Paired emitter-detector diode detection with dual wavelength monitoring for enhanced sensitivity to transition metals in ion chromatography with post-column reaction

The combination of post-column derivatisation and visible detection are regularly employed in ion chromatography (IC) to detect poorly absorbing species. Although this mode is often highly sensitive, one disadvantage is the increase in repeating baseline artifacts associated with out-of-sync pumping systems. The work presented here will demonstrate the use of a second generation design paired emitter-detector diode (PEDD-II) detection mode offering enhanced sensitivity to transition metals in IC by markedly reducing this problem and also by improving signal noise. First generation designs demonstrated the use of a single integrated PEDD detector cell as a simple, small (15 x 5 mm), highly sensitive, low cost photometric detector for the detection of metals in ion chromatography (IC). The basic principle of this detection mode lies in the employment of two linear light emitting diodes (LEDs), one operating in normal mode as a light source and the other in reverse bias serving as a light detector. The second generation PEDD-II design showed increased sensitivity for Mn(II)- and Co(II)-2-(pyridylazo) resorcinol (PAR) complexes as a result of two simultaneously acquiring detection cells - one analytical PEDD cell and one reference PEDD cell. Therefore, the PEDD-II employs two wavelengths whereby one monitors the analyte reaction product and the second monitors a wavelength close to the isosbestic point. The optimum LED wavelength to be used for the analytical cell was investigated to maximise peak response. The fabrication process for both the analytical and reference PEDD cells was validated by determining the reproducibility of detectors within a batch. The reproducibility and sensitivity of the PEDD-II detector was then investigated using signals obtained from both intra- and inter-day chromatograms

Determination of phosphate using a highly sensitive paired emitter-detector diode photometric flow detector

The use of a novel inexpensive photometric device, Paired Emitter Detector Diode (PEDD) has been applied to the colorimetric determination of phosphate using the malachite green spectrophotometric method. The novel miniaturized flow detector applied within this manifold is a highly sensitive, low cost, miniaturized light emitting diode (LED) based detector. The optical flow cell was constructed from two LEDs, whereby one is the light source and the second is the light detector, with the LED light source forward biased and the LED detector reversed biased. The photocurrent generated by the LED light source discharges the junction capacitance of the detector diode from 5 V (logic 1) to 1.7 V (logic 0) and the time taken for this process to occur is measured using a simple timer circuit. The malachite green (MG) method employed for phosphate determination is based on the formation of a green molybdophosphoric acid complex, the intensity of which is directly related to phosphate concentration. Optimum analytical parameters such as reaction kinetics, reagent to sample concentration ratio and emitter wavelength intensity were investigated for the spectrophotometric method. Linear calibration plots that obeyed the Beer-Lambert Law were obtained for phosphate in the range of 0.02-2 µM. The dynamic range, sensitivity and limits of detection are reported

Prognostic model to predict postoperative acute kidney injury in patients undergoing major gastrointestinal surgery based on a national prospective observational cohort study.

Background: Acute illness, existing co-morbidities and surgical stress response can all contribute to postoperative acute kidney injury (AKI) in patients undergoing major gastrointestinal surgery. The aim of this study was prospectively to develop a pragmatic prognostic model to stratify patients according to risk of developing AKI after major gastrointestinal surgery. Methods: This prospective multicentre cohort study included consecutive adults undergoing elective or emergency gastrointestinal resection, liver resection or stoma reversal in 2-week blocks over a continuous 3-month period. The primary outcome was the rate of AKI within 7 days of surgery. Bootstrap stability was used to select clinically plausible risk factors into the model. Internal model validation was carried out by bootstrap validation. Results: A total of 4544 patients were included across 173 centres in the UK and Ireland. The overall rate of AKI was 14·2 per cent (646 of 4544) and the 30-day mortality rate was 1·8 per cent (84 of 4544). Stage 1 AKI was significantly associated with 30-day mortality (unadjusted odds ratio 7·61, 95 per cent c.i. 4·49 to 12·90; P < 0·001), with increasing odds of death with each AKI stage. Six variables were selected for inclusion in the prognostic model: age, sex, ASA grade, preoperative estimated glomerular filtration rate, planned open surgery and preoperative use of either an angiotensin-converting enzyme inhibitor or an angiotensin receptor blocker. Internal validation demonstrated good model discrimination (c-statistic 0·65). Discussion: Following major gastrointestinal surgery, AKI occurred in one in seven patients. This preoperative prognostic model identified patients at high risk of postoperative AKI. Validation in an independent data set is required to ensure generalizability

Radiological and biochemical resolution of nutritional rickets with calcium

Aims: To determine the response to oral calcium in Nigerian children with rickets. Methods: In a teaching hospital in Western Nigeria, 26 children (13 boys, 13 girls, aged 2–5 years) with confirmed rickets received calcium lactate (2.7 g/day). Results: Within one month of treatment leg pain was relieved and the children were more active. The mean x ray score improved from 3.3 at baseline to 1.7 at three months and 0.9 at six months (arbitrary scoring system, 0–6). Twelve cases were healed radiologically after six months, 11 others improved considerably, two showed no significant improvement, and a non-compliant patient was worse. There was progressive reversal of biochemical features. Median plasma alkaline phosphatase fell from 519 (range 178–1078) to 283 (209–443) IU/l (p = 0.04) in four months, while mean 1,25-dihydroxyvitamin D fell from 473 (251–1057) to 281 (155–481) pmol/l (p = 0.04), and mean plasma calcium increased from 2.26 (1.63–2.54) to 2.37 (2.06–2.54) mmol/l (p = 0.13). Parathyroid hormone fell from 5.3 (0.4–21.5) to 1.7 (0.45–7.4) pmol/l. Type I collagen carboxy terminal cross linked telopeptide was very high at baseline (20 (7.2–103) to 14 (11–24) µg/l) (p = 0.03) and fell promptly to normal. Conclusion: Calcium supplementation alone effected healing of rickets in most of these Nigerian children and may provide sufficient treatment in this environment

Fingerprinting polychlorinated biphenyls in environmental samples using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

A GC × GC-TOFMS installed with a Rtx-PCB (60 m × 0.18 mm × 0.18 μm) in the first dimension and Rxi- 17 (1.5 m × 0.1 mm × 0.1 μm) column in the second dimension was used to separate 188 out of 209 congeners. A further 12 congeners were identified through additional data processing resulting in the identification of a total of 200 congeners. However, caution is advised if these 12 congeners were to be used in quantitative assessments. The remaining 9 co-eluting congeners were three doublets (CB65 + CB62, CB160 + CB163 and CB201 + CB204) and one triplet (CB20 + CB21 + CB33). This method was tested on five Aroclors and resulted in the separation of all congeners present in the heavier Aroclor mixtures A1254 and A1260. The suitability of this method for applications in biological matrices was demonstrated on extracted whiting and guillemot liver samples which resulted in the identification of 137 individual PCBs in the whiting liver sample and 120 in the guillemot sample. Fingerprinting was able to show clear differences in the PCB signature of the two animals. This highlights the potential of this method for PCB fingerprinting in environmental forensics studies and other assessments that require congener specific analysis