CN85106262A - The manufacture method that Operand is formed - Google Patents

Abstract

The present invention relates to a kind of method of making new Operand, it shows very big effect for the sterilization on skin, mucous membrane of animal and inanimacy surface, and it also provides extensive function of killing microorganism, and avirulence or excitant.The complexing that system idodine of the present invention is iodine and glucosan or the polymer that generates by sucrose and epoxychloropropane copolymerization and the complexing of iodine.The present invention relates to again and contains these complex compound disinfecting components, and prepares the method for these complex compounds.

Description

The manufacture method that Operand is formed

Iodine is nonmetalloid one of in the halogen family, also is unique at room temperature for solid-state in the halogen family.The chemical valence number of iodine is-1 to+7, and it is stable on thermodynamics that there is the compound of being formed in all oxidation forms of iodine.

Iodine is to be found in the 19th-century initial stage, and its use for the first time the treatment on be the treatment goitre (goiter) in the near future, be used in the sterilization of wound again, that is when U.S. war (American war), the treatment of the sterilization of wound and sterilization when generally iodine being used for war.From that time, iodine is acknowledged as a kind of more excellent bactericide (germicide), but because it has some intrinsic chemistry, physics and biological property are arranged, therefore, the sterilization of iodine has just had restriction for the mankind and animal.

The high vapour pressure of elemental iodine (elemental iodine) makes the fungicidal effectiveness difference of medicament composition, owing to the iodine composition of preparing sterilization along with the time volatilizees.In addition, its high vapour pressure has limited the purposes of iodine in a sealing at interval, for example body cavity or below wrapping, that is that this is all caused by iodine because of the damage of corroding and the stimulation of skin, mucous membrane and other important tissue.Though the toxicity of iodine is low, once took place unexpectedly to inject iodine liquid and caused death.According to the record that pathology worsens, the example major part of this iodism death is to regulate the result of go down (tissuehypataxia) and local damage because of tissue, and this is more serious than iodism.

The purposes of another restriction iodine sterilization is that its height water-insoluble (being 0.034% in the time of 25 ℃) is as utilizing alcohol (for example being dissolved in the iodine in the alcohol) or utilizing inorganic metal salt can increase the water-soluble (for example in the preparation of Shandong dagger-axe solution of iodine as lytic agent, sodium iodide or potassium iodide, sodium iodide and potassium iodide be used in Lu Ge (Lugols ') solution), this iodine liquid also contains identical murder by poisoning tissue and shows (toxic tissue manifestation), therefore, also limited the purposes of iodine bactericidal liquid usually.

When alcohol is used as the solvent of iodine, be unusual pain and harmful and be applied to wearing and tearing or injured skin or mucous membrane, in addition, when alcohol volatilize, burn the stretch pollution of corrosion and damage and tissue of the concentration of iodine increase thereby make also increased.

Metal iodine compound (metallic iodides) is used to make elemental iodine soluble in water, is through containing two atom iodine (I ₂) and iodide ion (I ^-) directly form water-soluble iodine complex compound (complex) and generate I, ^-Ion.This aqueous solution iodine does not change the murder by poisoning tissue reaction of elemental iodine, therefore burns and organizes pollution to take place as before.In fact, this undesirable reaction takes place more continually, and that is because denseer elemental iodine is applied to making aqueous solution iodine sterilization composition.

In water, iodine is dissociated into down column balancing:

Equilibrium constant K ₁, approximately be 4 * 10 ^-46, change with temperature.In hydrophily circle, this phenomenon of dissociating is further complicated and form various iodide ions for diatomic iodide (diatomic iodine), and most important be I, ^-Ion, the equilibrium constant K of following reaction equation ₂Be approximately 7.5 * 10 ²

Best, this two balanced reaction is merged to explain that diatomic iodide dissociates in the aqueous solution:

Wherein equilibrium constant K is worth about 3 * 10 ^-4,

In acid solution, iodine is a kind of retentivity oxidant, its redox equilibrium electromotive force is that 0.534V(is in the time of 25 ℃, the I-I galvanic couple), iodine can easily be oxidized to sulphate (Sulfate) to sulphite (sulfite), with thiosulfate (thiosulfate) easily is oxidized to tetrathionate (tetrathion-ate), but ferric iron and cupric (cupric) salt is reduced by iodide ion in acid solution, and generates free-iodine.In weak solution, but iodine complete oxidation SO ₂Become H ₂SO ₄, iodide are H then ₂SO ₄Be reduced into SO ₂, S and H ₂S and free-iodine discharges.In neutrality or dilute alkaline soln, iodine can present stronger a little oxidation, and this is because the formation of iodite ion, according to following reaction equation:

This aqueous solution is strong iodating agent, and it acts on health protein and other biological substances, produces oxidoreduction and change in alkaline physiology PH scope, and in proteinaceous tissue, iodine causes unsaturation to connect, and causes denaturation, disturbs necessary physiological reaction.

Poison the sense of organization in order to overcome aqueous solution iodine and water-alcohol solution iodine, keep its bactericidal action and function of killing microorganism simultaneously, so will prepare the water-soluble organic complex of iodine with organic polymer body.Just, elemental iodine and some organic polymer body chemical combination, for example, can make the water-soluble increase of elemental iodine, and this kind polymer-iodo-complexes is referred to as Operand with kollidon and the polymeric chemical combination of abstergent.

Past, the normal organic polymer body that generates Operand that uses was that a wide range long-chain macromolecule is formed, and also may be the character of ionic or nonionic, and interfacial agents or non-interfacial agents character are also arranged simultaneously.Having a kind of loose chain to link to form complex compound or Operand and equal 30% the content of iodine aqueous solution in weight ratio between iodine and organic polymer body is (except that other had note, percentage was percetage by weight in this literary composition) that can prepare.

General organic iodine preparation compound comprises two groups of different poly-and bodies.Polyvinylpyrrolidone, this is a kind of non-abstergent, nonionic and non-interfacial activity polymer; Various types of abstergents/interfacial activity polymer, it comprises nonionic, anion and cationic interfacial activity polymer.Two groups of polymers and elemental iodine complexing and form Operand, teepol and can't provide the complex compound of stablizing iodine usually.But some cation interfacial active agent such as U.S.3,039,916 is considered to the iodo-complexes applicable to the preparation sterilizing use.

Non-abstergent, nonionic organic polymer body usually can not be as the carriers of iodine in sterilization is used.Have only a kind of polymer polyvinylpyrrolidone to confirm to be formed with the iodine complexing sterilization composition of the Operand of usefulness now satisfactorily, polyvinylpyrrolidone is a kind of nonionic, non-abstergent, water-soluble synthetic organic polymer body; It is characterized in that it has unusual complexing power and comprises the colloidal state character of its physiology inertia, though the known more or less iodine of amount that has of polymer iodo-complexes, normally used polyvinylpyrrolidone-iodine (PVP-I) complex compound contains about 9 to 12% titration iodine.Kollidon-iodine (PVP-I) is a kind of dynamical bactericide, provides the whole microorganisms of various antagonism microbicidal effect.

Polyvinylpyrrolidone-iodine (PVP-I) shows the murder by poisoning nerve that it is low, and it does not stimulate mammiferous tissue basically, and it is non-sensitization in addition, does not cause pain when being used for wound or mucous membrane.

Therefore, polyvinylpyrrolidone-iodine (PVP-I) utmost point is used as the important bactericide of a kind of human body, animal and environment widely.Povidon iodine and manufacture method thereof are in U.S. Patent No. 2,739, and 922 records still, do not have the non-abstergent of other class, and it is applicable to this sterilisation purpose that the composition of the organic polymer body of nonionic confirms.

Usually the method for making the Operand complex compound be the two matter atom iodine of element and selected polymer under the dry situation of the universe or under the powdery situation, perhaps in the presence of a suitable solvent, contact to heat and quicken the complex compound generation.What just can obtain the Operand complex compound of carrier of corresponding polymerism and iodine after reaction finishes can make ratio again.

Many researchs are pointed out: organize neuron excitotoxicity although Operand has improved, the microbicidal ability that the Operand sterilization is mixed with is identical with the aqueous solution of known elements iodine or the microbicidel ability of alcoholic solution basically.Demonstrated Operand sterilization preparation than the aqueous solution of inorganic elements iodine or the superiority and the inherent structure of alcoholic solution, for residue neuron excitotoxicity attenuating basically, stimulate tissue to reduce, reduced the vapour pressure of iodine, especially do not pollute the feature of skin.

The Operand preparation is according to available iodine or titration iodine, and this can think to discharge the iodine of its bactericidal action from complex compound.But the iodine that so obtains can't reflect the contained total iodo quantity of Operand or its sterilizing ability.

Learn that from above-mentioned the optimal polymer of generation of Operand is a polyvinylpyrrolidone, it is unique non-abstergent, and nonionic organic polymer body is suitable for the manufacturing of anticorrosion Operand.

