WO1998038222A2 - Formes modifiees de cyclodextrine a canaux moleculaires, procedes pour leur preparation ainsi que leur utilisation - Google Patents

Formes modifiees de cyclodextrine a canaux moleculaires, procedes pour leur preparation ainsi que leur utilisation Download PDF

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Publication number
WO1998038222A2
WO1998038222A2 PCT/DE1998/000566 DE9800566W WO9838222A2 WO 1998038222 A2 WO1998038222 A2 WO 1998038222A2 DE 9800566 W DE9800566 W DE 9800566W WO 9838222 A2 WO9838222 A2 WO 9838222A2
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WO
WIPO (PCT)
Prior art keywords
cyclodextrin
modifications
molecular
cyclodextrin modifications
molecular channels
Prior art date
Application number
PCT/DE1998/000566
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German (de)
English (en)
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WO1998038222A3 (fr
Inventor
Gerhard Wenz
Marc Steinbrunn
Original Assignee
Universität Karlsruhe (Th)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority to AU68201/98A priority Critical patent/AU6820198A/en
Publication of WO1998038222A2 publication Critical patent/WO1998038222A2/fr
Publication of WO1998038222A3 publication Critical patent/WO1998038222A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2066—Fluorine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to the production and use of a new modification of ⁇ -, ⁇ - and ⁇ -cyclodextrins, the crystals of which have a structure permeated by molecular channels, and tubular polymers of these modifications.
  • ⁇ -cyclodextrin forms two crystal modifications from an aqueous solution, which differ in that one or two water molecules are built into the inside of the ring, while four or five water molecules are attached to the outside of the cyclodextrin ring [13, 14].
  • ⁇ -cyclodextrin is present as round toms with Cö symmetry (see Fig la).
  • the carbon and hydrogen atoms of all anhydroglucose units are identical, like the simple 1 H - and 13 C-
  • the object of this invention is to enable the production of a completely empty channel structure of the cyclodextrin host crystal in a simple manner and thereby to expand the field of application of these compounds.
  • This object is achieved according to the invention in that a method is made available with which such an empty molecular channel system is created in a sufficiently large amount. This takes place, starting from a channel-like inclusion compound of cyclodextrin and a suitable guest molecule, by removing the guest molecule, for example by thermally expelling the guest molecule, while maintaining the present structure. This creates a crystalline structure with high absorption capacity that is traversed by molecular channels. For example, in the case of iodine, the absorption capacity can be increased fourfold compared to normal cyclodextrins.
  • cyclodextrin channel structures are also able to absorb additional guest molecules. This can be an advantage if the included molecules are to be transported across phase boundaries, for example. Due to the solubility of cyclodextrins in polar media, especially in water, is compared to other absorbents, such as. B. activated carbon and zeolites, an advantage can be expected if, for example, cyclodextrins are used in a liquid / liquid extraction, the cyclodextrin then being able to be recovered from the aqueous phase. Another advantage is the biodegradability of cyclodextrins, so that disposal here could be done, for example, by composting.
  • cyclodextrin can be seen, for example, as an alternative to classic adsorbents such as activated carbon or zeolites in the purification of gases.
  • adsorbents such as activated carbon or zeolites
  • the adsorption capacity of conventional microporous materials, such as activated carbon, which has a pore diameter between 400 and 2000 pm, or various metal phosphates and zeolites with pore diameters between 1000 and 1200 pm [1, 2, 3] can be attributed to their large surface area. Most of the The cavities inside the material are available on the surface.
  • cyclodextrin channels allow the guest molecules to escape just as slowly, they can also be used to control molecular transport processes.
  • Controlling molecular transport processes is understood to mean the selective complexation and the directed transport of guest molecules in the interior of the host channel and their metered and controlled release of the included molecules.
  • This can be, for example, the transportation of pharmaceuticals or fragrances or the use as a depot for these pharmaceuticals or fragrances.
  • a special application of this channel structure could, for example, be the creation of an iodine depot preparation that can be used to treat thyroid dysfunction. Further possible applications can be seen through the use of these channel structures in the implementation in suspensions (e.g. alcohols). This solid structure should be expected to be more reactive than native cyclodextrin in this area.
