Microwave-assisted hydrogel synthesis: a new method for crosslinking polymers in aqueous solutions

It has been found that hydrogels may be formed by microwave irradiation of aqueous solutions containing appropriate combinations of polymers. This new method of hydrogel synthesis yields sterile hydrogels without the use of monomers, eliminating the need for the removal of unreacted species from the final product. Results for two particularly successful combinations, poly(vinyl alcohol) with either poly(acrylic acid) or poly(methylvinylether-alt-maleic anhydride), are presented. Irradiation using temperatures of 100–150 °C was found to yield hydrogels with large equilibrium swelling degrees of 500–1000 g g−1. Material leached from both types of hydrogel shows little cytotoxicity towards HT29 cells.

An efficient and rapid microwave-assisted synthesis of 1-acetyl-1H-indol-3-YL acetates

An efficient and rapid synthesis of 1-acetyl-1H-indol-3-yl acetate 1 and its derivatives 7 via the microwave-assisted cyclisation and decarboxylation of 2-[(carboxymethyl)amino]benzoic acids 5 is described. The latter were left to react with acetic anhydride using triethylamine as the base and were subjected to microwave irradiation for 1 minute, at 80 °C with initial power of 300 W. The target 1-acetyl-1H-indol-3-yl acetate 1 and derivatives 7 were isolated in 34-71% yield. In particular, synthesis of 1-acetyl-6-(trifluoromethyl)-1H-indol-3-yl acetate 7f and 1-acetyl-3-methyl-1H-indol-3-yl acetate 7h is reported for the first time.

Palladium(II) and platinum(II) complexes with tridentate iminophosphine ligands; synthesis and structural studies

The previously synthesised Schiff-base ligands 2-(2-Ph2PC6H4N = CH) - R' - C6H3OH (R' = 3-OCH3, HL1; 5-OCH3, HL2; 5-Br, HL3; 5-Cl, HL4) were prepared by a faster, more efficient route involving a microwave assisted co-condensation of 2-(diphenylphosphino) aniline with the appropriate substituted salicylaldehyde. HL1-4 react directly with (MCl2)-Cl-II (M = Pd, Pt) or (PtI2)-I-II(cod) affording neutral square-planar complexes of general formula [(MCl)-Cl-II(eta(3)-L1-4)] (M = Pd, Pt, 1 - 8) and [(PtI)-I-II(eta(3)-L1-4)] (M = Pd, Pt, 9 - 12). Reaction of complexes 1 - 4 with the triarylphosphines PR3 (R = Ph, p-tolyl) gave the novel ionic complexes [Pd-II(PR3)(eta(3)- L1-4)] ClO4 (13 - 20). Substituted platinum complexes of the type [Pt-II(PR3)(eta(3)- L1-4)] ClO4 (R = P(CH2CH2CN)(3) 21 - 24) and [Pt-II( P(p-tolyl)(3))(eta(3)-L-3,L-4)] ClO4 ( 25 and 26) were synthesised from the appropriate [(PtCl)-Cl-II(eta(3)-L1-4)] complex (5 - 8) and PR3. The complexes are characterised by microanalytical and spectroscopic techniques. The crystal structures of 3, 6, 10, 15, 20 and 26 were determined and revealed the metal to be in a square-planar four-coordinate environment containing a planar tridentate ligand with an O, N, P donor set together with one further atom which is trans to the central nitrogen atom.

Macrocyclic amines as structure-directing agents for the synthesis of three-dimensional antimony-sulfide frameworks

A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane ( cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)](x)[C10N4H26](1-x)[Sb4S7] (0.08 <= x <= 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S72- framework, constructed from layers of parallel arrays of Sb4S84- chains stacked at 90 to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimonysulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition- metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.