Main purpose of the present invention provides a kind of non-detergency, nonionic polymer, and it can form complex compound and provide high efficiency to contain the biocide preparation of iodine with elemental iodine.

Another object of the present invention provides nonionic, the organic carbohydrate polymer of non-detergency, and it can produce effective Operand with the elemental iodine complexing.

A further object of the present invention provides new nonionic, non-detergency Operand and sterilization thereof and corrosion-resistant composition.

Another object of the present invention provides a kind of method of producing new Operand.

Other purpose of the present invention and advantage can will be appreciated that after reading following specification and claim part.

Learn that from above-mentioned purpose the present invention mainly comprises iodine and glucosan complex compound, the perhaps complex compound of iodine and carbohydrate polymer, its carbohydrate polymer is generated by sucrose and epoxychloropropane copolymerization.

Glucosan is a kind of non-nutritive, polysaccharose, carbohydrate polymer, and it is generated carrying out condensation polymerization reaction under polycarboxylic acid and the catalyst and under step-down by carbohydrate.Glucosan is in U.S. Patent No. 3,766,105 and No.3,786,794 and Pfizer (Pfizer, Inc) New York can get it.

Glucosan is that a kind of white is to the yellowish-brown powder, it has water soluble and water-insoluble form, its mean molecule quantity is about 1,500 to 36,000, water-soluble glucosan mean molecule quantity about 2,500 to 18,000 and the mean molecule quantity of water-insoluble glucosan is between 6,000 to 36,000, (J.Res.Nat ' l.Bur.Standards 24 by " revise reduction and (Isbel) combined method " when the mean molecule quantity of glucosan, when 241(1940)) measuring, glucosan mean molecule quantity normal range (NR) is greatly about 1,000 to 24, between 000, and most molecular weight is within 4,000 to 12,000.When using " revising reduction and combined method " when measuring the glucosan mean molecule quantity, its mean molecule quantity is shown as 1.5 times by " revise reduction and with the Si Beier combined method " measured mean molecule quantity.But the polymeric mean molecule metering method of measurement known to any is characterized in measuring the mean molecule quantity of glucosan.

Find out clearly that from the molecular formula (being provided by Pfizer (Pfizer)) of glucosan signal the 1-6 chain is preponderated basically, that is because of first order hydrogen-oxygen group reactivity, although other grape sugar chains also may generate.In the glucosan of solubility, every part exists acid esters to change into glucosan, and when the part esterification of acid becomes to surpass glucosan partly, Zhi Lian (cross linking) will take place.Synthetic glucosan is not influenced by amylase (amylolytic) catalyst, and Animal nutrition and radiotracer (radioactive tracer) studies show that glucosan is non-toxicity.

Commercial, usually obtainable many grapes polymer be low-molecular weight water-soluble, the bonding aggressiveness of irregular glucose wherein contains a little tail base and citric acid (citric acid) remnant of being connected the Diakarmon on the polymer by single and diester linkage, irregular connect key and sometimes the effect that in many grapes, produced of diester (di-ester) cross linkage be to be combined into stronger antiacid or catalyzer hydrolytic polymerization body, this is strong compared with other hydrocarbon polymer such as carbohydrate (starch).

Usually be 1 with regard to commercial obtainable glucosan mean molecule quantity, 500, scope is between 162 to approximate 20,000 this molecular weight ranges guarantees that a kind of height water-soluble reaches than low viscosity, the main character that has is identical with sucrose, but do not have sugariness on the sense of taste, commercially available glucosan molecular weight is:

Molecular weight ranges percentage (%)

162～5，000????88.7

5，000～10，000????10.0

10，000～16，000????1.2

16,000～18,000 0.1 glucosans contain 5-hydroxymethylfurans sugar (5-hydroxymethylfururfural) and a little levulose (levoglucosan) (1-6 DEXTROSE ANHYDROUS) of trace, also have unreacted original composition such as glucose, Diakarmon and the citric acid of less amount in addition.

When the glucosan polymer combines with elemental iodine, its product is PDI (PDI), this glucosan iodo-complexes is that a kind of yellowish-brown is to amber powder, it begins fusing in the time of about 93 ℃, in the time of 127 ℃, be melt into fully and be a kind of liquid, glucosan iodine powder is a kind of highly-water-soluble, at high temperature become an aqueous solution russet, the glucosan content of iodine reaches 80%, even can make higher concentration solution, the water-soluble of this increase and iodine water-insoluble is approximately 0.034% one-tenth sharp contrast.The increase of this water solubility represents between stage of reaction of glucosan and iodine that complex reaction has taken place and generates noval chemical compound, and it has had new advantageous property.Glucosan-iodine aqueous solution (PDI) is acid under natural form, but can play cushioning effect and not disturb the generation or the bactericidal action of complex compound in whole physiological acid pH value scope.

Utilize the infrared spectrum of potassium bromide (KBr) ball glucosan iodine, scope system is by 4,000cm to 200cm shows a very little flat projection " shoulder ", and (shoulder) demonstrating one in 800cm to 300cm strengthens peak value (peak), soluble in water when glucosan iodine, its titration content of iodine can be by iodine of knowing and hypo solution (Na ₂S ₂O ₃) titration method measure.

This method of testing shows that glucosan iodine can be provided for the sufficient balance iodine of sterilization purpose, so that this material is effective bactericide.

Carry out glucosan iodine conductivity test, determine glucosan and I ^- ₃Or I ^-Carry out complexing, be because significantly less in the equivalent conductance of the zero-dose equivalent conductance (equivalence) during than iodine liquid (Lu Ge (Lugol s) solution), in addition, record the ratio of free ion and coupled ion again, be a constant when concentration descends, glucosan iodine demonstrates free ion concentration low than iodine solution.

According to embodiments of the invention, preparation iodine and polymeric complex compound, and this polymer is generated by sucrose and epoxychloropropane copolyreaction.This polymer molecule contains a difference structure and high hydroxy (hydroxyl) group of content, and its hydrogen-oxygen group causes polymeric high-dissolvability in polymer aqueous solution media.

The polymer that is formed by sucrose and epoxychloropropane copolymerization is by Pharmacia Fina Chemicals AB of Uppsala Sweden, sell its Fick that by name (Ficoll), for the convenience of discussing in the present invention, the polymer made by sucrose (sucrose) and epoxychloropropane (epichiorohydiin) replaces it with Fick you (Ficoll).

The molecule of Fick you (Ficoll) has the difference structure, and the hydrogen-oxygen group of the high-load that causes good solubility in aqueous medium is arranged.In Fick you (Ficoll), ionogen does not exist, it is again nonionic as glucosan, the non-back property of going, the organic carbohydrate polymer in non-interface, Fick that (Ficoll) its manufacture method and character can be by obtaining in " research (Ficoll For Cell Research) of your (Ficoll) pair cell of Fick " of being published at (Pharmacia) Fine Chemicals, you show Fick and the identical character of PD I complex compound by (Ficoll)-iodo-complexes, be meant the release of biocidal efficacies and iodine herein, the measurement of its balance is identical with the PDI complex compound with method for releasing.

The PDI(glucosan) all provide release steady, uniform anticorrosion iodine with your (Ficoll) iodine (FI) of Fick complex compound, when being used to have life or inanimate surfaces after after a while, and nonirritant or toxicity produce.This is a great advance, compared with above learn contain the stimulation that the inorganic iodine biocide preparation not only produces high toxicity, skin or surface, and uncontrollable sterilization iodine is in the release after after a while.

Learn from above, can't expect any non-detergency, nonionic, non-interface organic polymer body fully except that polyvinyl pyrrolidone, can be suitable for the manufacturing of Operand complex compound.But your (Ficoll) polymer of present known glucosan and Fick is two manufacturings that are suitable for required complex compound, produces enough and effectively bactericidal action.In addition, when making the complex compound similar to PVP-I, both all more have bigger water-soluble effect than polyvinylpyrrolidone and the very little elemental iodine of solvability the luxuriant and rich with fragrance sugared polymer of many grape and Fick that (Ficoll) polymer, therefore, in fact, when utilizing normal heptane (n-heptane) when extracting, the polymer iodo-complexes of PDI and FI, at the solid-state iodine that do not dissociate out down, that is to be iodo-complexes or FI complex compound and IO at PDI ₃ ^-Anion is reached balance and normal heptane and other organic solvent are undissolved.

Under classify the detailed description of the invention as, it only is intended as example explanation but not limits the scope of the invention.

Learn that from above-mentioned glucosan is water-soluble, the Diakarmon that the polymeric D-glucose of irregular key (D-glucose) contains trace is that tail base and citric acid remnants are linked to polymer by single or diester chain.Glucosan contains various grape sugar chains that may types, because the reactivity of first order hydroxy, 1-6 is bonded in glucosan and wraps up in and showing.Because the irregular bonding that produced and once in a while the crosslinked combination of diester make this polymer than other polymer such as starch to antiacid or antienzyme water Jie ability is strong.

