The vibrational Stark effect (VSE) has proven to be an effective method for the study of electric fields in proteins via the use of infrared probes. In order to explore the use of VSE in nucleic acids, the Stark spectroscopy of nine structurally diverse nucleosides was investigated. These nucleosides contained nitrile or azide probes in positions that correspond to both the major and minor grooves of DNA. The nitrile probes showed better characteristics and exhibited absorption frequencies over a broad range; i.e., from 2253 cm −1 for 2′-O-cyanoethyl ribonucleosides 8 and 9 to 2102 cm −1 for a 13 C-labeled 5-thiocyanatomethyl-2'-deoxyuridine 3c. The largest Stark tuning rate observed was |Δµ| = 1.1 cm −1 /(MV/cm) for both 5-cyano-2′-deoxyuridine 1 and N2-nitrile-2′-deoxyguanosine 7. The latter is a particularly attractive probe because of its high extinction coefficient (ε = 412 M −1 cm −1 ) and ease of incorporation into oligomers.
Overuse injuries of the lateral and medial elbow are common in sport, recreational activities, and occupational endeavors. They are commonly diagnosed as lateral and medial epicondylitis; however, the pathophysiology of these disorders demonstrates a lack of inflammation. Instead, angiofibroblastic degeneration is present, referred to as tendinosis. As such, a more appropriate terminology for these conditions is epicondylosis. This is a clinical diagnosis, and further investigations are only performed to rule out other clinical entities after conventional therapy has failed. Yet, most patients respond to conservative measures with physical therapy and counterforce bracing. Corticosteroid injections are effective for short-term pain control but have not demonstrated long-term benefit.
[reaction: see text] Silatranyluridine 1 and germatranyluridine 2 have been prepared in five steps from oxazolinouridine 3 in 27 and 29% yields, respectively. These compounds are novel transition-state analogues (TSAs) for RNA hydrolysis and offer a number of advantages over traditional vanadium- or rhenium-based TSAs. Germatrane 2 is completely stable in D(2)O at room temperature, and the half-life of silatrane 1 in D(2)O was found to be >7 days by (1)H NMR spectroscopy.
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