Activated mast cells in proximity to colonic nerves correlate with abdominal pain in irritable bowel syndrome

BACKGROUND & AIMS: The mechanisms underlying abdominal pain perception in irritable bowel syndrome (IBS) are poorly understood. Intestinal mast cell infiltration may perturb nerve function leading to symptom perception. We assessed colonic mast cell infiltration, mediator release, and spatial interactions with mucosal innervation and their correlation with abdominal pain in IBS patients. METHODS: IBS patients were diagnosed according to Rome II criteria and abdominal pain quantified according to a validated questionnaire. Colonic mucosal mast cells were identified immunohistochemically and quantified with a computer-assisted counting method. Mast cell tryptase and histamine release were analyzed immunoenzymatically. Intestinal nerve to mast cell distance was assessed with electron microscopy. RESULTS: Thirty-four out of 44 IBS patients (77%) showed an increased area of mucosa occupied by mast cells as compared with controls (9.2% +/- 2.5% vs. 3.3 +/- 0.8%, respectively; P < 0.001). There was a 150% increase in the number of degranulating mast cells (4.76 +/- 3.18/field vs. 2.42 +/- 2.26/field, respectively; P = 0.026). Mucosal content of tryptase was increased in IBS and mast cells spontaneously released more tryptase (3.22 +/- 3.48 pmol/min/mg vs. 0.87 +/- 0.65 pmol/min/mg, respectively; P = 0.015) and histamine (339.7 +/- 59.0 ng/g vs. 169.3 +/- 130.6 ng/g, respectively; P = 0.015). Mast cells located within 5 microm of nerve fibers were 7.14 +/- 3.87/field vs. 2.27 +/- 1.63/field in IBS vs. controls (P < 0.001). Only mast cells in close proximity to nerves were significantly correlated with severity and frequency of abdominal pain/discomfort (P < 0.001 and P = 0.003, respectively). CONCLUSIONS: Colonic mast cell infiltration and mediator release in proximity to mucosal innervation may contribute to abdominal pain perception in IBS patients.

Precipitation and latent heating distributions from satellite passive microwave radiometry. Part I: improved method and uncertainties

A revised Bayesian algorithm for estimating surface rain rate, convective rain proportion, and latent heating profiles from satellite-borne passive microwave radiometer observations over ocean backgrounds is described. The algorithm searches a large database of cloud-radiative model simulations to find cloud profiles that are radiatively consistent with a given set of microwave radiance measurements. The properties of these radiatively consistent profiles are then composited to obtain best estimates of the observed properties. The revised algorithm is supported by an expanded and more physically consistent database of cloud-radiative model simulations. The algorithm also features a better quantification of the convective and nonconvective contributions to total rainfall, a new geographic database, and an improved representation of background radiances in rain-free regions. Bias and random error estimates are derived from applications of the algorithm to synthetic radiance data, based upon a subset of cloud-resolving model simulations, and from the Bayesian formulation itself. Synthetic rain-rate and latent heating estimates exhibit a trend of high (low) bias for low (high) retrieved values. The Bayesian estimates of random error are propagated to represent errors at coarser time and space resolutions, based upon applications of the algorithm to TRMM Microwave Imager (TMI) data. Errors in TMI instantaneous rain-rate estimates at 0.5°-resolution range from approximately 50% at 1 mm h−1 to 20% at 14 mm h−1. Errors in collocated spaceborne radar rain-rate estimates are roughly 50%–80% of the TMI errors at this resolution. The estimated algorithm random error in TMI rain rates at monthly, 2.5° resolution is relatively small (less than 6% at 5 mm day−1) in comparison with the random error resulting from infrequent satellite temporal sampling (8%–35% at the same rain rate). Percentage errors resulting from sampling decrease with increasing rain rate, and sampling errors in latent heating rates follow the same trend. Averaging over 3 months reduces sampling errors in rain rates to 6%–15% at 5 mm day−1, with proportionate reductions in latent heating sampling errors.