Glucosan is polymeric synthetic, learn by above-mentioned, in United States Patent (USP) NO.3,766,165 and NO.3, disclose in 876,794, and polymer itself can be obtained by Pfizer (Pfizer), purposes known to previous comprises the multiple use of food additive, as reduce calorie and fill agent, these purposes comprise the additive of cooking food, chewing gum, the candy class, salad seasoning (salad dressings), dairy produce, boiled goods or the like and other edible product, in a word, many grapes are placed after a period of time still stable, still, deposit for a long time in high temperature it is faded a little.

More than 130 ℃, many grapes are melted into a kind of clear liquid, and this is identical with sucrose.The glucosan of N type can be obtained by Pfizer, is one limpid, faint yellow 70% solution, is partly to be neutralized by glucosan and potassium hydroxide.The viscosity of this kind N class glucosan is than the sugar of same concentration or the next height of Diakarmon.

Glucosan also can have the effect of humectant (humectant), the moisture content of absorption ability is arranged up to reaching equalization point under normal atmosphere pressure.10%(W/V) its pH value of the glucosan of the aqueous solution is about 2.5 to 3.5.

The safety that glucosan is used is by 32 different researchs, 5 kinds of animals and be among 8 human research and determine.Be not absorbed through the most of glucosan of human body.Another little part is main to form carbonic acid gas and volatile fatty acid for enteron aisle utilizes promptly the new battle array metabolism by enteric microorganism, and it can be absorbed by the body and utilize as a kind of energy.Glucosan be applied as FDA permission.And regulation is with made by D-grape and little part Diakarmon and citric acid, and the metabolic water-soluble depolymerization zoarium of part is identical, and glucosan can partly neutralize with potassium hydroxide.

When the glucosan with 0.10 gram is dissolved in the water of 25ml, and when analyzing its ultraviolet signature, the acquisition absorption spectrum is 800-190nm.In the 190-300nm zone, produce two peaks, its peak is at 193nm and 281nm, and the intensity of absorption is respectively 2.87 and 0.144, and ultraviolet spectrogram is represented it in Fig. 5.

Light transmittance percentage about infrared spectrum glucosan-KBr ball is measured as 400～200cm ^-1, can be observed everywhere infrared ray absorbing just 3,450～2,500cm ^-1, 1,800～1,200cm ^-1, 1,200～800cm ^-1With 800～300cm ^-1At 2970cm ^-1Locate to have to have narrow weak " shoulder " (strong density) wide peak (shoulder), 1,600cm ^-1There is a medium quite wide peak at the place and 1,000cm ^-1Locating a kind of strong quite wide peak can be observed, and this infrared spectrum analysis is represented in Fig. 6.

With concentration is the glucosan viscosity of function, can be recorded to the various solution methods of 60%W/V by 1%W/V by the preparation poly-dextrose-comprising.The viscosity of these solution has recorded and has been that function marks with concentration at 25 ℃, and in addition, the ratio of viscosities of the viscosity of glucosan and Diakarmon and sucrose is also illustrated in down in the tabulation 1.

Table one

Viscosity (CP millipoise)

% polymer W/V Diakarmon (sorbitol) sucrose glucosan

10%????-????-????10

30%????-????-????15

40%????-????-????24

50%????10????24????46

60%????24????40????100

70%????120????300????800

The above-mentioned viscosity system that surveys is provided by Pfizer (Pfizer).

The mean molecule quantity of Fick you (Ficoll) is 400,000 ± 100,000, and inherent viscosity (intrinsic viscosity) is 0.7dl/g approximately, and specific rotatory power (∞) ²⁰D is+56.5 °.The polysaccharose Fick you (Ficoll) but in the polymer dialysis material be less than 1%, comprise sodium chloride.Reactive and the stability of Fick that is to be existed to determine by hydroxy in the sucrose remnants wherein and glucosyl group, Fick you (Ficoll) in alkalescence or all be stable in the neutral liquid, when being lower than pH value 3, you can be hydrolyzed Fick very soon, especially in high temperature, can be hydrolyzed very soon, but you (Ficoll) carry out Fick 30 minutes sterilization of hot pressing (autoclaving) and do not have the structure of splitting and produce (degradation) at 110 ℃ in neutral liquid.on）。

Obtain by Pharmacia Fine Chemicals, Fick you (Ficoll) is supplied with the pulvis of drying, therefore in being situated between, hydrophily is easy to dissolving (slowly add simultaneously and stir) in solution, the Fick you (Ficoll) that equals 50%W/V concentration can obtain, and you the relative viscosity (relative visc-osity) of (Ficoll) solution represent following table two its Fick under variable concentrations:

Ficoll percentage (W/V) 10 20. 30 40 50

In the time of 20. ℃ 5 20. 60 80 600

Be different from sucrose itself, the osmotic pressure (Osmotic Pressure) of your (Ficoll) solution of Fick is low, but its density can be compared with sucrose.Because HMW and low dialysis ability, so Fick you for the cell membrane penetration capacity than low many of sucrose, the Fick that mainly was applied to the formation (canfiguration) of dense medium, wherein (Ficoll) ll in the past) be utilized to separate (separation) and isolate (isolation) cell and secondary cell particle.In protein solution, you also can be applied to Fick stabilizing agent and be applied in the dialysis.

Operand by iodine and glucosan or your polymer generation of Fick, and can add other suitable composition, these some compositions that are fit to comprise buffer, additional interfacial agents, with additional nonaqueous solvents, glycerine (glycerin) is exactly an example of these solvents.

Iodine and the content that the present invention's new Operand combines, also be exactly your polymer of glucosan Operand or Fick be will with other Operands as povidon iodine (polyvinyl-pyrrolidone iodine).Generally, content of iodine is between 1～20.% is chosen as 2～16% and optimal selection is 2～10%.

Glucosan complex compound or polysaccharose Fick that polymer and iodine can form by reacting to each other to make between elemental iodine and glucosan or your polymer of solid-state Fick, the speed of this reaction (formation of required complex compound) can be recorded by temperature control, this reaction is carried out slowly at room temperature, but reaction is accelerated in heating, best, be earlier required glucosan amount or your polymer of Fick to be dissolved in a long-pending property solvent, in water, and then addition element iodine, firmly be stirred to dissolving fully.Elemental iodine is inserted the polar solvent that its this base is the aqueous solution, as Shandong dagger-axe (Lugols) solution, or the NaI-I aqueous solution.

Other be fit to introduce that iodine enter polar solvent and the solution that forms Operand comprises KI-I, and hydroiodic acid (hydriodic acid) liquid.In the present example, the generation of good new Operand, be in polar solvent by your polymer of elemental iodine, alkali metal iodine and glucosan and/or Fick, in the aqueous solution, react to each other and form, in the case, the content that glucosan and Operand can produce in weight ratio iodine approximately reaches 20%, and this is based on applied glucosan polymer weight.

The adjuvant of other kind also dissolves in the polar solvent these adjuvants as buffer, interfacial agents, glycerine etc. during the PDI complex compound generates, introduce in the solution up to the composition of all needs, and solution fully stirs about 30 minutes of enough time, as must the time can cool off this solution, can filter and freeze the universe selectively to make crystallization or PDI Operand complex compound powder.Iodine can be introduced in the glucosan solution by any way.As, add the alkali metal iodine solution simultaneously, and then add a spot of hydroiodic acid and made appropriate and freeze the universe up to solution, then can analyze the content of iodine of this complex compound.This Operand also over time (after several weeks) analyze its content of iodine again, do not dissipate over time for the validity of determining this preparation, other suitable polar solvents that are used to make the Operand complex compound comprise that alcohol also has water and both mixing.

At room temperature, glucosan iodine powder is very soluble in water, and this solution is a reddish brown chamber, and the effective value of iodine (in the Operand solvent) can directly utilize normal sodium thiosulfate and record.This is a kind of classical oxidation-reduction reaction and commonly using on means of iodine chemical.For example, contain the glucosan iodo-complexes (PDI Operand) of 7.45% effective content of iodine, show that solvability is in water about 81%.Have 3.25% available iodine glucosan complex compound, be also illustrated in that solvability is 81% in the water.

The fusing point of various after measured PDIs, these samples are in advance once at P ₂O ₃Vacuum under dry 16 hours of the universe, the fusing point that records different samples again is listed in following table:

The sample fusing point (℃) observe

A kind of dark red liquid of 7.45% available iodine, 97～127 melt intos

A kind of red liquid of 3.25% available iodine, 93～127 melt intos

Independent a kind of clear liquid of glucosan 115～130 melt intos

PDI shows that its melting range increases, its fusing point is than next low of independent glucosan, the test of this fusing point is carried out on the magnificent frosted glass fusing point tester of the female scholar tiger of soup, and the fusing point of (Thomas Hoover Capillary Melting Point Apparatus) measured elemental iodine is 113.6 ℃.