  • the cyclodextrin guest compounds are first produced and then linked to one another by polymerization with difunctional reagents, such as epichlorohydrin, bisepoxides, diisocyanate. The corresponding guest molecule is then removed either thermally or by ultrafiltration.
  • difunctional reagents such as epichlorohydrin, bisepoxides, diisocyanate.
  • the corresponding guest molecule is then removed either thermally or by ultrafiltration.
  • Polymers produced in this way have significant advantages over existing polymers (20). These are in detail - no high-molecular fractions form, which lead to gelation with previously known polymers (20). - Polymers produced in this way are readily soluble. Crosslinking reactions, for example with other bifunctional reagents such as epichlorohydrin, can be carried out more quickly and easily.
  • the polymers have, compared to known cyclodextrin polymers, a significantly increased specific surface area and therefore have a significantly improved absorption behavior.
  • cyclodextrin polymers can be seen in the use of such polymers as absorbents in the purification of gases or liquids. Furthermore, their use as a carrier base for active pharmaceutical ingredients or fragrances is conceivable. Such polymers can also be immobilized on stationary phases and used for chromatographic separation.
  • the proposed method is based on the incorporation of linear guest molecules, the linear arrangement of the cyclodextrin molecules caused by this procedure and the final removal of the guest molecules from the cyclodextrin crystal or polymer.
  • Pentane, hexane, heptane and octane - hereinafter also referred to as guest - can be used as guest molecules.
  • longer-chain aliphatic hydrocarbons and other long-chain compounds such as esters, ethers, alcohols, cycloaliphatics, aromatics, unsaturated aliphatics, bridged aliphatics or norbornene can also be used.
  • Example 1 Inclusion compounds ⁇ -cyclodextrin-pentane and ⁇ -cyclodextrin-octane
  • WAXS: 2 ⁇ 5.05m, 5.25m, 7.36m, 11.08s, 12.02w, 12.60m, 14.45w,
  • the WAXS shows that the columnar structure is preserved during the annealing.
  • WAXS: 2 ⁇ 5.3m, 7.5s, 14.2m, 14.9m, 15.7m, 16.7m (see Fig. 3)
  • the aqueous phase is neutralized with acetic acid and ultrafiltered against an ultrafiltration membrane (Hoechst High Chem, UF-PES-4H, 4000 Da cutoff) with water. The solution is then freeze-dried. The product is a white foam. Yield: 3.4g
  • a 0.8 10 "4 M solution of KI 3 in water is prepared and the tubular polymer dissolved in it at 0.4 g / L.
  • the UV spectrum shows one compared to that of an equally concentrated solution of ⁇ -cyclodextrin significant increase in intensity, a shift of the absorption maximum to longer wavelengths (from 353 nm to 360 nm) and an additional shoulder at 430 nm.
  • This UV spectrum is similar to that of the KI 3 complex of the tubular polymer from (22).
  • each of the crystalline channel structures of the ⁇ - and ⁇ -cyclodextrin and of the ⁇ - and ⁇ -cyclodextrin previously dried in vacuo at 130 ° C. are placed in a sealed container with 5 ml of benzene in the presence of a drying agent (Blaugel).
  • the four samples are only in contact with benzene through the gas phase.
  • DSC measurements are carried out after five days. As in Example 1, the amount of heat required to remove the benzene is determined.
  • Figure 7 shows that the expulsion of the guest molecules begins at about 50 ° C and continues up to a temperature of 160 ° C.
  • the comparison of the integrated signals shows that the absorption capacity of the ⁇ -cyclodextrin can be increased four to five times.
  • the signals between 220 and 235 ° C are not due to the expulsion of the guest, but are characteristic of ß-cyclodextrin.
  • FIG. 1 shows the X-ray diffractograms (WAXS) of a) native ⁇ -cyclodextrin, b) ⁇ -cyclodextrin-pentane c)) ⁇ -cyclodextrin-pentane after annealing 2d at 80 ° C
  • FIG. 2 shows X-ray diffractograms (WAXS) of native ⁇ -cyclodextrin
  • FIG. 3 shows X-ray diffractograms (WAXS) of ⁇ -cyclodextrin-methylcyclohexane
  • FIG. 4 shows the X-ray diffractogram (WAXS) of native ⁇ -cyclodextrin
  • Figure 5 shows the X-ray diffractogram (WAXS) of ⁇ -cyclodextrin octane
  • Figure 6 shows the NMR-NMR spectrum of the tubular polymer in DMSO-d 6
  • Figure 7 shows the UV spectra of a 0.8 10 "4 M aqueous solution of KI 3 A) without addition B) with 0.4 g / L ⁇ -cyclodextrin, C) with 0.4g / L tubular polymer.
  • FIG. 8 shows free ⁇ -cyclodextrin a) in aqueous solution and b) in the crystal (according to Saenger [12]).
  • FIG. 9 shows the H-NMR spectrum of a - cyclodextrin - pentane - clathrate in DMSO-d6.
  • FIG. 10 shows the diffractogram of the inclusion compound of a-cyclodextrin-pentane-clathrate (powder uptake).
  • FIG. 11 shows a diffractogram of the inclusion compound of cyclodextrin-pentane clathrate after the guest molecule has been driven out (powder uptake).
  • FIG. 12 shows the 13 C-CP-MAS NMR spectrum of the inclusion compound of cyclodextrin - pentane - clathrate after the guest molecule has been driven out.
  • FIG. 13 shows the DSC measurement of the inclusion compound of pentane in cyclodextrin pentane - clathrate, a) first heating cycle, b) second heating cycle