Tripleclouds: an efficient method for representing horizontal cloud inhomogeneity in 1D radiation schemes by using three regions at each height

Radiation schemes in general circulation models currently make a number of simplifications when accounting for clouds, one of the most important being the removal of horizontal inhomogeneity. A new scheme is presented that attempts to account for the neglected inhomogeneity by using two regions of cloud in each vertical level of the model as opposed to one. One of these regions is used to represent the optically thinner cloud in the level, and the other represents the optically thicker cloud. So, along with the clear-sky region, the scheme has three regions in each model level and is referred to as “Tripleclouds.” In addition, the scheme has the capability to represent arbitrary vertical overlap between the three regions in pairs of adjacent levels. This scheme is implemented in the Edwards–Slingo radiation code and tested on 250 h of data from 12 different days. The data are derived from cloud retrievals using radar, lidar, and a microwave radiometer at Chilbolton, southern United Kingdom. When the data are grouped into periods equivalent in size to general circulation model grid boxes, the shortwave plane-parallel albedo bias is found to be 8%, while the corresponding bias is found to be less than 1% using Tripleclouds. Similar results are found for the longwave biases. Tripleclouds is then compared to a more conventional method of accounting for inhomogeneity that multiplies optical depths by a constant scaling factor, and Tripleclouds is seen to improve on this method both in terms of top-of-atmosphere radiative flux biases and internal heating rates.

A Gentle/S approach to robot assisted neuro-rehabilitation

Movement disorders (MD) include a group of neurological disorders that involve neuromotor systems. MD can result in several abnormalities ranging from an inability to move, to severe constant and excessive movements. Strokes are a leading cause of disability affecting largely the older people worldwide. Traditional treatments rely on the use of physiotherapy that is partially based on theories and also heavily reliant on the therapists training and past experience. The lack of evidence to prove that one treatment is more effective than any other makes the rehabilitation of stroke patients a difficult task. UL motor re-learning and recovery levels tend to improve with intensive physiotherapy delivery. The need for conclusive evidence supporting one method over the other and the need to stimulate the stroke patient clearly suggest that traditional methods lack high motivational content, as well as objective standardised analytical methods for evaluating a patient's performance and assessment of therapy effectiveness. Despite all the advances in machine mediated therapies, there is still a need to improve therapy tools. This chapter describes a new approach to robot assisted neuro-rehabilitation for upper limb rehabilitation. Gentle/S introduces a new approach on the integration of appropriate haptic technologies to high quality virtual environments, so as to deliver challenging and meaningful therapies to people with upper limb impairment in consequence of a stroke. The described approach can enhance traditional therapy tools, provide therapy "on demand" and can present accurate objective measurements of a patient's progression. Our recent studies suggest the use of tele-presence and VR-based systems can potentially motivate patients to exercise for longer periods of time. Two identical prototypes have undergone extended clinical trials in the UK and Ireland with a cohort of 30 stroke subjects. From the lessons learnt with the Gentle/S approach, it is clear also that high quality therapy devices of this nature have a role in future delivery of stroke rehabilitation, and machine mediated therapies should be available to patient and his/her clinical team from initial hospital admission, through to long term placement in the patient's home following hospital discharge.

Adaptive modelling with tunable RBF network using multi-innovation RLS algorithm assisted by swarm intelligence

In this paper, we propose a new on-line learning algorithm for the non-linear system identification: the swarm intelligence aided multi-innovation recursive least squares (SI-MRLS) algorithm. The SI-MRLS algorithm applies the particle swarm optimization (PSO) to construct a flexible radial basis function (RBF) model so that both the model structure and output weights can be adapted. By replacing an insignificant RBF node with a new one based on the increment of error variance criterion at every iteration, the model remains at a limited size. The multi-innovation RLS algorithm is used to update the RBF output weights which are known to have better accuracy than the classic RLS. The proposed method can produces a parsimonious model with good performance. Simulation result are also shown to verify the SI-MRLS algorithm.

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe12O19) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced along side ferric chloride among the starting materials. Though all of the Fe2+ ions in the starting material were converted to Fe3+ ions in the final product, Fe2+ was confirmed to participate differently from the Fe3+ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe2O3 and BaFe2O4 were improved when Fe2+ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl2/FeCl3 when only 2h of reaction time were needed. It was also found that the role of trivalent Fe3+ could be successfully replaced by Al3+. Up to 50% of their on could be replaced by Al3+ in the reactants to produce Al- doped products. It was also found that the ratio of Fe2+/M3+ could be increased in the presence of Al3+ to produce high quality barium ferrite.