Generally, when making Operand, have several factors to influence the validity and the quality of preparation, for example, the amount of contained iodide ion seriously influences the Operand overall stability in solution.Elemental iodine Jie is inversely proportional to from rate and iodide ion concentration in solution, the increase of pH value in the preparation in addition, minimizing Operand overall stability, but the increase of iodide ion content just has its minus effect, that is to say, increases the stability of Operand.In addition, the intensity of being closed by the chain that forms between your (Fico Ficoll) polymer of elemental iodine and glucosan or Fick or their combination is stored or their iodine that body discharges to the speed of reception place plays a critical effect by polymer determining.

Multiple Operand as, glucosan iodo-complexes (PDI) and povidon iodine (PVP-I) are that (Lugol ' s) solution is made by polymer glucosan and polyvinylpyrrolidone (PVP-K30) and first quality iodine or Shandong dagger-axe.Polyvinylpyrrolidone (PVP-K30) is a kind of quite high molecular weight polyisoprene zoarium, it has 95% at least, having mean molecule quantity is 40,000, this polymer produces the povidon iodine complex compound when with Iod R, can be learnt by above-mentioned, this complex compound water soluble and when imposing on a wound, as a kind of antibacterial agent.The speed that stores the iodine that discharges from polymer is determined by the intensity of key between iodine and polymer and the pH value of prescription.

Effective several prescriptions with varying strength are made by glucosan iodine (PDI) and polyvinylpyrrolidine iodine ketone complex compound, on different microorganisms, have antibacterial action.Four kinds of prescriptions that use PDI, interfacial agents, glycerine and buffer are to make in 5 o'clock at pH value.Effectively content of iodine is 2.0%, 1.0%, 0.25% to 0.1% in this preparation.Only utilize buffer to make four kinds of samples in addition, its effective iodine intensity, with originally when the PH5 the made iodine intensity of four kinds of preparations identical.

In addition, utilize PVP-I, interfacial agents, glycerine, reach buffer, same is 5 o'clock at PH, and four kinds of prescriptions are made by povidon iodine (PVP-I) complex compound, and effectively content of iodine also is by 2.0%, to 0.1% changes at 1.0%: 0.25% in the PVP-I preparation.Same, other four kinds of samples only utilize the buffer preparation, require available iodine intensity and be approximately 5 o'clock obtained available iodine intensity at pH value identical.

It is antibiotic to use following microorganism to do, and estimates:

Staphylococcus aureus #1(ATCC 6538) penicillin sensitivity

Staphylococcus aureus #4(GBL) anti-penicillin

Staphylococcus aureus #30(GBL-CDC) toxicogenic shock fatigue

Staphylococcus epidermidis albus (GBL) normal skin plant

B.Pumilus E601 sporozoite

Operand is applied to identical bacteria samples respectively, and its composition is detected as follows in test:

PDI complex compound 2.0% effective I ₂

27.78g PDI compound

30.0g glycerine

0.25g Ya Liba (CO-436)

（Alipal）

1.119g????CO-436

Buffer

Add water to 100cc

The PDI compound contains 1% effective I ₂

13.89g glucosan iodine

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

0.56g????CO-436

Buffer

Add water to 100cc

The PDI complex compound contains 0.25% effective I ₂

3.47g glucosan iodine

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

0.140g buffer

Add water to 100cc

The PDI complex compound contains 0.1% effective I ₂

1.38g glucosan iodine

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

0.056g buffer

Add water to 100cc

The PVPI complex compound contains 2.0% effective I ₂

20.0g????PVPI

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

4.18g buffer

Add water to 100cc

The PVPI complex compound contains 1% effective I ₂

10.31g????PVPI

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

2.09g buffer

Add water to 100cc

The PVPI complex compound contains 0.25% effective I ₂

2.58g????PVPI

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

0.523g buffer

Add water to 100cc

The PVPI complex compound contains 0.1% effective I ₂

1.031g????PVPI

30.0g glycerine

0.25g refined gift crust CO-436

（Alipal）

0.209g buffer

Add water to 100cc

The result who is tested represents with following each form:

Laboratory report

Table five

Attention:

When less than 15 seconds, in 10 ^-1Dilution, 15 seconds exposure, indication does not have flora (colonines), therefore, and meter＜10 Survivor/ml, this value be low to moderate 1 second (also be exactly＜15 seconds=fully the responsive limit of sterilization) (a) Staphylococcus aureus #1 for the most responsive filtration (strain) the 3/16 complete sterilization that is presented at 15 seconds is only arranged, (b) 5/6, (d) 6/15, (c) Staphylococcus aureus (toxicogenic shock) for the most anti-filtration (strain) in this incident, in the time of 15 seconds, as many as 8/16 Survivor is arranged.

Conclusion

1. relatively analyze demonstration and do not exist together and exist together mutually, see Table 1-4.

2.PDI complex compound 0.1% effective I ₂For least active, the effective I of PVPI2.0% ₂

Learn that by above-mentioned test though the glucosan iodo-complexes (PDI) that contains 2%, 1%, 0.25% and 0.1% available iodine is more more effective than the PVPI complex compound of the available iodine that contains same percentage.Only contain buffer, its available iodine content is that 1% and 0.25% glucosan iodo-complexes is the best prescription of all coccuses (cocci) and sporozoite (spores), yet the PVPI prescription that contains 2% available iodine is for least positive, this shows that glucosan iodine Operand complex compound of the present invention provides a tangible antibiotic and sterilizing use, have more progressive effect compared with PVPI Operand complex compounds of usefulness all.

Glucosan-iodine of the present invention (PDI) Operand complex compound viscosity is also analyzed, make itself and the contrast of independent glucosan solution, PDI Operand solution contains 50%W/V respectively when making, 40%W/V, 30%W/V, 20%W/V, 8%W/V, 5%W/V and 1%W/V iodine, these solution separately are the filter guiding principle filtrations by 0.45 μ, relative viscosity is to utilize Ubbelodhe glass capillary tube viscometer (Ubbelohde glass capillary viscometers) to measure, measure scope for 50～20% soln using OB, OC measures scope for the 10-1% soln using, measures with sample solution flushing time and pure water flushing time ratio 25 ℃ ± 0.05 ℃ relative viscosity.

The water content system of PDI complex compound utilizes card Fischer (E-Fischer) titration mode to be measured as 11.28%.Change iodine be measured at 7.45% and the dense fixed survey of iodide be 6.745%Kl.Therefore, glucosan and glucosan iodo-complexes total content are 74.52% weight.

It is measured that PDI and glucosan are checked normal viscosity, contain the height more next from measured PDI than the viscosity of independent glucosan solution, though all under the glucosan concentration that equates, measurement result can be estimated its intrinsic viscosity thus, the viscosity of the independent glucosan solution of the ratio of viscosities of PDI is big, this shows the expansion a little in the PDI complex solution of glucosan molecule, just such as textural iodine or the iodide of including of material needed polymer in iodoform.

The resistivity of PDI (Specific resistance) or equivalent conductance (equivalent conductanee) compare with the PVP-I Operand, and the solution resistance rate is defined in 1cm and wraps up in, and the electricity of per unit sectional area is led.

In order to analyze equivalent conductance, glucosan iodine and polyvinylpyrrolidone complex compound, except making iodine solution, make the standard liquid of checking of iodine again by following manufacturing.

The KI of the dissolving 100g of manufacturing system of this iodine solution is in the water of 150-200cc.The elemental iodine I of 50g ₂Add in the solution and stir, after add entry again to 500ml.The standard liquid of checking of iodine is to wrap up in dilution with the iodine solution of 5cc in measuring bottle (rolumetric flask) to form, and at room temperature stirs then to allow it overnight in one hour.

Glucose is in the water of 70cc more than the dissolving 10.0g of its method for making system of PDI, what the back added 5cc purchases iodine liquid, stirred gained then and added the volume markings of entry again after than solution to the 100cc measuring bottle, after at room temperature stirred one hour and same make it overnight.

In the water of 60cc, the iodine solution of 5cc is dissolved in the water of 25cc according to the PVP-K30 of 10g in its method for making of PVP-I system, then, adds at leisure in the PVP solution and rapidly with this iodine solution and to stir.The solution of this formation stirs at room temperature up to all jellies and all dissolves, and this solution stirring 1 hour half makes liquor capacity rise to 100cc(then and adds water), stir again hour, make it overnight.

Four kinds of above-mentioned each made solution utilized the 0.02N thiosulfate before analyzing its available iodine content, examine and determine and utilize potentiometric titration and 0.1N nitrate (Ag NO ₃), analyze its all iodide-cpds (I ₂+ I ^-).Same, it is that the polymer of 0.8g is dissolved in the 70cc water that PVP solution and independent glucosan contain the polymeric manufacturing of 8.0g/l, makes other volume reach the scale of required volume as other solution of preparation.Under same volume, the KCl solution of another kind of 0.5M is also manufactured.

