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81.
Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3 %. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.
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For a long time d10‐ML2 fragments have been known for their potential to activate unreactive bonds by oxidative addition. In the development of more active species, two approaches have proven successful: the use of strong σ‐donating ligands leading to electron‐rich metal centers and the employment of chelating ligands resulting in a bent coordination geometry. Combining these two strategies, we synthesized bis‐NHC chelate complexes of nickel(0) and platinum(0). Bis(1,5‐cyclooctadiene)nickel(0) and ‐platinum(0) react with bisimidazolium salts, deprotonated in situ at room temperature, to yield tetrahedral or trigonal‐planar bis‐NHC chelate olefin complexes. The synthesis and characterization of these complexes as well as a first example of C? C bond activation with these systems are reported. Due to the enforced cis arrangement of two NHCs, these compounds should open interesting perspectives for bond‐activation chemistry and catalysis.  相似文献   
84.
The biocatalytic production of flavor naturals that determine chemosensory percepts of foods and beverages is an ever challenging target for academic and industrial research. Advances in chemical trace analysis and post‐genomic progress at the chemistry–biology interface revealed odor qualities of nature’s chemosensory entities to be defined by odorant‐induced olfactory receptor activity patterns. Beyond traditional views, this review and meta‐analysis now shows characteristic ratios of only about 3 to 40 genuine key odorants for each food, from a group of about 230 out of circa 10 000 food volatiles. This suggests the foodborn stimulus space has co‐evolved with, and roughly match our circa 400 olfactory receptors as best natural agonists. This perspective gives insight into nature’s chemical signatures of smell, provides the chemical odor codes of more than 220 food samples, and beyond addresses industrial implications for producing recombinants that fully reconstruct the natural odor signatures for use in flavors and fragrances, fully immersive interactive virtual environments, or humanoid bioelectronic noses.  相似文献   
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The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B3H4+ analogues.  相似文献   
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The European Physical Journal A - We investigated multi-nucleon transfer reactions in collisions of 58Ni + 207Pb and 64Ni + 207Pb at Coulomb barrier energies. The new aspect is that we used a...  相似文献   
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Intermetallic compound TmCu2 crystalizes in the orthorhombic structure, orders antiferromagnetically (AF) and exhibits four different AF phases below T N = 6.5 K. In all these phases the Tm magnetic moment is parallel to the b-axis. The ground-state AF1 (T < 3.4 K) corresponds to the squared-up AF structure with propagation vector 01 = (5/8, 0, 0) and magnetic unit cell 8a × b × c. Narrow phases AF2 and AF3 (3.3 K < T < 3.7 K and 3.6 K < T < 4.6 K) are 'spin-slip'-derivatives from the AF1 structure, yielding propagation vectors 02 = (0.633, 0, 0.02) and 03 = (0.618, 0, 0), respectively. The phase AF4 (4.4 K < T < T N) is then incommensurate transversal spin-wave with the propagation 04 = (0.64, 0, 0). The co-existence of AF phases indicates the first-order transitions between them.  相似文献   
90.
We introduce a new concept for a wavelength-tunable frequency-doubled laser diode with a single control parameter. The concept is based on intracavity frequency doubling in an external resonator geometry with spatial separation of the spectral components. The use of a fan-structured periodically poled LiTaO(3) crystal permits tuning of both the fundamental and the second harmonic simultaneously with one aperture. We demonstrate tunability over more than 10 nm in the blue (480.4 to 490.6 nm) with output powers of the order of 50 nW.  相似文献   
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