High-birefringence nematic liquid crystal for broadband THz applications

Liquid crystals (LCs) have been studied extensively in the visible range for their dielectric tunability, and the characterisation in the terahertz (THz) range has gained increasing interest due to the need for active THz modulation and switching devices. In this paper, we use THz time-domain spectroscopy to measure the frequency-dependent birefringence and the absorption coefficient of a number of commercial and non-commercial nematic LCs, including E7, BL037, MDA-98-1602, LCMS-107, GT3-23001 and 1825, over a range of bias voltages at room temperature. Furthermore, several basic components of LC mixture are analysed to establish their contributions to birefringence and theoretical model is used to fit the absorption spectra. The large tunability and low loss measured for a range of samples show that the LCs are useful tunable dielectrics for compact, efficient and broadband THz devices.     

Use of a small particle solid‐core packing for improved efficiency and rapid measurement of sirolimus and everolimus by LC‐MS/MS

Measurement of whole blood sirolimus and everolimus is required in order to optimize patient treatment following solid organ transplant. Assay by LC‐MS/MS is increasingly preferred; however efficient use of the instrument and short turnaround times are crucial. Use of a 1.6 µm solid‐core packing HPLC column (Cortecs) gave significant increases in efficiency, sensitivity and throughput compared with an existing method, following simple protein precipitation of small‐volume (20 μL) whole blood samples. Sirolimus, everolimus and the stable isotopic internal standard (¹³C₂D₄ – everolimus) eluted at around 0.8 min, and total analytical run time was 2.2 min, saving almost 4 min per sample compared with an existing method. Within‐assay imprecision (CV) was 3.3–8.5%, and between‐assay imprecision was 2.2–10.8%. Retrospective assay of external quality assurance samples and comparison of patient samples assayed in parallel showed only small differences (between +6.8 and ?1.9%) in results using the Cortecs column when compared with the existing method. No significant interferences or ion suppression were observed. Copyright © 2015 John Wiley & Sons, Ltd.     

Mass fragmentographic quantitation of ethotoin and some of its metabolites in human urine.

A method for the determination of ethotoin and its p-hydroxylated and dealkylated metabolites in urine has been developed. Ethotoin and the metabolites were extracted from acidified urine with ethyl acetate and silylated before injection into a combined gas chromatograph--mass spectrometer. Four partly identified metabolites were recorded, but their exact quantitation was not possible as pure reference substances were not available. The limit of sensitivity was far below the amounts of ethotoin and of its metabolites found in urine from patients treated with therapeutic doses of ethotoin.     

Enzyme analysis by means of the air-gap electrode-determination of urease and arginase by monitoring of the initial reaction rate

The air-gap electrode has been used in kinetic chemical analysis, illustrated by the assay of the activities of the enzymes urease and arginase. The determinations are based on monitoring the initial reaction rates of the selective release of ammoniacal nitrogen, which in the arginine—arginase system was ensured by adding excess of urease. The reaction rates measured are in the range 2.5 · 10^-5—1.5 · 10^-3M min^-1; the relative standard deviation is ca. 2.8 %.     

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re I(CO)3(2,2'-bipyridine)} chromophore

Two multifunctional photoactive complexes [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+)=N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy=2,2'-bipyridine) were synthesized, characterized, and their redox and photonic properties were investigated by cyclic voltammetry; ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions; and time-resolved resonance Raman spectroscopy. The first reduction step of either complex occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans-->cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3)-->MeDpe(+ 3)MLCT (MLCT=metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximately 42 (73 %) and approximately 430 ps (27 %). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3)-->MeDpe(+) and Re(CO)(3)-->bpy (3)MLCT states, from which a MeDpe(+) localized intraligand (3)pipi* excited state ((3)IL) is populated with lifetimes of approximately 0.6 and approximately 10 ps, respectively. The (3)IL state undergoes a approximately 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle structural variations. The complex [Re(MeDpe(+))(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.     

Profiling of generic anti-phosphopeptide antibodies and kinases with peptide microarrays using radioactive and fluorescence-based assays

Kinases represent one of the largest enzyme families and key regulatory proteins in the cell. Only a small subset of these enzymes has been characterised so far. We have prepared different types of phosphopeptide and peptide microarrays displaying peptides deduced from annotated human phosphorylation sites and cytoplasmic domains of all annotated human membrane proteins. This approach was enabled by fully-automated high throughput micro-scale synthesis of peptides by the SPOT technology combined with chemo-selective immobilisation on modified glass slides. The phosphopeptide microarrays displaying 2923 peptides in total have been used for the characterisation of commercially available generic anti-phosphopeptide antibodies. This enabled us to detect Abl kinase activity on a microarray with anti-phosphotyrosine antibodies yielding results comparable to those obtained from a radioactive assay. More than 13 000 peptides deposited on six glass slides were used to profile casein kinase 2 (CK2) using a radioactive assay, since no generic antibody for the reliable detection of serine or threonine phosphorylation could be identified. All previously identified substrates were detected in the microarray experiment. In order to confirm whether substrates on the microarray are substrates in solution phase assays, more than 700 peptides were synthesised and tested with CK2 in a solution phase assay. All substrates identified in the solution phase assay were also detected on the microarray.     

X-ray absorption spectroscopy and density functional theory studies of [(H3buea)FeIII-X]n- (X = S2-, O2-, OH-): comparison of bonding and hydrogen bonding in oxo and sulfido complexes

Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe(III)H(3)buea(X)](n-) (X = S(2-), O(2-), OH(-)). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe(III)(-)O vs Fe(III)(-)S complexes. It was found that the Fe(III)(-)O bond, while less covalent, is stronger than the Fe(III)(-)S bond. This dominantly reflects the larger ionic contribution to the Fe(III)(-)O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe(IV)(-)O complex with the same ligand environment. It was found that hydrogen bonding to Fe(IV)(-)O is less energetically favorable than that to Fe(III)(-)O, which reflects the highly covalent nature of the Fe(IV)(-)O bond.     

Degradation kinetics of poly(lactic-co-glycolic) acid block copolymer cast films in phosphate buffer solution as revealed by infrared and Raman spectroscopies

Poly(lactic-co-glycolic) acid (PLGA) is an important copolymer used in drug delivery platforms where controlled release is required. In this work we investigated the in vitro degradation of four PLGA copolymers with L/G molar compositions of 50/50, 65/35, 75/25 and 95/5. ATR-IR and Raman spectroscopies were used to differentiate and quantify the degradation rates of glycolic and lactic units. Both techniques were used to determine the polymer composition as a function of degradation time and the degradation rate constants for the hydrolysis of glycolic and lactic units were calculated using a 1st order kinetics approach. Our results revealed a two stage process for the degradation of PLGA cast films in PBS in agreement with our previous work. The degradation rate constant for glycolic unit was found to be 1.3 times higher than for lactic units. In addition the degradation rate constants for L and G units were shown to decrease proportionally with increasing initial lactic content of the copolymer used to prepare the films.