Each electricity of seven kinds of above-mentioned made solution is led and electric capacity (capacitance).Analyzed under variable concentrations, be to utilize general radio capacitance testing device just can carry out.The testing liquid of checking standard liquid of iodine, PDI, PVP-I complex compound and independent PVP solution and independent glucosan, all being diluted to its concentration and being solution dilution to the concentration that 2ml/100,1ml/100,0.1ml/50,0.1ml/100 contain iodine is 20ml/100,100ml/100,1ml/100 and 1ml/100, for glucosan or independent PVP solution, parallel electricity is led and electric capacity utilizes a CEL3-J-1 flask, can be directly by reading on the general radio capacity measurement instrument.Potassium chloride (KCl) solution is measured during in 0.1M, 0.00 0.005M, 0.001M, 0.00005M and 0.0001M in concentration respectively.

This test determines that when the PVP solution concentration increased, its equivalent conductance reduced.But, reducing as PVP concentration, its equivalent conductance increases with exponential form.Under the glucosan situation, its equivalent conductance is 0.018ohm ^-1Cm ^-1, when Portugal's concentration of glucose increased, its equivalent conductance orthoscopic descended.This confirmed glucosan than polyethylene propane ketone be difficult to resolve from, (under Lu Ge (Lugol ' s) solution) situation, increase with its concentration, equivalent conductance reduces at iodine solution.

About glucosan-iodine Operand complex compound (PDI), when its concentration increase, electricity is led minimizing.But, descending as concentration, when just diluting, electricity is led orthoscopic and is risen.This confirms that in fact the diluted combination degree of PDI complex compound remains constant, and that is because teriodide and iodide are incorporated on the glucosan.The base value of glucosan equivalent conductance is 10% under zero-dose.The PDI equivalent conductance is 160.4ohm ^-1Cm ^-1, this is more than the equivalent conductance (216.8ohm of PVPI ^-1Cm ^-3) and iodine solution equivalent conductance (222.7ohm ^-1Cm ^-1) come lowly.This trend has confirmed I in the PDI Operand ^- ₃And/or I ^-Be incorporated on the glucosan.Equivalent conductance in the PDI Operand is big more, and its free ion concentration is big more and be attached on the glucosan polymer few more.

In PVP Operand situation, data confirms that some I are arranged ^- ₃And/or I ^-Be attached to PVP but than the PDI Operand for lacking.At iodine solution itself,, be not because iodine in solution, is dissociated fully in conjunction with taking place.In the PVPI complex compound, the square root of its equivalent conductance and its total ion concentration relation of being in line, its equivalent conductance increases with the increase of its concentration.

Compare with iodine solution, the glucosan iodo-complexes is a lower equivalent conductance value, and in this example of zero-dose scope, the additivity rule can't be set up.Ignore the influence of glucosan, because this influence is negligible, so must cause that this is hinting that ion is by the complexing of glucosan institute owing to free ion concentration descends in the decline of zero-dose equivalent conductance for electrical conductivity.But reversible balance do not concern in line with the square root of total ion concentration, and the equivalent conductance of the speed PDI under zero-dose should approach the equivalent conductance of independent iodine solution when its balancing steering dissociates fully.This expression " non-reversible " cohesive process (no covalent bond reaction takes place, and does not have losses of ions in the chemical reaction because titrimetry is illustrated in).

About polyvivyl-pyrrolidone-iodine complex, the total ion of PVP demonstration itself has a little loss, but the not loss of available iodine, this expression and iodine have the interactional possibility of the covalent bond of a little degree.But its zero-dose equivalent conductance is lower slightly than independent iodine solution equivalent conductance, and this shows that PVP is to I ^-Or I ^- ₃Seldom or do not have an adhesion.

This shows, learn based on above-mentioned data, glucosan positively with teriodide (I ^- ₃) or its iodide (I ^-) carried out complexing because the equivalent conductance when zero-dose separately iodine solution for example the Shandong dagger-axe (Lugol ' s) equivalent conductance of solution is few significantly.In PDI, the ratio of free ion and coupled ion is a constant, even no matter also is like this when concentration descends.Therefore, PDI show free ion concentration than the free ion concentration of iodine solution come low.This is related with hydrogen bond or osmotic equilibrium probably, when the equivalent conductance of PDI is low, is tending towards showing I ^- ₃Or I ^-With combining of glucosan.

About PVPI, might iodine be to be contained in the spiral polymer matrix, as if these data confirm few I ^- ₃Or I ^-Combine with PVP, it show PVP for the influence of the equivalent conductance of polyvinylpyrrolidone-iodine approximately than glucosan for big ten times of the influences of PDI complex compound.

Absorption rate testing is represented the complexing to iodine of glucosan and polyvinylpyrrolidone.From the speed of glucosan iodine that Operand discharges is between discharging from polyvinylpyrrolidone between iodine and the independent iodine.In other words, by the reduction order, release iodine speed is: iodine solution, glucosan iodine, betadin.

Measure the balance iodine concentration of the glucosan Operand complex compound that contains 7.45% and 3.25% available iodine respectively, compare with povidon iodine complex compound with available iodine 9.6% and independent iodine solution balance iodine concentration with these balance iodine measured values.Calculate the solution amount that contains 1.0g iodine respectively for these solution, then, above-mentioned each solution put into 80ml water respectively, then in 100ml amount and in add again water rare to volume be 100ml, each solution of gained is used to surveys its balance iodine concentration.For each four kinds of sample so making, use the aqueous solution to compare for four kinds with heptane and extract: the aqueous solution: heptane (heptane) is 3: 1,2: 1,1: 1,0.5: 1.The aqueous solution and heptane suck in the centrifuge tube of 20ml, shake 1 minute, and the back is at centrifuge 2000rpm(rev/min) temperature around centrifugation 2 minutes and the record down.

Then, 522.6nm wavelength place survey organic heptane mutually in the absorption of iodine, utilize following formula to convert the concentration (with ppm represent) of iodine at aqueous phase,

Ppm I ₂(heptane phase)=mg.I ₂Standard/I ₂Absorption

(absorption in sample) * 10

Ppm I ₂(water)=ppm I ₂(heptane)/KP

Kp(is at 23 ℃)=45.0=I ₂In the heptane in the solvability/solvability of 0.03g/ml iodine in water of 23 ℃.

This calculating is to be used in four kinds of different samples and heptane, and its result is marked on the figure, and is as follows from the result of extraction gained:

Balance iodine

PDI, 7.45% available iodine 103.3ppm

Independent iodine solution 141.7ppm

PVP-I complex compound 1.01ppm

These data clearly confirm, balance iodine amount is put less a lot from glucosan Operand release ratio iodine solution, be because iodine and glucosan complexing, when with known PVPI Operand relatively the time, discharge balance iodine by PDI and how much than PVPI, therefore stronger bactericidal action and disinfective action be provided.

The percentage of available iodine is by 0.01% to 20% variation in a kind of aqueous solution glucosan iodine sterilization Operand is formed, and it is that total amount with its special composition or solution changes change.

Ultraviolet light/visible absorbance the scanning that contains available iodine 7.45% glucosan iodo-complexes is compared with the scanning of independent glucosan solution.The above-mentioned PDI aqueous solution is made and is contained the 0.004%W/V available iodine, in ultraviolet ray/visible absorbance scanning of 600～190nm.Similarly, make the approximate 1 centinormal 1 independent glucosan solution (solution of 0.06% glucosan W/V) that contains of a kind of glucosan solution.From 600nm～190nm this independent glucosan solution is carried out ultraviolet ray/visible absorbance scanning.

Its result is as follows:

The peak

PDI????351.5nm，287.5nm，223nm，209nm

Independent glucosan solution 281nm, 192nm produces " shoulder " these results in 221nm and presents PDI complex compound and independent glucosan solution and have one significantly differently, and especially independent glucosan solution the peak do not occur being absorbed in 351nm and 209nm place.

At PDI solution, once there was the peak of absorption to occur in 351nm and 209nm place, and in corresponding independent glucosan solution, do not have, PDI solution does not absorb the peak at the 192nm place simultaneously, one strong absorption peak is arranged and also have the last one to absorb the peak at 287.5nm at the 223nm place, opposed with independent glucosan solution, a weak absworption peak appears 281, and one weak " shoulder " appears outside 221nm.On the absorption peak that PDI solution betides 351.5nm and 223nm be respectively with I ^- ₃And I ^-Absorption be corresponding, this is illustrated in and contains teriodide and iodate ion in the PDI complex compound.

The infrared spectrum that contains the PDI of 7.45% and 3.25% available iodine utilizes potassium bromide (KBr) ball to measure it, 4, and 000cm ^-1To 200cm ^-1Scan in the scope, two kinds of scannings are very similar with the noctovisor scan of independent glucosan solution, just 1, and 500cm ^-1To 1,200cm ^-1Locate somewhat different.In PDI scanning, have very little " shoulder " to occur, still 800 to 300cm ^-1The place can be observed the increase of its intensity.

