Determination of inorganic ions in mineral water by gradient elution moving boundary electrophoresis

A sensitive method was developed for the determination of the major inorganic ions in commercial mineral waters using gradient elution moving boundary electrophoresis with capacitively coupled contactless conductivity detection. This application was the first to demonstrate the separation of cations and anions simultaneously using gradient elution moving boundary electrophoresis. Seven ionic analytes (calcium, chloride, magnesium, nitrate, potassium, sodium, and sulfate) were separated in less than 7 min with detection values in the low μmol/L to sub-μmol/L range. Calculated values of the major ions in three commercial mineral waters were compared to reported values with good correlation. In another application, phosphate and arsenate were separated in less than 2 min with limits of detection of 300 and 140 nmol/L, respectively. For all standard analyses, the RSD for migration times and peak areas were under 3%.     

Quantitative assessment of mobile protein levels in human knee synovial fluid: feasibility of chemical exchange saturation transfer (proteinCEST) MRI of osteoarthritis

Purpose

To establish the feasibility of chemical exchange saturation transfer (proteinCEST) MRI in the differentiation of osteoarthritis (OA) knee joints from non-OA joints by detecting mobile protein and peptide levels in synovial fluid by determining their relative distribution.

Materials and Methods

A total of 25 knees in 11 men and 12 women with knee injuries were imaged using whole knee joint proteinCEST MRI sequence at 3 T. The joint synovial fluid was segmented and the asymmetric magnetization transfer ratio at 3.5 ppm MTR_asym (3.5 ppm) was calculated to assess protein content in the synovial fluid. The 85th percentile of synovial fluid MTR_asym (3.5 ppm) distribution profile was compared using the independent Student's t test. The diagnostic performance of the 85th percentile of synovial fluid MTR_asym (3.5 ppm) in differentiating OA and non-OA knee joints was evaluated.

Results

The 85th percentile of synovial fluid MTR_asym (3.5 ppm) in knee joints with OA was 8.6%±3.4% and significantly higher than that in the knee joints without OA (6.3%±1.4%, P<.05). A knee joint with an 85th percentile of synovial fluid MTR_asym (3.5 ppm) greater than 7.7% was considered to be an OA knee joint. With the threshold, the sensitivity, specificity and overall accuracy for differentiating knee joints with OA from the joints without OA were 54% (7/13), 92% (11/12) and 72% (18/25), respectively.

Conclusion

proteinCEST MRI appears feasible as a quantitative methodology to determine mobile protein levels in synovial fluid and identify patterns characteristic for OA disease.     

Joint ground and air emergency medical services coverage models: A greedy heuristic solution approach

Aeromedical and ground ambulance services often team up in responding to trauma crashes, especially when the emergency helicopter is unable to land at the crash scene. We propose location-coverage models and a greedy heuristic for their solution to simultaneously locate ground and air ambulances, and landing zones (transfer points). We provide a coverage definition based on both response time and total service time, and consider three coverage options; only ground emergency medical services (EMS) coverage, only air EMS coverage, or joint coverage of ground and air EMS in which the patient is transferred from an ambulance into an emergency helicopter at a transfer point. To analyze this complex coverage situation we develop two sets of models, which are variations of the Location Set Covering Problem (LSCP) and the Maximal Covering Location Problem (MCLP). These models address uncertainty in spatial distribution of motor vehicle crash locations by providing coverage to a given set of both crash nodes and paths. The models also consider unavailability of ground ambulances by drawing upon concepts from backup coverage models. We illustrate our results on a case study that uses crash data from the state of New Mexico. The case study shows that crash node and path coverage percentage values decrease when ground ambulances are utilized only within their own jurisdiction.     

Location coverage models with demand originating from nodes and paths: Application to cellular network design

Location covering problems, though well studied in the literature, typically consider only nodal (i.e. point) demand coverage. In contrast, we assume that demand occurs from both nodes and paths. We develop two separate models – one that handles the situation explicitly and one which handles it implicitly. The explicit model is formulated as a Quadratic Maximal Covering Location Problem – a greedy heuristic supported by simulated annealing (SA) that locates facilities in a paired fashion at each stage is developed for its solution. The implicit model focuses on systems with network structure – a heuristic algorithm based on geometrical concepts is developed. A set of computational experiments analyzes the performance of the algorithms, for both models. We show, through a case study for locating cellular base stations in Erie County, New York State, USA, how the model can be used for capturing demand from both stationary cell phone users as well as cell phone users who are in moving vehicles.     

Chemical exchange saturation transfer MR imaging of articular cartilage glycosaminoglycans at 3 T: Accuracy of B0 Field Inhomogeneity corrections with gradient echo method

Glycosaminoglycan Chemical Exchange Saturation Transfer (gagCEST) is an important molecular MRI methodology developed to assess changes in cartilage GAG concentrations. The correction for B₀ field inhomogeneity is technically crucial in gagCEST imaging. This study evaluates the accuracy of the B₀ estimation determined by the dual gradient echo method and the effect on gagCEST measurements. The results were compared with those from the commonly used z-spectrum method. Eleven knee patients and three healthy volunteers were scanned. Dual gradient echo B₀ maps with different ?TE values (1, 2, 4, 8, and 10 ms) were acquired. The asymmetry of the magnetization transfer ratio at 1 ppm offset referred to the bulk water frequency, MTR_asym(1 ppm), was used to quantify cartilage GAG levels. The B₀ shifts for all knee patients using the z-spectrum and dual gradient echo methods are strongly correlated for all ?TE values used (r = 0.997 to 0.786, corresponding to ?TE = 10 to 1 ms). The corrected MTR_asym(1 ppm) values using the z-spectrum method (1.34% ± 0.74%) highly agree only with those using the dual gradient echo methods with ?TE = 10 ms (1.72% ± 0.80%; r = 0.924) and 8 ms (1.50% ± 0.82%; r = 0.712). The dual gradient echo method with longer ?TE values (more than 8 ms) has an excellent correlation with the z-spectrum method for gagCEST imaging at 3 T.     

