Photolysis of 1 in argon-saturated acetonitrile yields 2, whereas in oxygen-saturated acetonitrile small amounts of benzoic acid and benzamide are formed in addition to 2. Similarly, photolysis of 2 in argon-saturated acetonitrile results in 1 and a trace amount of 3, whereas in oxygen-saturated acetonitrile the major product is 1 in addition to the formation of small amounts of benzoic acid and benzamide. Laser flash photolysis of 1 results in an absorption due to triplet vinylnitrene 4 (broad absorption with λ(max) at 360 nm, τ = 1.8 μs, acetonitrile) that is formed with a rate constant of 1.2 × 10(7) s(-1) and decays with a rate constant of 5.6 × 10(5) s(-1). Laser flash photolysis of 2 in argon-saturated acetonitrile likewise results in the formation of triplet vinylnitrene 4 but also ylide 5 (λ(max) at 440 nm, τ = 13 μs). The rate constant for forming 4 in argon-saturated acetonitrile is 1.6 × 10(7) s(-1). In oxygen-saturated acetonitrile, vinylnitrene 4 reacts to form the peroxide radical 6 (λ(max) 360 nm, ~0.7 μs, acetonitrile) at a rate of 2 × 10(9) M(-1) s(-1). Density functional theory calculations were performed to aid in the characterization of vinylnitrene 4 and peroxide 6 and to support the proposed mechanism for the formation of these intermediates.

Serendipity in the library stacks is generally regarded as a positive occurrence. While acknowledging its benefits, this essay draws on research in library science, information systems, and other fields to argue that, in two important respects, this form of discovery can be usefully framed as a problem. To make this argument, the essay examines serendipity both as the outcome of a process situated within the information architecture of the stacks and as a user perception about that outcome.

Depressed economic times often lead libraries to consider new practices, including alternatives to the traditional subscription model. This column discusses a pay-per-view (PPV) model for acquiring journal articles whereby a library creates an account with a content provider through which authenticated users can purchase articles at the library's expense. To gain insight into the current use of this model, the paper draws on both a literature review and the results of a survey assessing the practices of academic libraries with experience acquiring articles through unmediated, user-initiated pay-per-view transactions. The future of the PPV model as well as issues and challenges that it raises are also considered.

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IdealMany in the library profession insist on the crucial importance of securing perpetual access rights for acquisitions in electronic formats. In a widely cited article, for example, JimStemper and Susan Barribeau assess the current environment for perpetual access and advocate that, when negotiating e-journal acquisitions, libraries "should consider making the lack of