Efficiency of plasticization of PVC by higher-order di-alkyl phthalates and survey of mathematical models for prediction of polymer/diluent blend Tg's

Presently, a suitable theory to predict the T_g vs. composition relationship for a given polymer-plasticizer blend, based on detailed molecular structure and molecular energitics considerations, is not available. In particular, the plasticizer efficiency parameter, k, which is uniquely defined at low-to-moderate diluent concentrations, and is an essential variable in the Mauritz-Storey theory of the diffusion of large molecules in amorphous polymers in the rubbery state, must always be determined by experiment. In this work, k was determined by DSC for PVC that was plasticized over a range of concentrations with a number of higher branched and linear di-alkyl phthalates. The results will be used in our plasticizer diffusion theory as well as provide guidance in the future development of a general mathematical model for predicting k. It was seen that k decreased with increasing molecular weight for both the linear and branched phthalates. For a given molecular weight, the branched phthalates have higher k values than the linear structures. These results have been rationalized in terms of the additional free volume created by the inefficiency of packing polymer chains about these large penetrant molecules. The DSC scans also implied an increasing degree of microstructural heterogeneity with increasing plasticizer concentration. Finally, relationships between plasticizer diffusion coefficient in the rubbery state and the plasticized T_g were established for low-to-moderate diluent concentration for three of the plasticizers studied by utilizing experimental diffusion data from our earlier work on these systems.     

Evolutionary relationships among members of the genus Chlamydia based on 16S ribosomal DNA analysis

Nucleotide sequences from strains of the four species currently in the genus Chlamydia, C. pecorum, C. pneumoniae, C. psittaci, and C. trachomatis were investigated. In vitro-amplified RNA genes of the ribosomal small subunit from 30 strains of C. pneumoniae and C. pecorum were subjected to solid-phase DNA sequencing of both strands. The human isolates of C. pneumoniae differed in only one position in the 16S rRNA gene, indicating genetic homogeneity among these strains. Interestingly, horse isolate N16 of C. pneumoniae was found to be closely related to the human isolates of this species, with a 98.9% nucleotide similarity between their 16S rRNA sequences. The type strain and koala isolates of C. pecorum were also found to be very similar to each other, possessing two different 16S rRNA sequences with only one-nucleotide difference. Furthermore, the C. pecorum strains truncated the 16S rRNA molecule by one nucleotide compared to the molecules of the other chlamydial species. This truncation was found to result in loss of a unilaterally bulged nucleotide, an attribute present in all other eubacteria. The phylogenetic structure of the genus Chlamydia was determined by analysis of 16S rRNA sequences. All phylogenetic trees revealed a distinct line of descent of the family Chlamydiaceae built of two main clusters which we denote the C. pneumoniae cluster and the C. psittaci cluster. The clusters were verified by bootstrap analysis of the trees and signature nucleotide analysis. The former cluster contained the human isolates of C. pneumoniae and equine strain N16. The latter cluster consisted of C. psittaci, C. pecorum, and C. trachomatis. The members of the C. pneumoniae cluster showed tight clustering and strain N16 is likely to be a subspecies of C. pneumoniae since these strains also share some antigenic cross-reactivity and clustering of major outer membrane protein gene sequences. C. psittaci and strain N16 branched early out of the respective cluster, and interestingly, their inclusion bodies do not stain with iodine. Furthermore, they also share less reliable features like normal elementary body morphology and plasmid content. Therefore, the branching order presented here is very likely a true reflection of evolution, with strain N16 of the species C. pneumoniae and C. psittaci forming early branches of their respective cluster and with C. trachomatis being the more recently evolved species within the genus Chlamydia.     

Templated self-assembly of porphyrin cages

The development of self-assembling catalysts, although an often-tried approach, has achieved little success so far. Toward the construction of substrate selective catalysts, we have self-assembled a porphyrin cage based upon the recognition of the templates meso-dipyridyl ( DPyP ) or meso-tetrapyridyl porphyrin ( TPyP ) by glycoluril-based receptors that are functionalized with two pendant zinc porphyrins.     

Nonlinear circuit analysis using the method of harmonic balance—a review of the art. II. Advanced concepts

The harmonic balance method is a technique for the numerical solution of nonlinear analog circuits operating in a periodic, or quasi-periodic, steady-state regime. The method can be used to efficiently derive the continuous-wave response of numerous nonlinear microwave components including amplifiers, mixers, and oscillators. Its efficiency derives from imposing a predetermined steady-state form for the circuit response onto the nonlinear equations representing the network, and solving for the set of unknown coefficients in the response equation. Its attractiveness for nonlinear microwave applications results from its speed and ability to simply represent the dispersive, distributed elements that are common at high frequencies. The last decade has seen the development and application of harmonic balance techniques to model analog circuits, particularly microwave circuits. The first part of this article reviewed the fundamental achievements made during this time. In this part, the extension of the method to quasi-periodic regimes, optimization analysis, oscillator analysis, studies of various convergence strategies, and practical applications are discussed. A critical assessment of the various types of harmonic balance techniques is given. Examples of designs which have been modeled using the harmonic balance technique and built both in hybrid and MMIC form are presented.     

