Charge reversal of the conjugate base of formamide

Charge reversal collisional activation mass spectremetry of negative ions has been used in conjunction with positive ion collisional activation to investigate several isomeric [H₂, C, N, O]⁺ ions. Generation of m/z 44 ions from formamide, acetamide, JV-methylformamide, acetaldoxime and by charge reversal of the [M–1]^? ion formed from formamide yields several different isomeric structures. Charge reversal of the conjugate base of formamide appears to yield a mixture of singlet and triplet H₂NC?O⁺ ions; experiments with deuterium-labeled compounds have been used to support this. Ab initio molecular orbital calculations indicate that the triplet ion is a stable structure, existing in a potential minimum 390.6 kJ mol^?1 above the ground state singlet.     

Forensic analysis of condom and personal lubricants by capillary electrophoresis

Condoms may offer sexual assailants a simple and relatively effective means by which they may remove and dispose of the biological evidence of their contact with the victim. Without this valuable probative evidence, the investigator may need to turn to such alternative forms of physical evidence, such as the residue remaining from the condom lubricant, and any other additional lubricating substances, which may have been used by the assailant. In this study, 68 different condom and personal lubricant samples were analysed using micellar electrokinetic capillary chromatography (MEKC) with ultraviolet absorbance detection. The electropherograms were processed by principal component analysis (PCA) and classified with linear discriminant analysis. This classified 233 samples out of 263 into their correct sample group. An alternative method of classification in which the sample electropherograms were converted to vectors and a correlation was determined by the cosine of the angles between these vectors. This correctly classified 172 samples of the 296. Results indicate that the combination of CE with chemometric data treatment offers the potential of being a rapid and efficient means by which condom and personal lubricant samples may be differentiated. Although this analytical method at present lacks the sensitivity required for sexual assault swab analysis, it is hoped that future developments in instrumentation detection capabilities will permit its use one day as a routine casework tool.     

Toward a new genetic system with expanded dimensions: size-expanded analogues of deoxyadenosine and thymidine

We describe the design, preparation, and properties of two key building blocks of a size-expanded genetic system. Nucleoside analogues of the natural nucleosides dA and dT are reported in which the fusion of a benzo ring increases their size by ca. 2.4 A. The expanded dA analogue (dxA), having a tricyclic base, was first reported by Leonard nearly three decades ago. We describe a shortened and more efficient approach to this compound. The expanded dT analogue (dxT), a methylquinazolinedione C-glycoside, was previously unknown; we describe its preparation in eight steps from 5-methylanthranilic acid. The key glycoside bond formation employed Pd-mediated coupling of an aryl iodide precursor with a dihydrofuran derivative of deoxyribose. Both nucleosides are shown to be efficient fluorophores, emitting light in the blue-violet range. The base-protected phosphoramidite derivatives were prepared, and short oligonucleotides containing them were characterized. The two size-expanded nucleosides are key components of a new four-base genetic system designed to form helical paired structures having a diameter greater than that of natural DNA. Elements of the design of this expanded genetic molecule, termed xDNA, are discussed, including the possibility of up to eight base pairs of information storage capability.     

Absolute time-resolved x-ray laser gain measurement

We present the first direct measurement of the time evolution of the gain of a soft x-ray laser amplifier. The measurement is based on the injection of a seed pulse, obtained by high-order harmonic generation, into an x-ray laser medium. Strong amplification occurs when the seed pulse is synchronized with the gain period. By precisely varying the delay between the x-ray laser plasma creation and the seed pulse injection, the actual temporal evolution of the soft x-ray amplifier gain is obtained with a subpicosecond resolution.