New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers)

Summary Novel oxycarbonyl isocyanate telechelic polyisobutylenes have been prepared by conversion of hydroxylterminated polyisobutylenes with N-chlorocarbonyl isocyanate. This reaction is free from side-reactions and provides highly reactive isocyanate-terminated polyisobutylene prepolymers. Conversion of these prepolymers with glycol, urea, pentaerythritol, and polyethylene glycol led to linear chain extension, crosslinking, and multiblock copolymer formation, respectively.     

Living carbocationic polymerization

Summary The living synthesis of ,-di-tert.-chloropolyisobutylene ( ^t -Cl-telechelic PIB) has been accomplished by the use of the sterically hindered bifunctional initiator 1,3-di-(2-methoxy-2-propyl)-5-tert.-butylbenzene (tBu-m-DiCuOMe) in conjunction with BC1₃ coinitiator in CH₃Cl or CH₂Cl₂ diluents at –30°C and –10°C. The living nature of the polymerizations was demonstrated by linear ¯M_n versus W_PIB (g of PIB formed) plots starting at the origin and horizontal N (number of PIB moles) versus W_PIB plots. The molecular weight distributions are narrow (¯M_W/¯M_n < 2.0) and tend to decrease with increasing molecular weights. Number average end functionalities have been quantitated and found to be ¯F_n = 2.0±0.1.     

Spinning of poly(ethylene terephthalate) fibers from a melt pool without a spinneret

Monofilament fibers were spun continuously from the free surface of a pool of molten poly(ethylene terephthalate) without the aid of a spinneret. For take-up velocities in the range of 12 to 400 ft/min, the denier of the filaments produced was an inverse power function of take-up velocity, and the birefringence was an inverse power function of the filament diameter. Production rate and product uniformity were strongly dependent on take-up velocity and surface temperature of the melt pool.     

Decreasing the Sampling Time Interval in Radioactive Particle Tracking

The study of the movement of solids in multiphase reactors using radioactive particle tracking is currently limited to fairly modest particle velocities because of count‐rate limitations of the detection system. In this work, this restriction was overcome by increasing the activity of the radioactive tracer, by decreasing the sampling time interval and by modifying the particle tracking software to recognize which detectors were saturated and to use only the data from the remaining unsaturated detectors. Higher tracer activity resulted in lower standard deviation of the calculated tracer coordinates.     

Living carbocationic polymerization

Summary Living carbocationic polymerization of styrene (St) has been achieved by the use of the 1(p-methylphenyl)ethyl acetate (pMePhEtOAc)·BCl₃ complex in CH₃Cl solvent at –30°C using both the IMA and AMI techniques. The living nature of the polymerizations has been demonstrated by linear M_n versus W_PSt (weight of polystyrene) plots passing through the origin and horizontal N (moles of PSt) versus W_PSt plots starting at N=I_o (the number of moles of initiator used). The molecular weight distribution MWD of the PSts is broad (M_w/M_n=~5–6) due to slow initiation and/or slow exchange between dormant and active species relative to propagation. The structure of the ester initiator strongly affects the rate and outcome of living polymerization, e.g., cumyl acetate (CumOAc), cumyl propionate (CumOPr), and 2,4,6-trimethylphenylethyl acetate (TMePhEtOAc), do not lead to truly living St polymerizations. The findings with the latter esters is explained in terms of a two path process comprising a slow living polymerization and a faster conventional cationic chain reaction. With phenylethyl acetate (PhEtOAc) living polymerization is achieved, however, initiation (cation generation) is slow. Forced termination by pyridine or methanol, or heating to ambient temperature leads to-CH₂CH(C₆H₅)Cl end groups.     

Living carbocationic polymerization

Conventional cationic polymerization can be converted into living carbocationic polymerization (LC^⊕Pzn) by the introduction of common anion into the charge. Thus the conventional polymerization of isobutylene (IB) induced by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄ combination yields LC^⊕Pzn of IB upon the addition of tetrabutyl ammonium chloride (n-Bu₄NCl), most likely due to then-Bu₄NCl+TiCl₄ ?n-Bu₄N^⊕+TiCl ₅ ^⊕ equilibrium. A kinetic model has been developed and tested which corroborates these propositions. By this model we have gained for the first time quantitative insight into the quasiliving equilibrium.     

