Polymers for catalytic cation radical chemistry

Cation radical polymers which have cation radical functions at up to 5% of the poly(styrene) monomer sites have been prepared, and their effectiveness in catalyzing the cation radical Diels-Alder reaction is demonstrated.     

Tensile deformations in molten polymers

Summary This paper describes three complementary methods of measuring the rheological response of polymer melts under tension. A specially designed rheometer maintains constant stress throughout the deformation and gives well defined data, but is limited to high viscosity materials. The two other systems which have been studied are the deformation during the drawdown of an extrudate and that of convergent flow. A wide range of materials and degrees of deformation can be studied though the results are less precise. With empirical assumptions these systems yield data which are consistent with those obtained from the rheometer over a wide range of conditions.Viscous, elastic and plastic deformations are observed. The viscosity is, in general, independent of stress: its value is three times the limiting shear viscosity at low stress. Important departures from this rule occur for polythene and polypropylene. The viscosity of low density polythene increases with stress over a limited range of stress. This behaviour is associated with branching. Theviscosityof polypropylene decreases with stress. The elastic modulus at low stress is commonly in the range 10⁵–10⁶ dyn/cm² and is largely independent of temperature and molecular weight. At high stress there is a limiting elastic strain of about 2.0 units. Low density polythene has a plastic breaking stress of about 10⁷ dyn/cm². The breaking stress increases with temperature.

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Zusammenfassung Die Arbeit beschreibt drei sich ergänzende Methoden zur Messung des Theologischen Verhaltens polymerer Schmelzen unter Zugbeanspruchung. Ein speziell ausgelegtes Rheometer sorgt für eine konstante Spannung während der Deformation und ergibt eindeutige Meßgrößen. Es ist allerdings auf hochviskose Stoffe beschränkt. Die beiden anderen Methoden, die untersucht wurden, sind zum einen die Deformation während des Abziehens eines Extrudates und zum anderen die der konvergenten Strömung. Auf diese Weise können zahlreiche Stoffe und Verformungsgrade untersucht werden, obwohl die Ergebnisse weniger genau sind. Unter empirischen Annahmen ergeben diese Systeme Größen, die mit den mit Hilfe des Rheometers für einen weiten Bereich von Bedingungen ermittelten Ergebnissen übereinstimmen.Viskose, elastische und plastische Deformationen werden beobachtet. Die Viskosität ist im allgemeinen unabhängig von der Spannung; ihr Wert ist dreimal größer als die Grenz-Scherviskosität (bei geringer Spannung). Wichtige Abweichungen von dieser Regel treten bei Polyäthylen und Polypropylen auf. Die Viskosität von Polyäthylen niedriger Dichte wächst mit der Spannung in einem begrenzten Spannungsbereich. Dieses Verhalten ist von Verzweigungen begleitet. Die Viskosität des Polypropylens fällt dagegen mit der Spannung ab. Der Elastizitätsmodul liegt im allgemeinen zwischen 10⁵ und 10⁶ dyn/cm² und ist weitgehend von der Temperatur und dem Molekulargewicht unabhängig. Bei hoher Spannung zeigt sich eine begrenzende elastische Dehnung von etwa 2 Einheiten. Polyäthylen geringer Dichte hat eine plastische Bruchspannung von etwa 10⁷ dyn/cm². Die Bruchspannung wächst mit der Temperatur.

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Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968.     

On the dynamic response of viscoelastic fluids

Summary To define the dynamic shear behaviour of a viscoelastic fluid we require two functions — one elastic and one viscous. There are two simple alternatives based on the Voigt and Maxwell concepts which are mathematically interrelated. Current practice interprets the dynamic response of fluids as a function of angular frequency () in terms of the storage (G) and loss (G) moduli: the loss function is commonly converted to a viscosity = G/. As is well known the parameters andG are the elements of a Voigt model whereas it is near universal practice to interpret steady flow in terms of the Maxwell model. This paper shows how the interpretation of dynamic experiments on fluids in terms of the apparent Maxwell parameters is more simple, more sensitive, more consistent with steady flow behaviour, and physically more realistic.

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Zusammenfassung Zur Festlegung des dynamischen Scherverhaltens einer viskoelastischen Flüssigkeit benötigt man zwei Funktionen, eine für das elastische und eine für das viskose Verhalten. Dafür gibt es zwei einfache, mathematisch miteinander verknüpfte Alternativen, die entweder auf dem Voigtschen oder dem Maxwellschen Konzept gründen. Die übliche Praxis beschreibt das dynamische Verhalten der Flüssigkeiten als Funktion der Winkelgeschwindigkeit durch den SpeichermodulG und den VerlustmodulG bzw. die zugeordnete Viskosität = G/. Die Parameter undG sind bekanntlich die Elemente eines Voigt-Modells, wohingegen es nahezu allgemein üblich ist, das stationäre Fließen durch ein Maxwell-Modell zu beschreiben. Diese Arbeit zeigt nun, daß die Beschreibung dynamischer Versuche mit Hilfe von apparenten Maxwell-Parametern einfacher, empfindlicher, mit dem stationären Verhalten konsistenter und in physikalischer Hinsicht realistischer ist.

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Paper presented at British Society of Rheology conference. Rheometry: Methods of measurement and analysis of results, Shrivenham, April 8–11, 1975.

