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.

Vibrational spectra of α-amino acids in the zwitterionic state in aqueous solution and the solid state: DFT calculations and the influence of hydrogen bonding

The zwitterionic forms of the two simplest alpha-amino acids, glycine and l-alanine, in aqueous solution and the solid state have been modeled by DFT calculations. Calculations of the structures in the solid state, using PW91 or PBE functionals, are in good agreement with the reported crystal structures, and the vibrational spectra computed at the optimized geometries provide a good fit to the observed IR and Raman spectra in the solid state. DFT calculations of the structures and vibrational spectra of the zwitterions in aqueous solution at the B3-LYP/cc-pVDZ level were found to require both explicit and implicit solvation models. Explicit solvation was modeled by inclusion of five hydrogen-bonded water molecules attached to each of the five possible hydrogen-bonding sites in the zwitterion and the integration equation formalism polarizable continuum model (IEF-PCM) was employed, providing a satisfactory fit to observed IR and Raman spectra. Band assignments are reported in terms of potential-energy distributions, which differ in some respects to those previously reported for glycine and l-alanine.

The implementation of FT-Raman spectroscopy to study solid state moisture induced changes in the crystallographic nature of pharmaceutical excipients - a lesson in humidity

An aqueous solution of sucrose was lyophilised, producing amorphous sucrose. This wasthen stored under different humidity at 25ºC for 1 week, allowing some samples tocrystallise. FT-Raman spectroscopy and PXRD have been successfully shown toqualitatively distinguish between amorphous and crystalline samples of sucrose. The datafrom the two techniques is complementary.

Characterising noise signals in 2-phase solid gas flows

Pneumatic conveying of powder and granular material involve the mixed flow of solid particles in air. Characterisation of solid/gas flow regimes is important for the design, operation and control of plants involving such two-phase processes. This paper describes preliminary studies directed at identifying flow regimes in solid/gas flows by analysis of the process `noise' signals from a flow transmitter which has a relatively wide frequency response.

Influence of solder paste components on rheological behaviour

Rheological properties of solder pastes are very important for a high quality surface mount technology process. The stencil/screen printing process of solder pastes is one of the most critical steps in the SMT assembly process, as most of the assembly defects can often be shown to originate from paste rheology and associated poor printing performance. This paper concerns an investigation of the effect of solder paste composition on the rheological properties and behaviour of four different solder pastes. We report on the evaluation of three different paste formulations based on the no-clean flux composition, with different alloy composition, metal content and particle size using a range of rheological characterisation techniques - including viscosity measurements, yield stress, oscillatory and creep-recovery tests. Our results show that in the viscosity test, all solder pastes exhibited a shear thinning behaviour in nature with different highest maximum viscosity. In the region of shear thinning behaviour the paste 3 delivered the best results. Viscosity test helps to understand the solid and cohesive behaviour of solder pastes. Good solid and cohesive behaviour indicates a good paste roll and helps to avoid paste bleeding. The yield stress test has been used to study the effect of temperature on the flow behaviour of solder pastes. Yield stress was measured for a range of temperature from 15deg C to 35deg C with an increment of 5degC. The result indicated a decreasing of the yield stress point if the temperature was increased. Paste 4 has shown the minimum dependence on temperature. The oscillatory test has been used to find out the linear visco-elastic range and to study the solid and liquid like behaviours of solder pastes. Paste 1 indicated the biggest linear visco-elastic region (LVR) and the highest value of G' and G" which means solder paste 1 will be needed a higher squeegee pressure in the printing process. In the creep recovery test paste 4 showed the best- - recovery and the lowest values of creep and recovery compliance which indicated a good printing behaviour. The test also has showed the solder paste with smaller particle size exhibit less recovery

Solid phase velocity measurements utilising electrostatic sensors and cross correlation signal processing

Gas-solids two phase systems are widely employed within process plant in the form of pneumatic conveyors, dust extraction systems and solid fuel injection systems. The measurement of solids phase velocity therefore has wide potential application in flow monitoring and, in conjunction with density measurement instrumentation, solids mass flow rate measurement. Historically, a number of authors have detailed possible measurement techniques, and some have published limited test results. It is, however, apparent that none of these technologies have found wide application in industry. Solids phase velocity measurements were undertaken using real time cross correlation of signals from two electrostatic sensors spaced axially along a pipeline conveying pulverised coal (PF). Details of the measurement equipment, the pilot scale test rig and the test results are presented.

Laser Doppler velocimetry measurements of particle velocity profiles in gas-solid two-phase flows

The measurement of particle velocities in two-phase gas-solid systems has a wide application in flow monitoring in process plant, where two-phase gas-solids systems are frequently employed in the form of pneumatic conveyors and solid fuel injection systems. Such measurements have proved to be difficult to make reliably in industrial environments. This paper details particle velocity measurements made in a two phase gas-solid now utilising a laser Doppler velocimetry system. Tests were carried out using both wheat flour and pulverised coal as the solids phase, with air being used as the gaseous phase throughout. A pipeline of circular section, having a diameter of 53 mm was used for the test work, with air velocities ranging from 25 to 45 m/s and suspension densities ranging from 0.001 kg to 1 kg of solids per cubic meter of air. Details of both the test equipment used, and the results of the measurements are presented.

Preparation of o/w emulsions stabilized by solid particles and their characterization by oscillatory rheology

The purpose of this investigation was to examine the preparation and characterisation of hexane-in-water emulsions stabilised by clay particles. These emulsions, called Pickering emulsions, are characterised by the adsorption of solid particles at the oil/water (o/w) interface. The development of an elastic film at the o/w interface following the adsorption of colloidal particles helps to promote emulsion stability. Three different solid materials were used: silica sand, kaolin, and bentonite. Particles were added to the liquid mixtures in the range of 0.5–10 g dm−3. Emulsions were prepared using o/w ratios of 0.1, 0.2, 0.3, and 0.4. The effect of sodium chloride, on the stability of the prepared emulsions, was assessed in the range of 0–0.5 mol dm−3. In addition the use of a cationic surfactant hexadecyl-trimethylammonium bromide (CTAB) as an aid to improving emulsion stability was assessed in the concentration range of 0–0.05% (w/v). Characterisation of emulsion stability was realised through measurements of rheological properties including non-Newtonian viscosity, the elastic modulus, G', the loss modulus, G", and complex modulus, G*. The stability of the emulsions was evaluated immediately after preparation and 4 weeks later. Using the stability criteria, that for highly stable emulsions: G' > G" and both G' and G" are independent of frequency (varpi) it was concluded that highly stable emulsions could be prepared using a bentonite concentration of 2% (or more); an o/w ratio greater than 0.2; a CTAB concentration of 0.01%; and a salt concentration of 0.05 M or less—though salt was required.