Caustic imaging of gallium droplets using mirror electron microscopy

We discuss a new interpretation of mirror electron microscopy (MEM) images, whereby electric field distortions caused by surface topography and/or potential variations are sufficiently large to create caustics in the image contrast. Using a ray-based trajectory method, we consider how a family of rays overlaps to create caustics in the vicinity of the imaging plane of the magnetic objective lens. Such image caustics contain useful information on the surface topography and/or potential, and can be directly related to surface features. Specifically we show how a through-focus series of MEM images can be used to extract the contact angle of a Ga droplet on a GaAs (001) surface.     

Family psychosocial screening: should we focus on high-risk settings?

The objective of this study was to address the question of whether or not psychosocial screening should be focused on "high-risk" populations. A cross-sectional survey of mothers of young children was conducted in various clinics: 758 in teaching clinics, 444 in private practices, and 202 at a military clinic. The self-administered questionnaire covered demographic factors, problems in mothers family of origin, maternal depression, and substance abuse. Mothers in the teaching clinics were younger and had less education and lower incomes than mothers in private practices, with intermediate levels in the military clinic. However, a substantial proportion of mothers seen in all sites reported psychosocial problems. Approximately 20% of mothers in all sites reported a family history of alcoholism. Positive screens for maternal depression ranged from about 15% to 35%. Binge drinking was reported by 10% to 20% at different sites. Psychosocial problems were common even among families seen in "low-risk" settings. Focusing screening only on high-risk clinics would miss many families with psychosocial problems.     

Three-year outcome after balloon aortic valvuloplasty. Insights into prognosis of valvular aortic stenosis

BACKGROUND: To identify predictors of long-term outcome after balloon aortic valvuloplasty, we analyzed data on 674 adults (mean age, 78 +/- 9 years; 56% were women) undergoing this procedure at 24 clinical centers who had a mean initial increase in aortic valve area of 0.3 cm2. METHODS AND RESULTS: Baseline data included clinical, echocardiographic, and catheterization variables. Follow-up data included mortality, cause of death, rehospitalization, 6-month echocardiography, and functional status. Kaplan-Meier curves and log-rank tests were used to evaluate survival in subgroups. Multivariate Cox regression models were used to identify independent predictors of survival. Overall survival was 55% at 1 year, 35% at 2 years, and 23% at 3 years, with the majority of deaths (70%) classified as cardiac by an independent review committee. Rehospitalization was common (64%), although 61% of survivors at 2 years reported improved symptoms. Echocardiography at 6 months (n = 115) showed restenosis from the postprocedural valve area of 0.78 +/- 0.31 cm2 to 0.65 +/- 0.25 cm2 (P < .0001). With stepwise multivariate analysis, sequentially adding clinical, echocardiographic, and catheterization variables, the overall model identified independent predictors of survival as baseline functional status, baseline cardiac output, renal function, cachexia, female gender, left ventricular systolic function, and mitral regurgitation. Baseline and postprocedural variables were examined to identify which subgroup of patients has the best outcome after aortic valvuloplasty. A "lower-risk" subgroup (28% of the study population), defined by normal left ventricular systolic function and mild clinical functional limitation, had a 3-year survival of 36% compared with 17% in the remainder of the study group. CONCLUSIONS: Long-term survival after balloon aortic valvuloplasty is poor with 1- and 3-year survival rates of 55% and 23%, respectively. Although survivors report fewer symptoms, early restenosis and recurrent hospitalization are common.     

Absorption of di-linoleoylphosphatidylcholine after oral administration

Essentiale and Lipostabil contain "essential" phospholipids from the soybean, mainly 1,2-dilinoleoyl-phosphatidylcholine (CAS 998-06-1, DLPC) which is considered as the main active ingredient. A single oral dose of d15-DLPC loaded with deuterium 9 times in the choline and 6 times in the linoleic acid of the 1-position was given to volunteers. Sera from 11 blood samples taken within 48 h after application were examined by means of mass spectrometry with regard to d9-choline and d6-linoleic acid in the 1- and 2-position of serum phosphatidylcholines (PC) as well as in the serum triglycerides. d9-choline, i.e. the total of d15-PC and d9-PC, showed maximum values of 5.6% of the total serum PC concentration. Normally, about 1.3% of PC in the human serum is DLPC. Serum 1-linoleoyl-PC was increased by 32-40% after oral application of d15-DLPC. A minor uptake of d6-linoleic acid into the 2-position of serum PC, which is rich in linoleic acid, and into the serum triglycerides was observed with peak values of 2.3% and 6.1%, resp. The uptake of polyunsaturated PC species like DLPC and 1-linoleoyl-PC into the liver after oral application of drugs containing such species in high amounts like "essential" phospholipids with about 50% of DLPC let expect therapeutic effects on membranes into which this special species is incorporated.