The present invention does being described in more detail again at following clear and definite example, and it is not interpreted as limiting the scope of the invention.

Example 1

Contain 629.2mgI ₂The iodine solution of the 25ml of/ml (total iodine heavily is 15.73g in solution) freezes the universe, and it freezes universe example weight and is measured as 10.3g.Total iodine heavily is 0.123g in sample, and its iodine loss equals 99.3%.Freeze the universe again after this iodine solution and the reaction of glucosan polymer solution, its iodine loss is low.This expression glucosan polymer and iodine or teriodide ion forming complex because during not the existing of glucosan, are 99.3% from the iodine of iodine solution loss.

Example 2

0.7g powdery, (resublimed) iodine heavily distils, piecemeal is added on the 5% glucosan liquid of 70cc, under 35 ℃, continue to stir the solution of being produced is heated to 65 ℃, kept under this temperature 2 hours, this solution is overnight to be chilled to room temperature, to filter and to freeze the universe to fine powder and produce, and to analyze be 0.01% to the available iodine content of being made thus.

Example 3

3.5g powdery, heavily distillation (resublimed) iodine is incorporated in the 10% glucosan solution of 40 ℃ 200cc, stir the back.This mixture slowly is heated to 75 ℃, keeps this temperature 4 hours, after cool off, filter and freeze the universe.To analyze be 0.14% to the available iodine content of being made thus.

Example 4

5.25g powdery, heavily distillation (resublimed) iodine is incorporated in the 15% glucosan aqueous solution of 40 ℃ 200cc, stir the back, the mixture of this generation slowly is heated to 70 ℃, remained in this temperature 4 hours, this reaction solution cools off, filters on ice bath (icedath) and freeze the universe to fine powder and produces, and it is 0.48% that this manufacturing analyzes available iodine.

Example 5

6.5g powdery, heavy sublimed iodine stirs after being added in the 60% glucosan solution of 200cc, this mixture is warming up to 75 ℃ and the composition that stirs generation after 4 hours and is cooled to room temperature, filters and freezes the universe, analyzing its available iodine is 0.93%.

Example 6

6.5g heavy sublimed iodine 60% the glucosan aqueous solution that adds 200cc stir down at 40 ℃, after finishing the adding of iodine, the hydroiodic acid of 10 47-51% (hydriodic acid) adds, this mixture is warming up to 75 ℃, remained in this temperature 4 hours, the solution cooling and the filtration that are generated, analyzing its available iodine is 1.026%.

Example 7

6.5g heavy sublimed iodine under room temperature, be added in 60% the glucosan aqueous solution of 100cc, the hydroiodic acid that adds 10 is in this solution, this mixture at room temperature stirred 1 hour, froze the universe after the filtration, analyzing its available iodine is 0.22%.

Example 8

3.25g heavy sublimed iodine be incorporated in the 60% glucosan solution of 100cc, and stir, after the adding of having finished iodine, add this mixture of hydracid acid (hydrio-dic acid) of 10 again and at room temperature stir then and filter after 1 hour and freeze the universe, analyzing its available iodine is 0.29%.

Example 9

3.25g heavy sublimed iodine and 10 hydroiodic acids (hydriodic acid) 60% glucosan aqueous solution of at room temperature being incorporated in simultaneously 100cc, follow stirring, the mixture of this generation is heated to 75 ℃, kept this temperature 1 hour, be cooled to room temperature then and refilter, the available iodine that analyzes this composition is 0.7%.

Example 10

20.g more than glucose be incorporated in the water of 100cc, the iodine solution that contains the 4.44cc of 1.8g iodide and 3.2g iodine be incorporated in limpid more than glucose solution, add after the iodine solution, this mixture stirred 1 hour at room temperature, later, filter and freeze the universe to fine powder and produce, analyzing its available iodine is 8.9%.

Example 11

20.g glucosan is dissolved in the water of 100cc in room temperature, stirs, and prepares the iodine solution of 2.55cc as the manufacture method of example 10, is incorporated in the solution that this stirred, the mixture of formation stirred 1 hour subsequently, and its available iodine of filter analysis is 5.2%.

Example 12

In room temperature, the 400g glucosan is dissolved in 2, in the water of 000cc, manufacture method as example 10 is prepared the 83.63cc iodine solution, be incorporated in this solution, the mixture that stirs generation is heated to 65 ℃, remains on this temperature 1 hour, this solution cools off and sprays the formula universe dry (spray-dried) subsequently, and the available iodine content that is analyzed is 0.05%.

Example 13

At room temperature, the 20.g glucosan is dissolved in the water of 100cc, stirs, and prepares the iodine solution of 1.07cc as the method for making of example 10, is incorporated in this solution, stirs subsequently 1 hour, and this solution filters, and the available iodine content that is analyzed is 2.01%.

Example 14

Method for making as example 10 prepares the 1.6cc iodine solution, on one side the 20.% glucosan aqueous solution of the one after another drop of 100cc of being incorporated in stirs, this solution at room temperature stirred 1 hour, and subsequent filtration, the available iodine content that is analyzed are 3.2%.

Example 15

Method for making as example 10 prepares the 20.% glucosan aqueous solution that the 2.01cc iodine solution is incorporated in 100cc, stir on one side, at room temperature stirred this solution 1 hour, later, filter, the available iodine that analyzes is 4.03%.

Example 16

Method for making as example 10 prepares the 3.52cc iodine solution, the one after another drop of 20.% glucosan aqueous solution that is incorporated in 100cc, stir on one side, this solution at room temperature stirred 1 hour, later, filtered, and the available iodine that analyzes is 7.01%.

Example 17

Method for making as example 9 prepares the 2.69cc iodine solution, is incorporated in the 20.% glucosan aqueous solution of 100cc, stir on one side, this solution is heated to 55 ℃, keeps this temperature 1 hour, then, cooling and filtration, the available iodine that is analyzed is 5.1%.

Example 18

20.g glucosan at room temperature is dissolved in the water of 100cc, the iodine solution as example 19 preparation 4.54cc is incorporated in this solution, stir on one side, this solution is heated to 55 ℃ and was kept these temperature 1 hour, and the available iodine that is analyzed is 7.25%.

Example 19

At room temperature, glucose is dissolved in the water of 100cc more than the 20.g, adds the iodine solution of 0.4cc, stir on one side, be heated to 55 ℃ and kept this temperature 1 hour, cool off subsequently and filter, the available iodine that is analyzed is 1.06%.

Example 20

At room temperature, glucose is dissolved in 3 more than the 600g, in the water of 000cc, the iodine solution of 133cc is incorporated in glucosan solution then, then is heated to 55 ℃, keeps this temperature 1 hour, cool off behind this solution, filter and freeze the universe to fine powder and produce, its available iodine that analyzes is 7.19%.

Example 21

Under room temperature, solution is dissolved in the water of 17cc more than the 20.g, after, add the iodine solution of 4.28cc, after be heated to 55 ℃, remained in this temperature following 1 hour, then cooling, freeze the universe after filtering, its available iodine that analyzes is 5.34%.

Example 22

At room temperature, the dissolving 600g more than glucose in 3, in the water of 000cc, by the potassium iodide (KI) of 43.55g and the made iodine solution of iodine of 112.37g, get the iodine solution of 155.0 cc, add in the glucosan solution, subsequently, this solution stirring and be heated to 55 ℃.Kept this temperature 1 hour, this solution cooling and filtration after 6 weeks, are analyzed this filtrate (Filtrate) under room temperature, and available iodine is 8.39%.

Freeze the universe for whole part by the made solution of this example, it is 7.69% that its interpretation of result goes out available iodine.

Example 23

At room temperature, glucose is dissolved in the water of 4cc more than the 20.g, then in 75 ℃ of heating down of oil bath (cil bath), stir on one side, when stirring in oil bath, the iodine of 2.0g adds a part ofly.Heating and continuous stirring 1 hour half, then cooling, the universe is dry in the vacuum of phosphorus pentoxide afterwards, and this glucosan iodine compound is 20.5g, and the available iodine of its gained is 0.1%.

Example 24

The glucose powder is dissolved in the water of 100cc more than the 40g, in a part of this clear solution that in 15 minutes, adds of the heavy sublimed iodine that heats 9.72g under 60 ℃ while stirring, heating while stirring under 70 ℃, be heated to 90～95 ℃ then and continue to stir 30 minutes, after, this solution is chilled to room temperature, go up cooling at ice bath (icebath) again, filter afterwards, this crystallization universe in the vacuum of anhydrous calcium chloride (calcium chlorode) is dry, and its available iodine that analyzes is 0.62%.

