather is predominantly a Fe⁰ species, in which the metal is covalently bonded to NO^? by two π‐bonds. A metal–N σ‐bond is not observed.     

Fe or FeNO Catalysis? A Quantum Chemical Investigation of the [Fe(CO)3(NO)]−‐Catalyzed Cloke–Wilson Rearrangement

A quantum chemical investigation of the Bu₄N[Fe(CO)₃(NO)]‐catalyzed Cloke–Wilson rearrangement of vinyl cyclopropanes is reported. It was found that allylic C?C bond activation can proceed through a S_N2′ or S_N2‐type mechanism. The application of the recently reported intrinsic bond orbital (IBO) method for all structures indicated that one Fe?N π bond is directly involved. Further analysis showed that during the reaction oxidation occurs at the NO ligand exclusively.     

The [(NHC)B(H)C6F5]+ Cations and Their [B](H)−CO Borane Carbonyls

Hydride abstraction from the heterocyclic carbene borane adducts (NHC)BH₂C₆F₅ (NHC: IMes or IMe₄) gave the B−H containing [(NHC)B(H)C₆F₅]⁺ borenium cations. They added carbon monoxide to give the respective [(NHC)B(H)(C₆F₅)CO]⁺ boron carbonyl cations. Carbon nucleophiles add to the boron carbonyl to give [B](H) acyls. Hydride reduced the [B]CO cation to hydroxymethylborane derivatives.     

Photochemical Transformations with Iodine Azide after Release from an Ion‐Exchange Resin

This report discloses the photochemical homolytic cleavage of iodine azide after its formation following release from polymer‐bound bisazido iodate(I) anions. A series of radical reactions are reported including the 1,2‐functionlization of alkenes and the unprecedented chemoselective oxidation of secondary alcohols in the presence of primary alcohols.     

Defect Structure in Te-doped GaAs single Crystals after Plastic Deformation (I). Twins and Stacking Faults

At temperatures above the brittle-to-ductile transition (490 °C) in Te-doped GaAs three types of predominant defect configurations have been observed after uniaxial compression along a [001] direction: (i) twins and stacking faults (500 … 520 °C), (ii) slip zones of dislocations (≈ 550 °C) and (iii) dislocation cells (580 … 590 °C). In Part I quantitative details of the appearance of twins and stacking faults are given. Most frequently found were 30° partials in twins and stacking faults.