Synthesis of 7,7'-dihydroxy-8,8'-biquinolyl (azaBINOL) via Pd-catalyzed directed double C-H functionalization of 8,8'-biquinolyl: emergence of an atropos from a tropos state

7,7'-Dihydroxy-8,8'-biquinolyl (azaBINOL) was prepared from 2-chloroaniline in four steps: (1) the Skraup reaction, (2) Ni-catalyzed reductive coupling of 8-chloroquinoline, (3) Pd(II)-catalyzed double C-H functionalization of 8,8'-biquinolyl mediated by PhI(OAc)(2), and (4) saponification. During the third step, an axially chiral (atropos type) biaryl molecule was directly generated from an essentially achiral (tropos type) biaryl starting material.     

A study of situationally aware routing for emergency responders

This paper presents tests conducted on routes determined from a Dijkstra-based shortest path problem and a Variance-Constrained Shortest Path problem under varying conditions of traffic and weather in a simulated ‘smart environment’. Utilizing envisioned future advanced transportation systems’ real-time information on traffic parameters allows data fusion techniques to provide situation awareness to its users. Taking advantage of this real-time data, the routing methodologies and data capture techniques studied in this paper provides Emergency Medical Services with better routes when responding to a vehicular crash. Comparing the performance of both routing methodologies in terms of both their ability to provide better routes as well as computation times demonstrates two alternatives for aiding in future emergency response.     

Clustering intelligent transportation sensors using public transportation

Advanced transportation sensors use a wireless medium to communicate and use data fusion techniques to provide complete information. Large-scale use of intelligent transportation sensors can lead to data bottlenecks in an ad-hoc wireless sensor network, which needs to be reliable and should provide a framework to sensors that constantly join and leave the network. A possible solution is to use public transportation vehicles as data fusion nodes or cluster heads. This paper presents a mathematical programming approach to use public transportation vehicles as cluster heads. The mathematical programming solution seeks to maximize benefit achieved by covering both mobile and stationary sensors, while considering cost/penalty associated with changing cluster head locations. A simulation is developed to capture realistic considerations of a transportation network. This simulation is used to validate the solution provided by the mathematical model.     

Mass spectrometric studies of the path of carbon in photosynthesis: positional isotopic analysis of (13)C-labelled C(4) to C(7) sugar phosphates

The (EIMS) electron ionization mass spectrometric fragmentation patterns of the methoxime- and ethoxime-trimethylsilyl (TMS) derivatives of C(4) to C(7) sugars involved as phosphates in the Calvin pathway of photosynthesis in plants were analysed by gas chromatography/EIMS using specifically labelled (13)C analogs. In general, most but not all of the major ions in the mass spectra arise from single carbon-carbon bond cleavages of the straight-chain derivatives. The results confirm that GC/MS of the alkoxime-TMS derivatives is a viable method for measuring (13)C incorporations at individual carbon atoms in each of the sugar phosphates during photosynthetic experiments with (13)CO(2).     

Suppression of nitric oxide production in mouse macrophages by soybean flavonoids accumulated in response to nitroprusside and fungal elicitation

Background

The anti-inflammatory properties of some flavonoids have been attributed to their ability to inhibit the production of NO by activated macrophages. Soybean cotyledons accumulate certain flavonoids following elicitation with an extract of the fungal pathogen Diaporthe phaseolorum f. sp. meridionalis (Dpm). Sodium nitroprusside (SNP), a nitric oxide donor, can substitute for Dpm in inducing flavonoid production. In this study, we investigated the effect of flavonoid-containing diffusates obtained from Dpm- and SNP-elicited soybean cotyledons on NO production by lipopolysaccharide (LPS)- and LPS plus interferon-γ (IFNγ)-activated murine macrophages.

Results

Significant inhibition of NO production, measured as nitrite formation, was observed when macrophages were activated in the presence of soybean diffusates from Dpm- or SNP-elicited cotyledons. This inhibition was dependent on the duration of exposure to the elicitor. Daidzein, genistein, luteolin and apigenin, the main flavonoids present in diffusates of elicited cotyledons, suppressed the NO production by LPS + IFNγ activated macrophages in a concentration-dependent manner, with IC₅₀ values of 81.4 μM, 34.5 μM, 38.6 μM and 10.4 μM respectively. For macrophages activated with LPS alone, the IC₅₀ values were 40.0 μM, 16.6 μM, 10.4 μM and 2.8 μM, respectively. Western blot analysis showed that iNOS expression was not affected by daidzein, was reduced by genistein, and was abolished by apigenin, luteolin and Dpm- and SNP-soybean diffusates at concentrations that significantly inhibited NO production by activated macrophages.

Conclusions

These results suggest that the suppressive effect of flavonoids on iNOS expression could account for the potent inhibitory effect of Dpm- and SNP-diffusates on NO production by activated macrophages. Since the physiological concentration of flavonoids in plants is normally low, the treatment of soybean tissues with SNP may provide a simple method for substantially increasing the concentration of metabolites that are beneficial for the treatment of chronic inflammatory diseases associated with NO production.