Example 25

The weight sublimed iodine of 1g is dissolved in the carbon tetrachloride (CCl of 20.cc ₄) in, the glucose powder is incorporated in limpid iodine solution more than the 5.0g, stir on one side, this suspended substance stirred 15 minutes again, filter, the hydroiodic acid (concentration of 47-51%) that adds 0.3cc again added with one after another drop of adding in five minutes, then, stirred again 4 hours, utilize air-breathing filtration, generate half Powderedly, the dry solid-state weight that obtains of the vacuum universe that the back is changed under the phosphorus at five oxygen two is 2.9g, its available iodine is 0.19% and its viscous solid product is 1.5g, and it has content of iodine is 3.8%.

Example 26

20.g more than the glucose powder be dissolved in the water of 100cc, stir, the iodine solution that adds 10cc then in glucosan solution, iodine solution that this added system by the iodine of the potassium iodide of 8.2g and 13g in the water of 25cc, one glucosan solution stirring half an hour of this iodine, it is glucosan one iodine Operand complex compound that filtration reaches to freezing the universe to a fine powder, and it is 10.34% that this analysis of components goes out its available iodine.

Example 27

20.g more than your (Ficoll) polymer of carbohydrate Fick be dissolved in the 200ml measuring bottle, add water to 200ml.4.0g the iodine that grinds add solution, slowly be heated to 95 ℃ later, keep this temperature 1 hour half, this solution is cooled to room temperature, filters and freezes the universe, this iodine solid-state complex is analyzed to such an extent that its available iodine is 1.6%.

Example 28

Your (Ficoll) 700 of carbohydrate Fick more than the 50g " polymer is dissolved in the measuring bottle of 500ml; and add entry then to 500ml, the powder iodine of 10g is incorporated in this solution, heats under 95 ℃ 5.5 hours later; overnight this solution, filter and freeze the universe, and the available iodine analysis that is obtained is 2.1%.

Example 29

2g iodine is dissolved in 1 of 75ml, in the 2-dichloroethane, again this solution is incorporated in 20.g " Fick that (Ficoll) 700 " polymer and is dissolved in 1 of 200ml, in the 2-dichloroethane, stir on one side, this suspension is heated to 79 ℃, keeps 2 hours in this temperature, this product place cooling overnight, filter and freeze the universe to a fine powder and produce, analyzing its available iodine is 0.1%.

Example 30

20.g it " Fick that (Ficoll) " polymer is dissolved in the water of 100ml, the back adds the iodine solution of 4.84ml, stirs 2 hours under room temperature, and it is 9.62% that the fluid analysis of gained goes out its available iodine.

Example 31

Prepare the iodine solution of 7.45ml as the method for making of example 10, " Fick you (Ficoll) " polymer solution is dissolved in the 100ml solution of water to be incorporated in 20.%, stirs simultaneously, and at room temperature continuous stirring is 1 hour, and analyzing its available iodine later is 14.5%.

Example 32

7.0ml iodine solution be incorporated in 20.% " Fick you (Ficoll) 700 " polymer solution aqueous solution of 100ml, on one side stir, later, this solution at room temperature stirred 1 hour again, to filter and analyze its available iodine be 13.04% to this solution then.

Example 33

0.42ml iodine solution add in the aqueous solution of your 700# polymer solution of 20% Fick of 100ml, at room temperature stirred 1 hour, analyze this solution then, measuring its available iodine is 1.25%.

Example 34

2.2ml iodine solution be incorporated in 20.% " Fick you (Ficoll) 700 " polymer aqueous solution of 100ml, this solution at room temperature stirred 1 hour and analyzed its available iodine, available iodine content is 4.95%.

Example 35

7.3ml iodine solution 20.% " Fick you (Ficoll) " polymer aqueous solution of being incorporated in 100ml at room temperature stirred 1 hour, it is 15.29% that the interpretation of result of this solution goes out its available iodine.

Example 36

4.4ml iodine solution be incorporated in 20.% " Fick you (Ficoll) " polymer aqueous solution of 100ml, stir and 55 ℃ of heating 1 hour down, this solution is cooled to room temperature and filtration and analyzes content of iodine, its available iodine that analyzes is 7.66%.

Example 37

4.4ml iodine solution 20.% " Fick you (Ficoll) " polymer aqueous solution of being incorporated in 100ml be stirred in 55 ℃ of heating 1 hour down, this solution cooling, its as a result it " it is 9.33% that your (Ficoll)-iodo-complexes liquor analysis of Fick goes out its available iodine.

Example 38

7.26ml iodine solution 20.% " Fick you (Ficoll) " polymer aqueous solution of being incorporated in 100ml stir and be heated to 55 ℃, generating it " Fick you (Ficoll) "-iodo-complexes liquor analysis, to go out its available iodine be 12.29%.

Example 39

20.% " Fick that (Ficoll) " polymer aqueous solution of 100ml is heated to 45 ℃, adds the iodine solution of 7.3ml, stirs, and keeps 1 hour in this temperature, and cool off the back, and this solution filters and analyzes its available iodine is 14.3%.

Example 40

4.6ml iodine solution be incorporated in 100ml 20.% " your (Ficoll) polymer of Fick aqueous solution kept 1 hour 45 ℃ of following temperature, stirred, and to cool off, filter, analyze its available iodine be 9.05% to this solution of back then.

Example 41

7.6ml iodine solution be incorporated in 20.% " Fick you (Ficoll) 700 " polymer aqueous solution of 100ml, stir down in 65 ℃, this temperature keeps cooling off after 1 hour and analyzing its iodine composition, it is measured that to go out available iodine be 15.1%.

Example 42

4.6ml iodine solution be incorporated in 20.% " Fick you (Ficoll) " polymer aqueous solution of 100ml, stir down in 65 ℃, this temperature kept 1 hour, this solution cooling and analyze its available iodine content, recording out its available iodine is 8.8%.

Example 43

20.g it " Fick that (Ficoll) 700 " " polymer is dissolved in the water of 150cc; prepare the iodine solution of 20.cc as the method for making of example 10; add limpid " Fick that (Ficoll) " polymer solution; stir; result's solution stirred 1 hour half in addition; filter on one side, and it " Fick that (Ficoll) " iodine Operand complex compound freezes the universe to forming a fine powder as a result, and measured its available iodine is 24%.

Example 44

1.39g more than glucose-iodine and 7.0% available iodine complex compound and be dissolved in the water of 50cc.The glycerine of 30g, 0.06g the polysorbate 80 of buffer (be 15g grind mixing of phosphoric acid-sodium and 71g anhydrous citric acid) and 0.25g, be incorporated in the PDI solution, these compositions are dissolved in this solution fully, afterwards, quantitatively change measuring bottle over to, and adding distil water is to 100ml in 100ml, this as a result its available iodine of solution testing be 0.1%W/V.

Example 45

Contain glucose iodo-complexes (PDI) more than the 1.39g of 7.0% available iodine, be dissolved in the water of 50ml, 1g glycerine, as example 44 made 0.06g buffers, and the polysorbate 80 of 0.25g is added in the PDI solution entirely, and these compositions are dissolved fully, and the quantitative immigration of this solution is in the measuring bottle of 100ml, add distilled water to 100ml, its as a result its available iodine of solution testing be 0.1%W/V.

Example 46

Contain glucose iodo-complexes more than the available iodine 7.07%27.78g, be dissolved in the water of 50ml, the glycerine of 30g, 0.25g Ya Liba (Alipal) CO-436,1.119g buffer is incorporated in this solution, all compositions thoroughly dissolve, and this solution quantitatively is moved into the measuring bottle of 100ml afterwards, this solution is added water to 100ml again, and testing its available iodine is 2.0%.

Example 47

13.89g more than the glucose iodo-complexes be dissolved in the water of 50ml 30g glycerine, 0.25g Ya Liba (Alipal) CO-436 and 0.56g buffer, be incorporated in entirely in the above-mentioned solution, the measuring bottle of quantitative then immigration 100ml, adding water to liquor capacity is 100ml, testing its available iodine is 1.0%.

Example 48

Contain glucose iodo-complexes more than the 7.07% available iodine 3.47g, be dissolved in the water of 50ml, the glycerine of 30g, 0.25g Ya Liba (Alipal) CO-436 and 0.14g buffer all add and be dissolved in the PDI complex solution, this solution quantitatively moves into the measuring bottle of 100ml, adding water, to make volume be 100ml, chemically examines to such an extent that its available iodine is 0.25%.

Example 49

1.39g more than the glucose iodo-complexes be dissolved in the water of 50ml, the glycerine of 30g, 0.25g the buffer of Ya Liba (Alipal) CO-436 and 0.14g all adds and is dissolved in the solution of PDI, quantitatively move in the measuring bottle of 100ml after this solution, adding water to liquor capacity is 100ml, and its available iodine of analyzing is 0.1%.

Example 50

13.95g more than the glucose iodo-complexes be dissolved in the water of 50cc, the glycerine of 1g, 0.25g the buffer of Ya Liba (Alipal) CO-436 and 0.56g adds in the PDI solution entirely, this solution quantitatively moves into the measuring bottle of putting 100ml, adding water to liquor capacity is 100ml, and its available iodine of analyzing is 1%.

