Real-Time Monitoring of the Mechanical Properties of a Soy Protein and Rubber Polymer during its Production Using Transient Infrared Spectroscopy

Soy protein–based polymers offer promising performance properties, but their characteristics are sensitively dependent on production conditions, so on-line monitoring could help provide the needed control during production. Mid-infrared spectroscopy combined with partial least squares offer the needed analysis, but the opacity of many materials in the mid-infrared range limits its conventional application. Transient infrared spectroscopy is a method of acquiring mid-infrared spectra from moving streams in real time that avoids the opacity problem. We apply transient infrared spectroscopy to a polymer of soy protein and polyisoprene-graft-maleic anhydride–modified natural rubber during its compounding extrusion to measure tensile strength and Young's modulus.     

A New Photochemical Reaction of Sulfonic Acid Esters

Abstract

In 1968 Zen and coworkers reported that thep-tolylsulfonyl group could be removed from carbohydrate systems by photochemical reaction (eq 1).¹ Since then other investigators have used this deprotection process in carbohydrate synthesis.^2-10 Mechanistic studies^11-16 have shown that tosylate photolysis is promoted by compounds (e.g., triethylamine) that donate an electron to an excitedp-toluenesulfonate to generate a radical anion (1). This intermediate then fragments to form the anion of the deprotected sugar (Scheme 1). Since generating a radical anion is the central element in this photochemical process, structural changes that impact radical anion formation should influence the reaction. Replacing the p - tolylsulfonyl group with the pentafluorophenylsulfonyl group generates a more stable radical anion (2) because the electronegative fluorine atoms can help stabilize the negative charge. Since we have a continuing interest in the photochemistry of sulfonic acid esters, we synthesized the pentafluorobenzenesulfonates (pentaflates) 3-6 and studied their photochemistry under electron transfer conditions.     

Acetals: a new organocatalysis chemotype for one-pot enantioselective α-amination

Conditions are described for one-pot Brønsted acid and organocatalysed enantioselective α-amination of acetals and associated functionalities. Of the organocatalysts screened, proline tetrazole gave the highest ee, while aqueous monochloroacetic acid proved to be the best Brønsted acid activator regarding minimizing racemization and maximizing product yield. The reaction opens up the way for using masked carbonyl functionalities in organocatalysis.     

Conceptual modelling and the project process in real simulation projects: a survey of simulation modellers

A survey was used to obtain information on the processes and methods used by simulation experts in real projects. The 102 survey respondents answered questions about their most recent simulation project. This paper presents some of the survey results, focussing mainly on conceptual modelling and the pattern of time allocation to different topics. There are a wide range of findings that include the modellers making changes to the initial conceptual model during subsequent tasks in most of the projects usually by adding complexity, model coding taking on average about twice the time of other topics, and the topics generally occurring in single blocks of time (at the resolution of the survey data collection) but with considerable overlaps. The results give an insight into the way experts approach simulation projects and their problem solving strategies. A potential application is in training novice modellers, particularly in developing ‘craft skills’. The results also provide an empirical basis for further research, especially in conceptual modelling.     

Glycoconjugated Metallohelices have Improved Nuclear Delivery and Suppress Tumour Growth In Vivo

Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric Fe^II metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53^+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.     

Density functionals with asymptotic-potential corrections are required for the simulation of spectroscopic properties of materials

Five effects of correction of the asymptotic potential error in density functionals are identified that significantly improve calculated properties of molecular excited states involving charge-transfer character. Newly developed materials-science computational methods are used to demonstrate how these effects manifest in materials spectroscopy. Connection is made considering chlorophyll-a as a paradigm for molecular spectroscopy, 22 iconic materials as paradigms for 3D materials spectroscopy, and the V_N⁻ defect in hexagonal boron nitride as an example of the spectroscopy of defects in 2D materials pertaining to nanophotonics. Defects can equally be thought of as being “molecular” and “materials” in nature and hence bridge the relms of molecular and materials spectroscopies. It is concluded that the density functional HSE06, currently considered as the standard for accurate calculations of materials spectroscopy, should be replaced, in most instances, by the computationally similar but asymptotically corrected CAM-B3LYP functional, with some specific functionals for materials-use only providing further improvements.

Spectroscopic transitions in materials that involve charge transfer require asymptotically corrected density functionals. As most transitions do have some charge transfer character, use of such methods are generally warranted.     

13C and 1H NMR analysis of structural defects in PVC: Application to the production of defects at various polymerization stages

High resolution ¹H and ¹³C NMR data were obtained on PVC and PVC reduced with Bu₃SnH. The reduction is never complete and CH₂Cl groups preferentially remain. It causes almost complete formation of cyclopentane structures from both internal and chain end unsaturation. ¹H NMR gives total unsaturation as well as chain end unsaturation except if there are interferences with initiator residues; in that case, its combination with ¹³ C NMR of reduced PVC gives the chain end unsaturation. By the last method short branches and long ends are determined. Residual primary chlorine in all kinds of branches (methyl, ethyl, butyl, long ends) is taken into account. Long end contents are to be corrected (factor around 1.5), due to incomplete relaxation in standard analysis conditions. ¹H NMR of reduced PVC can be used to get the total non-reduced structures, both -CH₂Cl and -CHCl-. PVC was prepared by suspension or solution (trichlorobenzene) polymerization at 55° C, using dicetyl peroxydicarbonate as an initiator. The initiator residue content is higher in suspension PVC at very low conversion, and then levels off at a low value; in solution polymerization, it chiefly depends on the monomer/initiator ratio. At low conversion, more chain end and less short branches are present in suspension polymerization. Otherwise, only the butyl branch content shows a definite trend to increase with conversion. In solution polymerization, the number of defects is chiefly dependent on the initial monomer concentration; it is generally much higher than in suspension, except for the chloromethyl branches where both processes give about the same results.     

Thermodynamics of the dissociation of Bis H+ in seawater from 5 to 40°C

Electromotive-force measurements of cells without transference were used to determine the dissociation constant of the protonated form of the weak base 2-amino-2-methyl-1, 3-propanediol (Bis) in synthetic seawaters corresponding to salinities of 20, 35, and 45. Hydrogen electrodes and silver-silver chloride electrodes were used, together with standard potentials determined in an earlier investigation. The pK increases in linear fashion with the salinity (S) of the medium, for values of S from 0 to 45. The solvent effect is given by 8.802+0.00378S at 25°C with a mean deviation of 0.001. The medium effect of seawater on H° at 25°C is less than 200 cal-mol^–1 and less than 0.2 cal-^oK-mol^–1 on S°.