A framework for analysis of data quality research

Organizational databases are pervaded with data of poor quality. However, there has not been an analysis of the data quality literature that provides an overall understanding of the state-of-art research in this area. Using an analogy between product manufacturing and data manufacturing, this paper develops a framework for analyzing data quality research, and uses it as the basis for organizing the data quality literature. This framework consists of seven elements: management responsibilities, operation and assurance costs, research and development, production, distribution, personnel management, and legal function. The analysis reveals that most research efforts focus on operation and assurance costs, research and development, and production of data products. Unexplored research topics and unresolved issues are identified and directions for future research provided     

High PCO does not alter pHi, but raises [Ca2+]i in cultured rat carotid body glomus cells in the absence and presence of CdC12

We measured the effect of high PCO (500-550 Torr) on the pHi and [Ca2+]i in cultured glomus cells of adult rat carotid body (CB) as a test of the two models currently proposed for the mechanism of CB chemoreception. The metabolic model postulates that the rise in glomus cell [Ca2+]i, the initiating reaction in the signalling pathway leading to chemosensory neural discharge, is due to [Ca2+] release from intracellular Ca2+ stores. The membrane potential model postulates that the rise in [Ca2+]i comes from influx of extracellular Ca2+ through voltage-dependent Ca2+ channels (VDCC) of the L-type. High PCO did not change pHi at PO2 of 120-135 Torr, showing that CO-induced changes in [Ca2+]i are not due to changes in pHi. High PCO caused a highly significant rise in [Ca2+]i from 90+/-12 nM to 675+/-65 nM, both in the absence and in the presence of 200 microM CdCl2, a potent blocker of L-type VDCCs. This result is fully consistent with release of Ca2+ from glomus cell intracellular stores according to metabolic model, but inconsistent with influx of extracellular Ca2+ through VDCCs according to the membrane potential model.     

Advanced pain & symptom management (a case study-workshop discussion)

Coexpression of the rat beta 1 subunit with rat brain and skeletal muscle sodium channel alpha subunits in Xenopus oocytes normalizes currents by accelerating sodium current decay kinetics, shifting steady state availability relationships, and accelerating recovery from inactivation. Unlike brain and skeletal muscle, the heart alpha subunit expressed without beta 1 has native-like decay kinetics in oocytes. Messenger RNA for beta 1 has been found in heart, but whether and how it affects cardiac sodium channel function are unclear. We studied coexpression of human heart alpha subunit with beta 1 in Xenopus oocytes using two microelectrode voltage-clamp and macropatch techniques. Coexpression with beta 1 caused a significant positive shift of 3-7 mV in the midpoint of the steady state inactivation relationship but did not affect single-channel conductance, activation, current decay, or recovery from inactivation. Sensitivity to lidocaine block, however, was decreased for both resting state block (Kd = 0.5-1.3 mM) and phasic block in response to pulse trains, but inactivated state block was not affected (Kd = approximately 10 microM). Coexpression with beta 1 increased the rate of recovery from lidocaine block, which accounted for the major part of the observed differences in tonic and phasic block. A beta 1 construct with the cytoplasmic tail removed also produced these effects, demonstrating that the beta 1 cytoplasmic tail was not involved in altering lidocaine block. We conclude that the beta 1 subunit is capable of affecting function of the cardiac sodium channel in oocytes by decreasing tonic and phasic lidocaine block with small effects on gating.     

Purification of a 5-HT uptake inhibitor from the venom of Cerastes vipera

Heart rate (HR) and heart rate variability (HRV) are risk markers in cardiac disease. HRV is also an index of the sympathovagal modulation of heart rate. Their relations have been rarely analyzed. We aimed to study such relations in normal adult conscious rats by using a novel bradycardic agent, a sinus node inhibitor, S-16257. Placebo-drug crossover designs were used while monitoring HR with telemetry and analyzing HRV in both time and frequency domains. S-16257 (2 mg/kg; n = 10) decreased HR by 29% and markedly increased HRV in parallel. By using various combinations of S-16257, atropine (2 mg/kg), and propranolol (4 mg/kg), a positive relation was shown between RR interval and various indexes of HRV: the slower the HR, the greater the HRV. Nevertheless, there is one exception to this correlation. When S-16257 was associated with both atropine and propranolol, the deep bradycardia was accompanied by a reduction of HRV, which indicates that the physiologic negative correlation between HR and HRV is not an intrinsic property of the pacemaker but is highly dependent on the two components of the autonomic system.