PSO assisted NURB Neural Network Identification

A system identification algorithm is introduced for Hammerstein systems that are modelled using a non-uniform rational B-spline (NURB) neural network. The proposed algorithm consists of two successive stages. First the shaping parameters in NURB network are estimated using a particle swarm optimization (PSO) procedure. Then the remaining parameters are estimated by the method of the singular value decomposition (SVD). Numerical examples are utilized to demonstrate the efficacy of the proposed approach.

Quantitative precipitation estimation over ocean using Bayesian approach from microwave observations during the typhoon season

We have developed a new Bayesian approach to retrieve oceanic rain rate from the Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI), with an emphasis on typhoon cases in the West Pacific. Retrieved rain rates are validated with measurements of rain gauges located on Japanese islands. To demonstrate improvement, retrievals are also compared with those from the TRMM/Precipitation Radar (PR), the Goddard Profiling Algorithm (GPROF), and a multi-channel linear regression statistical method (MLRS). We have found that qualitatively, all methods retrieved similar horizontal distributions in terms of locations of eyes and rain bands of typhoons. Quantitatively, our new Bayesian retrievals have the best linearity and the smallest root mean square (RMS) error against rain gauge data for 16 typhoon overpasses in 2004. The correlation coefficient and RMS of our retrievals are 0.95 and ~2 mm hr-1, respectively. In particular, at heavy rain rates, our Bayesian retrievals outperform those retrieved from GPROF and MLRS. Overall, the new Bayesian approach accurately retrieves surface rain rate for typhoon cases. Accurate rain rate estimates from this method can be assimilated in models to improve forecast and prevent potential damages in Taiwan during typhoon seasons.

A procedure for the simultaneous determination of total nitrogen and total phosphorus in freshwater samples using persulphate microwave digestion

In the absence of a suitable method for routine analysis of large numbers of natural river water samples for organic nitrogen and phosphorus fractions, a new simultaneous digestion technique was developed, based on a standard persulphate digestion procedure. This allows rapid analysis of river, lake and groundwater samples from a range of environments for total nitrogen and phosphorus. The method was evaluated using a range of organic nitrogen and phosphorus structures tested at low, mid and high range concentrations from 2 to 50 mg l-1 nitrogen and 0.2 to 10 mg l-1 phosphorus. Mean recoveries for nitrogen ranged from 94.5% (2 mg I-1) to 92.7% (50 mg I-1) and for phosphorus were 98.2% (0.2 mg l-1) to 100.2% (10 mg l-1). The method is precise in its ability m reproduce results from replicate digestions, and robust in its ability to handle a variety of natural water samples in the pH range 5-8.

Assessment of intercalibration methods for satellite microwave humidity sounders

Three methods for intercalibrating humidity sounding channels are compared to assess their merits and demerits. The methods use the following: (1) natural targets (Antarctica and tropical oceans), (2) zonal average brightness temperatures, and (3) simultaneous nadir overpasses (SNOs). Advanced Microwave Sounding Unit-B instruments onboard the polar-orbiting NOAA 15 and NOAA 16 satellites are used as examples. Antarctica is shown to be useful for identifying some of the instrument problems but less promising for intercalibrating humidity sounders due to the large diurnal variations there. Owing to smaller diurnal cycles over tropical oceans, these are found to be a good target for estimating intersatellite biases. Estimated biases are more resistant to diurnal differences when data from ascending and descending passes are combined. Biases estimated from zonal-averaged brightness temperatures show large seasonal and latitude dependence which could have resulted from diurnal cycle aliasing and scene-radiance dependence of the biases. This method may not be the best for channels with significant surface contributions. We have also tested the impact of clouds on the estimated biases and found that it is not significant, at least for tropical ocean estimates. Biases estimated from SNOs are the least influenced by diurnal cycle aliasing and cloud impacts. However, SNOs cover only relatively small part of the dynamic range of observed brightness temperatures.