Example 51

13.95g more than the glucose iodo-complexes be dissolved in the water of 50ml, the glycerine of 1g, 0.25g the buffer of Ya Liba (Alipal) CO-436 and 0.056g is incorporated in the PDI complex compound entirely, the solution of generation quantitatively moves into the measuring bottle in 100ml, its cumulative volume adds water to 100ml, and the available iodine that is analyzed is 0.1%.

Example 52

Contain glucose iodo-complexes more than 7.0% the available iodine 14.1g, 1g glycerine, and Han Fuxi (Hamposyl) the L-30(30% solution of 0.25g) be incorporated in full 0.914g buffer in the water of 80ml a part of be incorporated in the above-mentioned solution to pH value between 4.9～5.1, this solution quantitatively moves into the measuring bottle in 100ml, add water, make its volume to 100ml, last, measured PH-value is 5.01, and available iodine is 1%.

Example 53

14.1g more than the glucose complex compound, 1g glycerine and 0.3g ammonium sulfate (ammonium myrth sultate) (60% concentration) CL is in the water of 80ml, as example 44 made preparation citric acid/disodium hydrogen phosphate (diso-dium phosphate) buffers, a part of being incorporated in the solution to fall pH value to 5.01.This solution quantitatively is moved into the measuring bottle of 100ml, adds entry and makes its volume rise to 100ml, and its last pH value is 5.0, and its available iodine is 1%.

Example 54

Contain glucose iodo-complexes more than the 7.0% available iodine 14.1g, 1g glycerine, and Mi Laidian (Mirataine) CBS of 0.25g is dissolved in the water of about 80ml, the a part of buffer that adds, to its pH value be 5.0, this solution quantitatively moves into later the measuring bottle in 100ml, adding water to volume is 100ml, last its pH value is 5.0, and available iodine is 1%.

Example 55

14.0g more than the glucose iodo-complexes, 1.0g glycerine and 0.25g Han Fuxi (Homposyl) TL-40, be dissolved in the water of about 80ml, according to citric acid/disodium hydrogen phosphate (disodium phosphate) buffer that example 44 is made, a part ofly be incorporated in that to make its pH value in the solution be 5.5, several 10%, hydrochloric acid splashes into solution, and to make its pH value be 5.0, this solution quantitatively moves into the measuring bottle in 100ml, and adding water to its volume and be 100ml, to survey its available iodine be 1.0%, and the pH value of this solution is 5.0.

Example 56

The iodine solution for preparing 5cc according to the method for making of example 10, being incorporated in 20g glucosan polymer is dissolved in the water of 100cc, stir, the solution that is generated is heated to 55 ℃ and this temperature and kept 1 hour, and this solution filters in cooled on ice, chemical examination and freeze the universe, chemically examine again after freezing the universe, post analysis available iodine before not freezing the universe is 8.69% again, and the available iodine that freezes behind the universe is 8.15%.

Example 57

Contain 6.21mgI ₂/ cc, be incorporated in as the iodine solution of example 10 obtained 12cc that the glucose polymerisation body is dissolved in the water of 100cc more than the 20g, stir, the solution that is generated is heated to 55 ℃, kept 1 hour in this temperature, this glucosan iodine liquid (PDI) complex compound chemical examination, and cooling are filtered, and freeze the universe, freeze chemical examination again behind the universe, the back chemical examination records this solution and contains 18.6% available iodine, freezes that available iodine is 17.05% after the universe.

Example 58

The iodine solution of the 4cc that gets according to the method for making of example 10 is incorporated in it " Fick you Ficoll400 " polymer of 20.g and is dissolved in the water of 100cc, stirs.This solution is heated to 55 ℃, keeps this temperature 1 hour, cools off behind " Fick that (Ficoll) " polymer iodo-complexes solution, filters, and freezes the universe, and chemically examines to such an extent that its available iodine is 9.25%.

Example 59

The iodine solution of 400ml is incorporated in 20g, and " Fick that (Ficoll) 70 " polymer is dissolved in the water of 100cc,, stir.This solution is heated to 55 ℃, remains on this temperature 1 hour, and this solution cooling is filtered, and freezes the universe and chemical examination, and its available iodine is 8.91%.

Example 60

Glucose is dissolved in the water of 3000cc more than the 600g, firmly stirs, to producing to a limpid solution.Contain 63gI ₂The iodine solution of 71cc is incorporated in limpid solution afterwards, stirs.Later be heated to 55 ℃, kept this temperature 1 hour, this product at room temperature cools off and filters, and this fluid product freezes the universe, chemically examines to such an extent that its available iodine is 3.25%.

Example 61

Glucose is dissolved in the water of 3000cc more than the 600g, firmly stirs, to producing to a limpid solution, by 137gI ₂The iodine solution of made 155cc joins in the glucosan solution, stirs.The finished product that produces is heated to 55 ℃, remains on this temperature 1 hour.

This solution is cooled to room temperature and filtration, and the PDI complex compound can be used in liquid state, but that the PDI complex compound is preferably used is solid-state, and the total thing of PDI network freezes the universe, and chemical examination, and analyzing its available iodine is 7.45%.

Example 62

The potassium iodide of 82g (KI) is dissolved in the water of 200cc, adds iodine (I ₂) at room temperature, stirred 1 hour, filter and generate solution and chemical examination, learn that its available iodine is 888.44mg I ₂/ cc.

This iodine solution is to be used in the method for making above-mentioned various PDI complex compounds and " Fick that (Ficoll) " polymer one iodo-complexes to make, as previously mentioned.

Example 63

10g glucosan and 2g iodine (particle size is 40 sieve mesh holes) mix fully and are placed in 40Z.Wide mouth bottle (Wide-mouth jar).Among syringe (syringe) adding 0.12cc, on bottle cap, this mixture shook 24 hours, did not have significant reaction between glucosan and the iodine crystallization.

Example 64

Glucose thoroughly mixes with the elemental iodine of 2g more than the 10g, places a 40Z, and wide mouth bottle is good bottle cap by the water of syringe adding 0.63cc, shakes this mixture 24 hours, and no significant reaction takes place.

Example 65

Glucose thoroughly mixes with the elemental iodine of 2g more than the 10g, place a 40Z, wide mouth bottle, the water that adds 1.33cc by syringe, on bottle cap, shook this mixture 24 hours, can be observed glucosan one water (polydextrose-water) gelinite (gel) and produce, this glue is slightly green, but as seen crystallization iodine be in gelinite (gel), and no significant reaction.

On state that above-mentioned what narrate only is range format or the shape that is intended to not limit as example the present invention clearly.

Claims (15)

1, the present invention be a kind of by iodine (Iodine) and glucosan (Poly dextro-se) or with sucrose (sucrose) and epoxychloropropane (epichlorohydrin) polymer, generate new complex compound method, it is characterized in that the glucosan aqueous solution or complex compound and (A) solid-state iodine carry out complexing, perhaps with (B) potassium iodide (KI) in iodine carry out complex reaction, this reaction is to take place between room temperature and 75 ℃, cool off this reactant mixture and make glucosan-iodine (plaly-dextrose-Iadine) complex compound sediment, then, separate this sediment.

2, according to the method for claim 1, the sterilization complex compound that it is characterized in that iodine is that iodine and glucosan or sucrose and epoxychloropropane carry out complexing.

3, method as claimed in claim 2, the sterilization complex compound that it is characterized in that iodine are iodine and glucosan complexing.

4, method as claimed in claim 2, the sterilization complex compound that it is characterized in that iodine are iodine and sucrose and epoxychloropropane copolymerization complex.

5, method as claimed in claim 2 is characterized in that wherein content of iodine is to reach 20%.

6, method as claimed in claim 3 is characterized in that wherein content of iodine is to reach 20%.

7, method as claimed in claim 4 is characterized in that wherein content of iodine is to reach 20%.

8, method as claimed in claim 2 is characterized in that wherein content of iodine is 2-10%.

9, method as claimed in claim 3 is characterized in that wherein content of iodine is 2-10%.

10, method as claimed in claim 4 is characterized in that wherein content of iodine is 2-10%.

11, method as claimed in claim 1 is characterized in that the sterilization be made up of above-mentioned novel complex and microbicidal composition comprise that a kind of complex compound with claim 2 distributes and make the carrier of topical application.

12, method as claimed in claim 2 is characterized in that the sterilization be made up of above-mentioned novel complex and microbicidal composition comprise that a kind of complex compound with claim 3 distributes and make the carrier of topical application.

13, method as claimed in claim 2 is characterized in that the sterilization be made up of above-mentioned novel complex and microbicidal composition comprise that a kind of complex compound with claim 4 distributes and make the carrier of topical application.

14, method as claimed in claim 2 is characterized in that wherein also comprising a kind of interfacial agents.

15,, it is characterized in that wherein also comprising a kind of buffer as the method for claim 14.