[Show abstract][Hide abstract] ABSTRACT: Selected carbanions react with carbon disulfide in a modified LCQ ion trap mass spectrometer to form adducts, which when collisionally activated, decompose by processes which in some cases identify the structures of the original carbanions. For example (i) C(6)H(5)(-) + CS(2)--> C(6)H(5)CS(2)(-)--> C(6)H(5)S(-) + CS, occurs through a 3-membered ring ipso transition state, and (ii) the reaction between C(6)H(5)CH(2)(-) and CS(2) gives an adduct which loses H(2)S, whereas the adduct(s) formed between o-CH(3)C(6)H(5)(-) and CS(2) loses H(2)S and CS. Finally, it is shown that decarboxylation of C(6)H(5)CH(2)CH(2)CO(2)(-) produces the beta-phenylethyl anion (PhCH(2)CH(2)(-)), and that this thermalized anion reacts with CS(2) to form C(6)H(5)CH(2)CH(2)CS(2)(-) which when energized fragments specifically by the process C(6)H(5)CH(2)CH(2)CS(2)(-)--> C(6)H(5)CH(2)(-)CHC(S)SH --> [(C(6)H(5)CH(2)CH[double bond, length as m-dash]C[double bond, length as m-dash]S) (-)SH] --> C(6)H(5)CH(2)CCS(-) + H(2)S. Experimental findings of processes (ii) and (iii) were aided by deuterium labelling studies, and all reaction profiles were studied by theoretical calculations at the UCCSD(T)/6-31+G(d,p)//B3LYP/6-31+G(d,p) level of theory unless indicated to the contrary.
[Show abstract][Hide abstract] ABSTRACT: The development of a technique of electrical stimulation to release secretions from the dermal macroglands of anurans has permitted analysis of the secretions of numerous species without the need to kill the subjects. Sequential photography of the process involving stimulation of the parotoid glands of the cane toad. Bufo marinus, demonstrates the temporal characteristics. Liberation of the secretions commences after five seconds and maximum discharge is attained after 25 s. (C) Koninklijke Brill NV. Leiden. 2009
[Show abstract][Hide abstract] ABSTRACT: Many species of frogs of the genus Litoria secrete bioactive peptides from their skin glands. These peptides are normally host-defence compounds and may have one, or more of the following activities; smooth muscle contraction, analgesic, antimicrobial, antiviral, lymphocyte proliferator (immunomodulator) and neuronal nitric oxide synthase (nNOS) inactivation. Two frog species of the Litoria rubella Group that have been studied before, namely, Litoria electrica and Litoria rubella, are different from other species of the genus Litoria in that they produce small peptides that show neither membrane, lymphocyte nor nNOS activity. In this study we have used electrospray mass spectrometry together with Edman sequencing to identify eight skin peptides of the third member of this Group, Litoria dentata: surprisingly, none of these peptides show activity in our biological screening program. However, two major peptides (FPWL-NH(2) and FPWP-NH(2)) from L. electrica and L. rubella are opioids at the micromolar concentration.
Rapid Communications in Mass Spectrometry 04/2009; 23(8):1189-95. DOI:10.1002/rcm.3988 · 2.25 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory have shown that cyclization of both the ground state triplet and the corresponding singlet state of CCCSi may rearrange to give cyclic isomers which upon ring opening may reform linear C(3)Si isomers in which the carbon atoms are scrambled. The cyclization processes are energetically favorable with barriers to the transition states from 13 to 16 kcal mol(-1). This should be contrasted with the analogous process of triplet CCCC to triplet rhombic C(4), which requires an excess energy of 25.8 kcal mol(-1). A similar cyclization of doublet CCCP requires 50.4 kcal mol(-1) of excess energy; this should be contrasted with the same process for CCCN, which requires 54.7 kcal mol(-1) to effect cyclization.
The Journal of Physical Chemistry A 12/2008; 112(49):12714-20. DOI:10.1021/jp807403s · 2.69 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Deprotonation of CH2=CHCN with HO- in the chemical ionization source of a VG ZAB 2HF mass spectrometer gives CH2=-CCN which fragments through [H- (HCCCN)] to give [CCCN]-. Similar reactions with 13CH2CHCN and CH2CH13CN give [13CCCN]- and [CC13CN]-. Collision induced dissociations of these anions, together with calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory indicate that the anions do not rearrange under conditions used to charge strip them to their neutrals. A comparison of the charge reversal (-CR+) and neutralization/reionization (-NR+) mass spectra of [CCCN]- indicate that neutral C3N species (formed by charge stripping of the anion) decompose by loss of C. Experimental studies with the 13C labeled analogues indicate that the loss of C occurs subsequent to or accompanying partial carbon scrambling of the CCCN backbone. Theoretical studies suggest that this scrambling may occur during equilibration of CCCN and CCNC via a decomposing "rhombic" C3N intermediate.
The Journal of Physical Chemistry A 01/2008; 111(50):12932-7. DOI:10.1021/jp076315j · 2.69 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The skin secretion of the Dainty Green Tree Frog Litoria gracilenta contains 16 peptides, which protect the animal from predators, both large and small. A combination of negative and positive ion electrospray mass spectrometry together with Lys-C enzymic digest and Edman sequencing identifies three new wide-spectrum caerin 1 antibiotics, namely Caerin 1.17 [GLFSVLGSVAKHLLPHVAPIIAEKL-NH2], Caerin 1.18 [GLFSVLGSVAKHLLPHVVPVIAEKL-NH2], and Caerin 1.19 [GLFKVLGSVAKHLLPHVAPIIAEKL-NH2], and a narrow spectrum antibiotic Caerin 3.5 [GLWEKVKEKANELVSGIVEGVK-NH2].
[Show abstract][Hide abstract] ABSTRACT: The hypothiocyanate anion (OSCN)(-) is reported to be a major product of the lactoperoxidase/H(2)O(2)/(SCN)(-) system, and this anion is proposed to have significant antimicrobial properties. The collision induced (CID) negative ion mass spectrum of "(OSCN)(-)" has been reported: there is a pronounced parent anion at m/z 74, together with fragment anions at m/z 58 (SCN)(-) and 26 (CN)(-). These fragment anions are consistent with structure (OSCN)(-). However there is also a lesser peak at m/z 42 (OCN(-) or CNO(-)) in this spectrum which is either formed by rearrangement of (OSCN)(-) or from an isomer of this anion. The current theoretical investigation of (OSCN)(-) and related isomers, together with the study of possible rearrangements of these anions, indicates that ground-state singlet (OSCN)(-) is a stable species and that isomerization is unlikely. The three anions (OSCN)(-), (SCNO)(-), and (SNCO)(-) have been synthesized (in the ion source of a mass spectrometer) by unequivocal routes, and their structures have been confirmed by a consideration of their collision induced (negative ion) and charge reversal (positive ion) mass spectra. The CID mass spectrum of (SCNO)(-) shows formation of m/z 42 (CNO(-)), but the corresponding spectra of (OSCN)(-) or (SNCO)(-) lack peaks at m/z 42. Combined theoretical and experimental data support earlier evidence that the hypothiocyanite anion is a major oxidation product of the H(2)O(2)/(SCN)(-) system. However, the formation of m/z 42 in the reported CID spectrum of "(OSCN)(-)" does not originate from (OSCN)(-) but from another isomer, possibly (SCNO)(-).
The Journal of Physical Chemistry A 05/2006; 110(14):4930-6. DOI:10.1021/jp058144t · 2.69 Impact Factor