Review of Chemometrics Applied to Spectroscopy: 1985-95, Part 2

INTRODUCTION

Before beginning Part 2 of this review, a caveat noted by Deming and Palasota is brought to the reader's attention: [1] “Press et al. [2] have emphasized that data ‘consist of numbers, of course. But these numbers are fed into the computer, not produced by it. These are numbers to be treated with considerable respect, never to be tampered with, nor subjected to a numerical process whose character you do not completely understand. You are well advised to acquire reverence for data that is rather diferent fiom the “sporty” attitude which is sometimes allowable, or even commendable, in other numerical tasks.’ Yet by and large within chemometrics, preprocessing often seems to be carried out with little understanding of its fundamental efect on the structure of the data.”     

Scalable Detection of Anomalous Patterns With Connectivity Constraints

We present GraphScan, a novel method for detecting arbitrarily shaped connected clusters in graph or network data. Given a graph structure, data observed at each node, and a score function defining the anomalousness of a set of nodes, GraphScan can efficiently and exactly identify the most anomalous (highest-scoring) connected subgraph. Kulldorff’s spatial scan, which searches over circles consisting of a center location and its k ? 1 nearest neighbors, has been extended to include connectivity constraints by FlexScan. However, FlexScan performs an exhaustive search over connected subsets and is computationally infeasible for k > 30. Alternatively, the upper level set (ULS) scan scales well to large graphs but is not guaranteed to find the highest-scoring subset. We demonstrate that GraphScan is able to scale to graphs an order of magnitude larger than FlexScan, while guaranteeing that the highest-scoring subgraph will be identified. We evaluate GraphScan, Kulldorff’s spatial scan (searching over circles) and ULS in two different settings of public health surveillance. The first examines detection power using simulated disease outbreaks injected into real-world Emergency Department data. GraphScan improved detection power by identifying connected, irregularly shaped spatial clusters while requiring less than 4.3 sec of computation time per day of data. The second scenario uses contaminant plumes spreading through a water distribution system to evaluate the spatial accuracy of the methods. GraphScan improved spatial accuracy using data generated from noisy, binary sensors in the network while requiring less than 0.22 sec of computation time per hour of data.     

High-Modulus Wholly Aromatic Fibers. II. Partially Ordered Polyamide-Hydrazides

Partially ordered polyarnide-hydrazides were produced by the poly condensation of diacid chlorides with aminobenz-hydrazides, the order that results being a consequence of the considerably more rapid reaction of a diacid chloride with the hydrazide group in competition with the aromatic amine group of the aminobenzhydrazide. Fibers were produced from a series of such polymers containing from 50 mole % meta-oriented phenylene rings to 100 mole % para-oriented ones. Fiber from the wholly para-oriented type of polymer exhibited very high strength and modulus: 12.5 and 468 g/den, respectively, at 4.3% elongation-to-break. Although the crystallinity and density observed for hot-drawn fibers of partially ordered completely para-oriented polyarnide-hydrazides were comparable to the crystallinity and density of fibers of the isomeric wholly ordered polymer, the partially ordered polymers were more readily spun to the ultra-high strength and high modulus type fibers, probably because their greater solubility made them easier to spin.     

High-Modulus Wholly Aromatic Fibers. I. Wholly Ordered Polyamide-Hydrazides and Poly-1,3,4-oxadiazole—Amides

