Wavelength-dependent rearrangements of an α-dione chromophore: a chemical pearl in a bis(hypersilyl) oyster.

The symmetric bissilyl-dione 3 reveals two well-separated n → π* absorption bands at λmax = 637 nm (ε = 140 mol-1 dm3 cm-1) and 317 nm (ε = 2460 mol-1 dm3 cm-1). Whereas excitation of 3 at λ = 360/365 nm affords an isolable siloxyketene 4 in excellent yields, irradiation at λ = 590/630 nm leads to the stereo-selective and quantitative formation of the siloxyrane 5. These remarkable wavelength-dependent rearrangements are based on the electronic and steric properties provided by the hypersilyl groups. While the siloxyketene 4 is formed via a hitherto unknown 1,3-hypersilyl migration via the population of a second excited singlet state (S2, λmax = 317 nm, a rare case of anti-Kasha reactivity), the siloxyrane 5 emerges from the first excited triplet state (T1via S1λmax = 637 nm). These distinct reaction pathways can be traced back to specific energy differences between the S2, S1 and T1, an electronic consequence of the bissilyl substited α-dione (the "pearl"). The hypersilyl groups act as protective ''oyster shell", which are responsible for the clean formation of 4 and 5 basically omitting side products. We describe novel synthetic pathways to achieve hypersilyl substitution (3) and report an in-depth investigation of the photorearrangements of 3 using UV/vis, in situ IR, NMR spectroscopy and theoretical calculations.

C=C-Ene-Reductases Reduce the C=N Bond of Oximes.

Although enzymes have been found for many reactions, there are still transformations for which no enzyme is known. For instance, not a single defined enzyme has been described for the reduction of the C=N bond of an oxime, only whole organisms. Such an enzymatic reduction of an oxime may give access to (chiral) amines. By serendipity, we found that the oxime moiety adjacent to a ketone as well as an ester group can be reduced by ene-reductases (ERs) to an intermediate amino group. ERs are well-known enzymes for the reduction of activated alkenes, as of α,ß-unsaturated ketones. For the specific substrate used here, the amine intermediate spontaneously reacts further to tetrasubstituted pyrazines. This reduction reaction represents an unexpected promiscuous activity of ERs expanding the toolkit of transformations using enzymes.

Multienzyme One-Pot Cascade for the Stereoselective Hydroxyethyl Functionalization of Substituted Phenols.

The operability and substrate scope of a redesigned vinylphenol hydratase as a single biocatalyst or as part of multienzyme cascades using either substituted coumaric acids or phenols as stable, cheap, and readily available substrates are reported.

Supplemental oxygen reduces serotonin levels in plasma and platelets during colorectal surgery and reduces postoperative nausea and vomiting.

BACKGROUND AND OBJECTIVE: it has been shown that supplemental oxygen reduces the incidence of postoperative nausea and vomiting (PONV) in patients undergoing colon surgery. Serotonin is a potent trigger of PONV. Theoretically, supplemental oxygen decreases gut ischaemia during surgery and in this way minimizes the release of serotonin. We investigated the release of serotonin during and after colorectal surgery with normal and supplemental oxygen administration. METHODS: patients (n = 53) undergoing colon surgery were randomly assigned to one of two intraoperative ventilation regimens: group A (n = 30) received 80% oxygen and 20% nitrogen mixed with desflurane and group B (n = 23) received 30% oxygen and 70% nitrogen mixed with desflurane. To verify oxygenation status, we measured the arterial oxygen partial pressure (pO2) by blood gas analysis and the intramuscular tissue oxygenation using a polarographic microoxygen sensor (Licox, GMS, Mielkendorf, Germany). Serotonin levels in plasma and in platelets were measured using high-performance liquid chromatography (HPLC) before the beginning of surgery (T0), at the end of surgery (T1), and 2 h (T2), 8 h (T3) and 24 h (T4) postoperatively. PONV was assessed in the early (0-4 h) and overall (0-24 h) postoperative period by an anaesthesiologist unaware of patients' treatment regime. RESULTS: at T1, T2 and T3, serotonin levels were significantly (T1 '80% group' 80 ± 68.2 vs. '30% group' 147 ± 130.5; T2 '80% group' 78.4 ± 61 vs. '30% group' 139 ± 103; T3 '80% group' 76.2 ± 49.5 vs. '30% group' 124 ± 73.7; P < 0.05) reduced in the '80% oxygen group'. Patients in the '80% group' showed a significantly higher pO2 and subcutaneous tissue oxygenation (ptO2). The overall incidence of PONV was significantly reduced in the '80% oxygen group' ('80% group' 7% vs. '30% group' 35%). CONCLUSION: an inspired oxygen fraction of 0.8 reduces serotonin levels significantly and decreases PONV significantly in patients undergoing colon surgery.

Role of oxidative stress and the antioxidant network in cutaneous carcinogenesis.

Melanoma and nonmelanoma skin cancers are among the most prevalent cancers in the human population. Solar ultraviolet radiation is considered a major etiological factor but the relationship between dose, timing, and nature of exposure to tumor development is still unclear. Free radicals are generated by normal physiologic processes, including aerobic metabolism and inflammatory response, but may inflict cellular damage when generation is increased and antioxidant defense mechanisms are overwhelmed. Important findings supporting the free radical hypothesis in skin carcinogenesis are: (1) Reactive oxygen species (ROS) are generated in UVA- and UVB-irradiated skin in excessive doses, (2) the natural cutaneous antioxidant defense is impaired upon UV-exposure, (3) free radicals are involved in all steps of carcinogenesis, (4) supplementation with antioxidants can inhibit skin carcinogenesis, and (5) conditions that increase ROS generation enhance photocarcinogenesis. These findings provide a promising rationale for the development of powerful new antioxidant strategies in the prevention and therapy of skin cancer.