Uop Lcc

Ronald P Rohrbach

Mary J Maliarik

Joseph Levy

Mark B Koch

Haya Zemel

George W Lester

Dale S Scherl

Blaise J Arena

Thomas P Malloy

Paul R Kurek

Edward J St Martin

Elaine F Schumacher

A large class of crosslinked cyclodextrin resins soluble in water to an extent under about 200 ppm but soluble in an organic solvent to an extent of at least 0.1 weight percent have good film-forming properties with a wide variety of solid phase substrates. The films exhibit excellent adhesive properties toward virtually all solid surfaces which consequently can be readily coated with a thin film having a multiplicity of cyclodextrin moieties available at the surface for seperation and/or purification. Such coated substrates can be prepared in a variety of sizes, shapes, and cyclodextrin loading quite conveniently and relatively inexpensively.

Cyclodextrin films on solid substrates

The yellow pigments which result from reaction of the Monascus pigments monascorubrin and rubropunctatin with amines followed by reduction of the ring carbonyl moiety to an hydroxyl group have excellent properties for their use as food colorants. Yellow pigments made from amino acid esters, dipeptide esters, and amines of sugar alcohols have particular promise as desirable food colorants which are effective at levels which impart no objectionable taste to foods.

Reduced monascus pigment derivatives as yellow food colorants

Polyisocyanate crosslinked cyclodextrin resins prepared within a certain mole ratio of polyisocyanate to cyclodextrin are soluble in solvents such as pyridine and dimethylformamide but highly insoluble in water. Such resins have excellent adhesive properties toward virtually all solid surfaces which consequently can be readily coated with a thin film having a multiplicity of cyclodextrin moieties available at the surface for separation and/or purification. Such coated substrates can be prepared in a variety of sizes, shapes, and cyclodextrin loading quite conveniently and relatively inexpensive.

Method of preparing cyclodextrin-coated surfaces

Composites on a porous support of an insolubilized, crosslinked cyclodextrin show improved mass transfer characteristics relative to discrete particles of the same insolubilized cyclodextrin. Dicarboxylic acid dihalides are particularly effective crosslinking agents. The composites can be prepared quite simply and cost effectively by impregnating a support, such as alumina, with a cyclodextrin, then reacting the cyclodextrin within the impregnated support with a suitable dicarboxylic acid dihalide, such as one from the alkane dicarboxylic acid series containing from 4 through 12 carbon atoms.

Crosslinked cyclodextrins supported on porous refractory inorganic oxides

A process for the continuous production of cyclodextrins employs as a feedstock an aqueous solution of partially hydrolyzed starch with a dextrose equivalent between about 10 and about 15 as the feedstock for an immobilized cyclodextrin glycosyltransferase. In one variant the feedstock is sent to a membrane which removes cyclodextrins and glucose and the retentate is recycled to an immobilized glycosyltransferase so as to effectively utilize the feedstock. In another variant the effluent is passed through a water immiscibled liquid organic compound which forms a solid insoluble complex with cyclodextrins, the solids are continually removed, and the aqueous phase is recycled to an immobilized cyclodextrin glycosyltransferase as in the prior variant.

Method of cyclodextrin manufacture using an immobilized cyclodextrin

The yield of cyclodextrins formed in the hydrolysis of starch catalyzed by a cyclodextrin glycosyltransferase can be substantially increased by the addition of certain water-soluble solutes. Alcohols containing 1 to 6 carbon atoms form one such class, with ethanol and isopropyl alcohol being especially effective. Where an immobilized cyclodextrin glycosyltransferase is used yields of beta-cyclodextrin can be increased from approximately 20% to almost 40% using 15% isopropyl alcohol in a thinned starch feedstock, with glucose production being increased by only about 25%.

Increasing cyclodextrin yields by the addition of various solutes to

A support matrix which immobilizes enzymes by ion exchange forces comprises a core support deposited on which is a functionalized polyethylenimine insoluble in water. Such support matrices may be prepared from a virtually limitless variety of core supports since the functionalized polyethylenimines of this invention show excellent adhesive properties even to smooth surfaces. Such support matrices are particularly useful where the enzyme to be immobilized has a rather limited inherent half-life. The functionalized polyethylenimine is a carboxylic acid amide of polyethylenimine, a sulfonic acid amide of polyethylenimine or polyalkylated polyethylenimine.