Several completely ordered polyamide-hydrazide copolymers were prepared via low temperature poly condensation of aromatic diacid chlorides with symmetrical aromatic diamines containing preformed dihydrazide linkages. Highly crystalline, hot-drawn fibers of the polyamide-hydrazide containing only para-oriented phenylene units showed unusually high strength and exceptionally high initial modulus: 10.8 and 508 g/den, respectively, at 2.9% elongation-to-break. The as-spun fibers also exhibited rather high tensile strength and unusually high initial modulus: 8.2 and 291 g/den, respectively, at 9.4% elongation-to-break. The hot-drawn fiber retained considerable strength at elevated temperatures, exhibiting a tenacity of 1.4 g/den and an initial modulus of 169 g/den at 350°C. Heat-aging of the as-spun fiber at 185°C in air showed that 66% of the original tenacity, 41% of the elongation, and 86% of the modulus were retained even after 336 hr. Substitution of as little as 25 mole % meta-oriented phenylene rings for para-oriented ones resulted in loss of the ultra-high strength and modulus, giving tensile properties comparable to those of fibers from wholly aromatic polyamides of the meta-oriented type. Fibers from the polyamide-hydrazides containing 50 mole % meta-oriented rings showed similar properties. Although ordered oxadiazole-amide copolymers were obtained from diamines containing two preformed oxadiazole linkages separated by m-phenylene rings, fibers could not be spun from them. Fiber of an ordered oxadiazole-amide copolymer was obtained, however, by heat treatment of the wholly p-phenylene ordered poly amide-hydrazide copolymer precursor fiber. Such a fiber exhibited a tenacity of 15.3 g/den, 3.6% elongation-to-break, and 564 g/den initial modulus.     

Highly luminescent europium(III) complexes with naphtoiltrifluoroacetone and dimethyl sulphoxide

The synthesis, luminescence properties, experimental determination and theoretical calculation of the emission quantum yield of Eu(NTA)₃.2L complexes, where NTA is naphtoiltri-fluroacetone and L denotes H₂O or DMSO (dimethyl sulphoxide), were reported. The compounds were characterized by elemental analysis (carbon, hydrogen and europium), thermal analysis, UV-visible absorption and photoluminescence spectroscopies. The experimental quantum yields were determined based on a method previously proposed by Bril and collaborators. The Eu(NTA)₃.2DMSO compound shows a high value for the Ω₂ intensity parameter (35.8 × 10^?20 cm²), reflecting the hypersensitive nature of the ⁵D₀ → ⁷F₂ transition and indicating that the lanthanide ion is in a highly polarizable chemical environment. The experimental quantum yield measured for that compound, 0.75, is one of the highest so far reported for solid-state europium complexes. The theoretical calculations of the quantum yield were carried out by solving an appropriate set of rate equations and by using empirical spectroscopic parameters and energy transfer rates. The theoretical results agree well with the experimental data for both complexes. The photostability of Eu(NTA)₃.2DMSO at 358K was evaluated in order to verify whether this complex can be applied as a phosphor for blue light emitting devices.     

The role of technology in the past and future development of the doubly labelled water method

The doubly labelled water method is an isotope-based technique that is used to measure the energy demands of free-living animals and humans. It is based on the observation that, in the body, the oxygen in carbon dioxide is in complete isotope exchange equilibrium with the oxygen in body water. Hence, a label of isotopic oxygen in body water is eliminated by both respiratory CO(2) and water turnover, whereas a similarly introduced label of deuterium is eliminated only by water flux. The difference in isotope fluxes therefore permits estimation of CO(2) production, which is correlated to energy demands. The doubly labelled water method has been advanced predominantly by technological advances in mass spectrometry. Although it was first described in the 1950s, it was only used on small animals and in low numbers because the costs of the isotopes were a primary constraint. However, advances in mass spectrometry precision and accuracy in the 1980s made it possible to reduce the quantities of isotope used, and hence apply the method on humans, although still in small numbers. The advent of continuous flow inlets in the 1990s made possible the processing of samples in much larger numbers and the sample sizes of studies have expanded. Ironically, however, the technique is now under treat because of technological advances in another area (positron emission tomography), which has generated an enormous demand for (18)O and pushed up the price of isotopes. A continuation of this trend might drive prices to levels where sustained application of the method in human studies is questionable. Replacing determination of isotope enrichments currently performed by isotope ratio mass spectrometry with determinations made by stable isotope infrared laser spectrometry may be a technological advance that will get us out of this problem.