Complexes with Dyes

Several dye coloration scales are used to characterize starch varieties. Perhaps the oldest is the differentiation between starches based on the uptake of Saphranin and Gentiana Violet (see Table XXXVIII).787 Co-vello788 presented another coloration scale which is based on the use of six common acidic and basic dyes (see Table XXXIX). Like the Saphranin and Gentiana Violet dyes, these dyes adsorb directly on starch. Table XL presents a list of synthetic dyes tested in starch dyeing.789-790 Zwikker791 observed the reactions of mechanically damaged starch granules and amylo- 

Dyeability of Starches with Saphranin and Gentiana Violet on the 15-Point Scale 7 

Dyeing of Starch with Acidic and Basic Dyes788 

Starch Variety Fuchsin Acidic Basic Methyl Violet Methylene Blue Congo Red Eosin 

Little or No Dyeing Effect Medium Dyeing Effect Strong Dyeing Effect 

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As in the case of proteins (Section 2.5), the complexation with dyes... 

Fig. 5 (a) Stem-Volmer plot of QD fluorescence quenching in complex with dye 36. (b) Sequence of single complex emission spectra of dye 36/QD in PMMA. Reprinted with permission from [57], Copyright 2008 American Chemical Society... 

Glazer, A. N. Benson, S. C. DNA complexes with dyes designed for energy transfer as fluorescent markers. PCT Int. Appl. WO 9417397, 1994. 

Uses Anti-soil redeposition agent in laundry liq. and powds. shows surf. act. and can stabilize colloidal dispersions forms complexes with dyes and a variety of aromatic compds. forms hard, solv.-resist. films Properties Powd. sol. in water on neutralization (pH > 4.5 or higher) high m.w. Toxicology LD50 (oral) > 5000 mg/kg low toxicity, no skin/eye irritation Gaftex ACP1004 [ISP]... 

Finding the End Point with a Visual Indicator Most indicators for complexation titrations are organic dyes that form stable complexes with metal ions. These dyes are known as metallochromic indicators. To function as an indicator for an EDTA titration, the metal-indicator complex must possess a color different from that of the uncomplexed indicator. Furthermore, the formation constant for the metal-indicator complex must be less favorable than that for the metal-EDTA complex. 

The concentration of fluoride in drinking water may be determined indirectly by its ability to form a complex with zirconium. In the presence of the dye SPADNS, solutions of zirconium form a reddish colored compound, called a lake, that absorbs at 570 nm. When fluoride is added, the formation of the stable ZrFe complex causes a portion of the lake to dissociate, decreasing the absorbance. A plot of absorbance versus the concentration of fluoride, therefore, has a negative slope. 

Naphthalenediol. 1,5-Dihydroxynaphthalene or Asurol is a colorless material which darkens on exposure to air. It is manufactured by the fusion of disodium 1,5-naphthalenedisulfonate with sodium hydroxide at ca 320°C in high yield. 1,5-Naphthalenediol is an important coupling component, giving ortho-a2o dyes which form complexes with chromium. The metallised dyes produce fast black shades on wool. 1,5-Naphthalenediol can be aminated with ammonia under pressure to 1,5-naphthalenediamine. 

Nickel also has been used as a dye site in polyolefin polymers, particularly fibers. When a nickel compound, eg, the stearate or bis(p-alkylphenol) monosulfide, is incorporated in the polyolefin melt which is subsequently extmded and processed as a fiber, it complexes with certain dyes upon solution treatment to yield bright fast-colored fibers which are useful in carpeting and other appHcations (189). Nickel stearate complexing of disperse mordant dyes has been studied (190). 

Table 5. Typical Basic Dyes Used as Complexes with Heteropolyacids...

Aromatic amines form addition compounds and complexes with many inorganic substances, such as ziac chloride, copper chloride, uranium tetrachloride, or boron trifluoride. Various metals react with the amino group to form metal anilides and hydrochloric, sulfuric, or phosphoric acid salts of aniline are important intermediates in the dye industry. 

Metallic additions to the melt, usually in the form of copper sulfate, brighten the shade of certain dyes, such as the Bordeaux range made from phenazones and the greens made from the indophenols the metal forms a complex with the dye. However, copper-containing dyes cannot be appHed to material that requires vulcanization. 

Certain organic compounds form reversible gels with poly(vinyl alcohol). Congo red, for example, yields a red gel that melts sharply at about 40°C. Other organic compounds that form temperature-reversible complexes with PVA include a2o dyes, resorcinol, catechol, and gaUic acid (168—170). 

Reaction with vatious nucleophilic reagents provides several types of dyes. Those with simple chromophores include the hernicyanine iodide [16384-23-9] (20) in which one of the terminal nitrogens is nonheterocyclic enamine triearbocyanine iodide [16384-24-0] (21) useful as a laser dye and the merocyanine [32634-47-2] (22). More complex polynuclear dyes from reagents with more than one reactive site include the trinuclear BAB (Basic-Acidic-Basic) dye [66037-42-1] (23) containing basic-acidic-basic heterocycles. Indolizinium quaternary salts (24), derived from reaction of diphenylcyclopropenone [886-38-4] and 4-picoline [108-89-4] provide trimethine dyes such as (25), which absorb near 950 nm in the infrared (23). 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

Mordant dyes have hydroxy groups in their molecular stmcture that are capable of forming complexes with metals. Although a variety of metals such as iron, copper, aluminum, and cobalt have been used, chromium is most preferable as a mordant. Alizarin or Cl Mordant Red 11 [72 8-0] (1) (Cl 58000), the principal component of the natural dye obtained from madder root, is the most typical mordant dye (see Dyes, natural). The aluminum mordant of alizarin is a well-known dye by the name of Turkey Red and was used to dye cotton and wool with excellent fastness. However, as is the case with many other mordant dyes, it gave way to the vat or the azoic dyes, which are applied by much simpler dyeing procedures. 

Charge-Transfer Forces. An electron-rich atom, or orbital, can form a bond with an electron-deficient atom. Typical examples are lone pairs of electrons, eg, in nitrogen atoms regularly found in dyes and protein and polyamide fibers, or TT-orbitals as found in the complex planar dye molecules, forming a bond with an electron-deficient hydrogen or similar atom, eg, —0 . These forces play a significant role in dye attraction. 

Level Dyeing Techniques. It is exceptionally difficult to obtain level dyeings on acryhc, and temperature and pH control depend on fiber type and are not always adequate. Sodium sulfate in limited amounts can be used to some effect. The sulfate ions compete for the dye with the fiber SO3 sites and so retard the rate of dyeing by forming a dye complex with the ions. The effect of sodium sulfate is best with dyes having the lowest... 

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