Support matrix and immobilized enzyme system

The preparation of syrups which contain a high glucose or maltose content may be effected in a two-step process. In the first step, a feedstock such as starch which has been pretreated with alpha-amylase to adjust the dextrose equivalent is contacted with an enzyme such as amyloglucosidase or beta-amylase immobilized on a solid support. The contact time is adjusted by correlating the residence time and the liquid hourly space velocity so as to provide a conversion percentage of starch in the range of from about 50% to 85%, thus avoiding the formation of undesired conversion products. The partially hydrolyzed reaction mixture from the enzyme treatment is then passed through an ultrafiltration membrane whereby the permeate comprising the high glucose or maltose content is recovered, while the retentate is recycled for admixture with the partially hydrolyzed reaction mixture or for further treatment with the immobilized enzyme.

Production of high sugar syrups

Support matrices are prepared by titanating the surface hydroxyl groups of refractory inorganic oxides with a titanium tetrahalide, such as TiCl.sub.4, reacting each of the remaining halogens of the surface-titanated oxide with one of the amino groups of diamine, and thereafter reacting the remaining amino group with one of the functional groups of a dialdehyde or diisocyanate. Titanating is carried out by contacting a refractory inorganic oxide with titanium tetrahalide, preferably in the absence of a solvent for the titanium tetrahalide, removing excess and unreacted titanium tetrahalide and heating the titanated inorganic oxide at a temperature of from about 80.degree. C. to about 200.degree. C. in an inert atmosphere of nitrogen, argon or helium, or in a vacuum. Such support matrices may be used to bind enzymes, affording effective immobilized enzyme systems.

Support matrices and immobilized enzyme systems

Thermal deactivation of amyloglucosidase is substantially retarded at elevated pressures relative to atmospheric pressure. The productivity of glucose formation from amyloglucosidase-catalyzed hydrolysis of starch or partially hydrolyzed starch is significantly increased when the hydrolysis is performed at a pressure greater than about 500 psig.

Increasing the stability of amyloglucosidase

Commercial glucose solutions used as feedstock for enzymatic conversion of glucose to fructose by glucose isomerase often contain materials which act as poisons toward the enzyme. It has been found that these poisons can be removed, or destroyed, by treatment of the feedstock with oxidizing agents, chief of which is hydrogen peroxide.

Pretreatment of glucose feedstock

Commercial glucose solutions used as feedstocks for enzymatic conversion of glucose to fructose by glucose isomerase often contain materials which act as poisons toward the enzyme. It has been found that these poisons can be removed, or destroyed, by treatment of the feedstock with reducing agents which are water soluble and water stable metal hydrides, such as sodium borohydride.

Pretreatment of glucose feedstock with reducing agents

An improved method of preparing support matrices, characterized as inorganic oxides impregnated with a polyamine cross-linked with a bifunctional reagent so as to furnish a plurality of pendant functional groups, comprises impregnating the oxide at a pH less than about 4 and subsequently curing the polyamine-impregnated oxide at a pH from about 8 to about 12. This improved method leads to subsequently prepared immobilized enzyme systems whose activity is increased by about 35%.

Method of preparing a support matrix

An improved method of preparing support matrices for immobilization of reactive chemical entities, such as enzymes, comprises deposition of a polyamine on core support, such as an inorganic oxide, contacting the polyamine-coated core support with a bifunctional reagent which cross-links the polyamine and provides pendant functional groups, and recovering the matrix, wherein the improvement comprises means of depositing the polyamine as a thin, uniform film.

Support matrices for immobilized enzymes

An improved method of preparing support matrices for immobilization of reactive chemical entities, such as enzymes, comprises deposition of a polyamine on a core support, such as an inorganic oxide, contacting the polyamine-coated core support with a bifunctional reagent which cross-links the polyamine and provides pendant functional groups, and recovering the matrix, wherein the improvement comprises deposition of the polyamine as a thin, uniform film from solvents of low surface tension.

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Forest Lake, IL, United States of America

Ronald P Rohrbach