Inverse least-squares modeling of vapor descriptors using polymer-coated surface acoustic wave sensor array responses.

In previous work, it was shown that, in principle, vapor descriptors could be derived from the responses of an array of polymer-coated acoustic wave devices. This new chemometric classification approach was based on polymer/vapor interactions following the well-established linear solvation energy relationships (LSERs) and the surface acoustic wave (SAW) transducers being mass sensitive. Mathematical derivations were included and were supported by simulations. In this work, an experimental data set of polymer-coated SAW vapor sensors is investigated. The data set includes 20 diverse polymers tested against 18 diverse organic vapors. It is shown that interfacial adsorption can influence the response behavior of sensors with nonpolar polymers in response to hydrogen-bonding vapors; however, in general, most sensor responses are related to vapor interactions with the polymers. It is also shown that polymer-coated SAW sensor responses can be empirically modeled with LSERs, deriving an LSER for each individual sensor based on its responses to the 18 vapors. Inverse least-squares methods are used to develop models that correlate and predict vapor descriptors from sensor array responses. Successful correlations can be developed by multiple linear regression (MLR), principal components regression (PCR), and partial least-squares (PLS) regression. MLR yields the best fits to the training data, however cross-validation shows that prediction of vapor descriptors for vapors not in the training set is significantly more successful using PCR or PLS. In addition, the optimal dimension of the PCR and PLS models supports the dimensionality of the LSER formulation and SAW response models.

A method for chemometric classification of unknown vapors from the responses of an array of volume-transducing sensors.

A method for the characterization and classification of unknown vapors based on the responses on an array of polymer-based volume-transducing vapor sensors is presented. Unlike conventional pattern recognition methods, the sensor array pattern vector is converted into another vector containing vapor descriptors. Equations are developed to show how this approach can be applied to arrays of sensors where each sensor responds to the fractional volume increase of the polymer upon vapor sorption. The vapor sorption step of the response is modeled with linear solvation energy relationships using solvation parameters as vapor descriptors. The response model also includes the vapor concentration, the sensitivity to fractional volume increases, and the specific volume of the vapor as a liquid. The response model can be solved for the vapor descriptors given the array responses and sensitivity factors, following an approach described previously for purely gravimetric sensors. The vapors can then be classified from a database of candidate vapor descriptors. Chemiresistor vapor sensors coated with composite polymer films containing conducting particles represent a volume-transducing sensor technology to which this new classification method should apply. Preliminary equations are also presented for sensors that respond on the basis of both the mass and the volume of a sorbed vapor. Surface acoustic wave sensors with acoustically thin polymer films that respond to both mass and modulus effects may fit this classification approach.

Hydrogen bond acidic polymers for surface acoustic wave vapor sensors and arrays.

Four hydrogen bond acidic polymers are examined as sorbent layers on acoustic wave devices for the detection of basic vapors. A polysiloxane polymer with pendant hexafluoro-2-propanol groups and polymers with hexafluorobisphenol groups linked by oligosiloxane spacers yield sensors that respond more rapidly and with greater sensitivity than fluoropolyol, a material used in previous SAW sensor studies. Sensors coated with the new materials all reach 90% of full response within 6 s of the first indication of a response. Unsupervised learning techniques applied to pattern-normalized sensor array data were used to examine the spread of vapor data in feature space when the array does or does not contain hydrogen bond acidic polymers. The radial distance in degrees between pattern-normalized data points was utilized to obtain quantifiable distances that could be compared as the number and chemical diversity of the polymers in the array were varied. The hydrogen bond acidic polymers significantly increase the distances between basic vapors and nonpolar vapors when included in the array.

Neural substrates for the effects of rehabilitative training on motor recovery after ischemic infarct.

Substantial functional reorganization takes place in the motor cortex of adult primates after a focal ischemic infarct, as might occur in stroke. A subtotal lesion confined to a small portion of the representation of one hand was previously shown to result in a further loss of hand territory in the adjacent, undamaged cortex of adult squirrel monkeys. In the present study, retraining of skilled hand use after similar infarcts resulted in prevention of the loss of hand territory adjacent to the infarct. In some instances, the hand representations expanded into regions formerly occupied by representations of the elbow and shoulder. Functional reorganization in the undamaged motor cortex was accompanied by behavioral recovery of skilled hand function. These results suggest that, after local damage to the motor cortex, rehabilitative training can shape subsequent reorganization in the adjacent intact cortex, and that the undamaged motor cortex may play an important role in motor recovery.

Specific staining of iododeoxyuridine and bromodeoxyuridine in tumors double labelled in vivo: a cell kinetic analysis.

The simultaneous and specific staining of iododeoxyuridine (IdUrd) and chlorodeoxyuridine (CldUrd) allows for more accurate estimates of potential doubling time (Tpot). Because CldUrd is not approved for human use, the procedure was adapted for the staining of IdUrd and bromodeoxy-uridine (BrdUrd). The fluorescein isothiocyanate-conjugated B44 antibody (B44-FITC) stained both IdUrd and BrdUrd in tumor nuclei labelled singly with one or the other pyrimidine analogue. However, when MCaK tumors in exponential growth in vivo were pulse labelled with both IdUrd and BrdUrd, the staining of BrdUrd was not seen, and the labelling pattern reflected specificity to IdUrd. These observations were confirmed using tumors pulse labelled with IdUrd and/or BrdUrd at 6 h and/or 0.3 h prior to tumor removal in all possible combinations. Simultaneous specific staining of BrdUrd by Br3 and of IdUrd by B44-FITC was documented by quantification of labelling indices (LIs) from double-labelled tumors. The specificity of B44-FITC for IdUrd in double-labelled tumors was due to a greater affinity of this antibody for IdUrd than for BrdUrd. This technique allowed for two independent estimates of LI and Tpot when tumors were double labelled for 3.0 and 5.5 h. Both IdUrd and BrdUrd are approved for clinical use, and this double-labelling technique should prove to be valuable for measuring the cell kinetics of solid tumors in vivo.