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With 13 figures and 2 tables     

Identification and Preliminary Structure-Activity Relationship Studies of 1,5-Dihydrobenzo[e][1,4]oxazepin-2(3H)-ones That Induce Differentiation of Acute Myeloid Leukemia Cells In Vitro

Acute myeloid leukemia (AML) is the most aggressive type of blood cancer, and there is a continued need for new treatments that are well tolerated and improve long-term survival rates in patients. Induction of differentiation has emerged as a promising alternative to conventional cytotoxic chemotherapy, but known agents lack efficacy in genetically distinct patient populations. Previously, we established a phenotypic screen to identify small molecules that could stimulate differentiation in a range of AML cell lines. Utilising this strategy, a 1,5-dihydrobenzo[e][1,4]oxazepin-2(3H)-one hit compound was identified. Herein, we report the hit validation in vitro, structure-activity relationship (SAR) studies and the pharmacokinetic profiles for selected compounds.     

A STEM/EELS method for mapping iron valence ratios in oxide minerals

The valence state of iron in minerals has useful applications in the geosciences for estimating redox conditions during mineral formation or re-equilibration. STEM/EELS techniques offer the advantage over other methods of being able to measure Fe valence with very high spatial resolution across mineral grains and grain boundaries. We have modified an EELS method for point analyses of iron valence ratios (Fe(3+)/SigmaFe) making it possible to generate line scans and maps of Fe valence. We demonstrate this method with measurements at an interface between iron-bearing oxides in a finely intergrown sample of magnetite and ilmenite. The STEM/EELS method is based on a calibrated relationship between Fe(3+)/SigmaFe and the relative intensities of the Fe L(3) and L(2) white lines in core energy-loss spectra for oxide and silicate minerals. Our method overcomes problems of energy drift in spectrum images by aligning energy-loss edges at a fixed energy position prior to background removal. An automated routine for batch processing of core loss spectra, including additional background removal and calculation of Fe L(3)/L(2) intensity ratios, allows for rapid Fe(3+)/SigmaFe determinations of multiple point analyses or spectrum images and the preparation of Fe valence maps, with an analytical error of +/-0.05 to +/-0.09 in the Fe(3+)/SigmaFe measurements.     

A fluidic diode, valves, and a sequential-loading circuit fabricated on layered paper

Current microfluidic paper-based devices lack crucial components for fluid manipulation. We created a fluidic diode fabricated entirely on a single layer of paper to control the wicking of fluids. The fluidic diode is a two-terminal component that promotes or stops wicking along a paper channel. We further constructed a trigger and a delay valve based on the fluidic diode. Furthermore, we demonstrated a high-level functional circuit, consisting of a diode and a delay valve, to manipulate two fluids in a sequential manner. Our study provides new, transformative tools to manipulate fluid in microfluidic paper-based devices.     

Expedient Iron‐Catalyzed Coupling of Alkyl,Benzyl and Allyl Halides with Arylboronic Esters

While attractive, the iron‐catalyzed coupling of arylboron reagents with alkyl halides typically requires expensive or synthetically challenging diphosphine ligands. Herein, we show that primary and secondary alkyl bromides and chlorides, as well as benzyl and allyl halides, can be coupled with arylboronic esters, activated with alkyllithium reagents, by using very simple iron‐based catalysts. The catalysts used were either adducts of inexpensive and widely available diphosphines or, in a large number of cases, simply [Fe(acac)₃] with no added co‐ ligands. In the former case, preliminary mechanistic studies highlight the likely involvement of iron(I)–phosphine intermediates.     

Stretching flow instabilities at the exits of extrusion dies

As liquid leaves an extrusion die, the surface layers are rapidly stretched. Stretching flows may become unstable in two ways: by breaking, or in a ductile manner producing an uneven “necked” sample which, in continuous extrusion and drawing, is sometimes called “draw resonance”. There is a quantitative correlation between the extrusion defect known as “sharkskin” and the cohesive failure of polymer melts. By extruding under closely defined conditions, it is possible to introduce a transitory “structure” into the surface layer of the extrudate greatly enhancing its cohesive strength and eliminating this defect. A similar quantitative correlation is established between the uneven coating thickness sometimes obtained during coextrusion of a high viscosity melt on the surface of a low viscosity melt and the tensile drawing instability known as “draw resonance”. Simple criteria are established to avoid this problem in practical flow engineering.     

GC-MS Analysis of the 8-Aminoquinoline Antimalarial [NPC1161] and its Carboxy Metabolite in Plasma and Red Blood Cells of Primates

This study describes a novel and simple GC-MS procedure developed for the determination of the concentration of the 8-aminoquinoline antimalarial agent NPC1161 and its carboxy metabolite in plasma and red blood cells. Preliminary pharmacokinetic data were generated for the two enantiomers of NPC1161 in monkeys. NPC1161, the internal standard, and desalkyl metabolite were converted to their mono-heptafluorobutyrates, while the carboxy metabolite underwent an intramolecular cyclization to give a lactam product. The calibration curves were linear ranging from 10 to 2,000 ng mL⁻¹. The developed GC-MS method is sensitive and reproducible for measuring blood level of this antimalarial drug.     

TMEDA in Iron‐Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic “ate” Complex Formation

The reactions of iron chlorides with mesityl Grignard reagents and tetramethylethylenediamine (TMEDA) under catalytically relevant conditions tend to yield the homoleptic “ate” complex [Fe(mes)₃]^? (mes=mesityl) rather than adducts of the diamine, and it is this ate complex that accounts for the catalytic activity. Both [Fe(mes)₃]^? and the related complex [Fe(Bn)₃]^? (Bn=benzyl) react faster with representative electrophiles than the equivalent neutral [FeR₂(TMEDA)] complexes. Fe^I species are observed under catalytically relevant conditions with both benzyl and smaller aryl Grignard reagents. The X‐ray structures of [Fe(Bn)₃]^? and [Fe(Bn)₄]^? were determined; [Fe(Bn)₄]^? is the first homoleptic σ‐hydrocarbyl Fe^III complex that has been structurally characterized.