Vibrational spectroscopic studies of the structure of di-amino acid peptides. Part II: cyclo(L-Asp-L-Asp) in the solid state and in aqueous solution

Solid-state protonated and N,O-deuterated Fourier transform infrared (IR) and Raman scattering spectra together with the protonated and deuterated Raman spectra in aqueous solution of the cyclic di-amino acid peptide cyclo(L-Asp-L-Asp) are reported. Vibrational band assignments have been made on the basis of comparisons with previously cited literature values for diketopiperazine (DKP) derivatives and normal coordinate analyses for both the protonated and deuterated species based upon DFT calculations at the B3-LYP/cc-pVDZ level of the isolated molecule in the gas phase. The calculated minimum energy structure for cyclo(L-Asp-L-Asp), assuming C-2 symmetry, predicts a boat conformation for the DKP ring with both the two L-aspartyl side chains being folded slightly above the ring. The C=O stretching vibrations have been assigned for the side-chain carboxylic acid group (e.g. at 1693 and 1670 cm(-1) in the Raman spectrum) and the cis amide I bands (e.g. at 1660 cm(-1) in the Raman spectrum). The presence of two bands for the carboxylic acid C=O stretching modes in the solid-state Raman spectrum can be accounted for by factor group splitting of the two nonequivalent molecules in a crystallographic unit cell. The cis amide II band is observed at 1489 cm(-1) in the solid-state Raman spectrum, which is in agreement with results for cyclic di-amino acid peptide molecules examined previously in the solid state, where the DKP ring adopts a boat conformation. Additionally, it also appears that as the molecular mass of the substituent on the C-alpha atom is increased, the amide II band wavenumber decreases to below 1500 cm(-1); this may be a consequence of increased strain on the DKP ring. The cis amide II Raman band is characterized by its relatively small deuterium shift (29 cm(-1)), which indicates that this band has a smaller N-H bending contribution than the trans amide II vibrational band observed for linear peptides.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.

Managing alcohol related aggression in the emergency department (Part II)

Violence in the emergency department (ED) is a global problem. In our first paper, we highlighted the potential psychological effects of alcohol intoxication, the literatures discussion of alcohol related violence in the emergency department and the importance of developing positive nurse/service user relationships. In this second paper, we discuss personal and organisational strategies clinical nursing staff may consider appropriate to minimise the risk of assault when caring for service users projecting alcohol related aggression.

Managing alcohol related aggression in the emergency department (Part 1)

Internationally, violence in the emergency department (ED) is of a constant concern to emergency practitioners. Frequently, both original research papers and anecdotal reports emphasise the phenomenon of alcohol related aggression in the ED. In this first paper, we highlight the literatures discussion of alcohol related violence in the emergency department and the potential psychological effects of alcohol intoxication. In the second we offer personal and organisational strategies clinical nursing staff may consider appropriate to minimise the risk of assault when caring for service users projecting alcohol related aggression.

Drug calculations part 2: alternative strategies to the formula

Drug calculations are an essential skill for nurses. The clinical skill of performing a drug calculation has come under recent scrutiny,resulting in the development of essential skills clusters inwhich pre-registration nurses must be competent before qualifying (Nursing and Midwifery Council 2007). The focuson drug calculation skills places renewed emphasis on how these skills are taught in higher education institutions and how they are learned by students theoretically and in clinical practice.

Drug calculations part 1: a critique of the formula used by nurses

The role of mathematics is integral to nursing practice, and careful and accurate calculations are important to help prevent medication errors. This two-part article examines different methods for solving drug calculation problems. The first part critiques the commonly taught nursing drug calculation formula. Part 2, to be published next week, explores a range of other methods that are used in practice to calculate drug dosages.

Ultra-wideband cognitive interrogator network for indoor location tracking - part 1: system architecture and network performance analysis

We explore the potential application of cognitive interrogator network (CIN) in remote monitoring of mobile subjects in domestic environments, where the ultra-wideband radio frequency identification (UWB-RFID) technique is considered for accurate source localization. We first present the CIN architecture in which the central base station (BS) continuously and intelligently customizes the illumination modes of the distributed transceivers in response to the systempsilas changing knowledge of the channel conditions and subject movements. Subsequently, the analytical results of the locating probability and time-of-arrival (TOA) estimation uncertainty for a large-scale CIN with randomly distributed interrogators are derived based upon the implemented cognitive intelligences. Finally, numerical examples are used to demonstrate the key effects of the proposed cognitions on the system performance

‘Nothing will prevent me from doing a good job’. The professionalisation of part-time teaching staff in further and adult education

Approximately 85,000 part-time teaching staff working in further education (FE) and adult and community learning (ACL) are often seen as ‘a problem’. The intrinsic ‘part-timeness’ of these staff tends to marginalise them: they remain under-recognised and largely unsupported. Yet this picture is over-simplified. This article examines how part-time staff make creative use of professional autonomy and agency to mitigate problematic ‘casual employment’ conditions, reporting on results from Learning and Skills Development Agency-sponsored research (2002–2006) with 700 part-time staff in the learning and skills sector. The question of agency was reported as a key factor in part-time employment. Change is necessary for the professional agency of part-timers to be harnessed as the sector responds to ambitious sectoral ‘improvement’ agendas following the Foster Report and FE White Paper. Enhanced professionalisation for part-time staff needs greater recognition and inclusion in change agendas.