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un procédé et une nouvelle forme modifiée de cyclodextrines. Ces cyclodextrines cristallisent avec des molécules hôtes aliphatiques linéaires, comme par exemple du pentane, sous forme de composé d'inclusion. Comme le montrent les radiographies, ces molécules hôtes sont expulsées du cristal tandis que la structure est conservée, de sorte qu'il subsiste un cristal à canaux moléculaires. Cette modification cristalline présente, par rapport à la structure cristalline connue jusqu'à présent de la cyclodextrine, un pouvoir d'absorption des molécules hôtes notablement supérieur. Il est probable qu'en particulier les molécules organiques, comme les hydrocarbures aliphatiques et aromatiques ou bien les hydrocarbures fluorés et chlorés, qui par leurs dimensions sont mieux adaptés à la cavité de cette cyclodextrine, sont absorbées aussi bien et certainement même mieux que l'iode.
PCT/DE1998/000566 1997-02-27 1998-02-26 Formes modifiees de cyclodextrine a canaux moleculaires, procedes pour leur preparation ainsi que leur utilisation WO1998038222A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68201/98A AU6820198A (en) 1997-02-27 1998-02-26 Cyclodextrin modifications with molecular channels, method for the production and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19707855.9 1997-02-27
DE19707855 1997-02-27

Publications (2)

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WO1998038222A2 true WO1998038222A2 (fr) 1998-09-03
WO1998038222A3 WO1998038222A3 (fr) 1998-12-17

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DE (1) DE19808063A1 (fr)
WO (1) WO1998038222A2 (fr)

Cited By (1)

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CN114618266A (zh) * 2020-12-10 2022-06-14 中国石油天然气股份有限公司 一种增溶吸收剂及其制备方法、有机废气的处理方法

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US20020168286A1 (en) * 2000-08-18 2002-11-14 Demeyere Hugo Jean Marie Reduction of odor from a process
AU2002246302A1 (en) * 2001-03-23 2002-10-08 University College Dublin Macrocyclic oligosaccharide derivatives which form manoscale assemblies
DE102006007796B3 (de) * 2006-02-20 2008-01-10 Kist-Europe Forschungsgesellschaft Mbh Verfahren zur selektiven Behandlung von schwer abbaubaren und/oder toxischen Verbindungen in Abwasser oder Wasser
WO2013135248A2 (fr) * 2012-03-13 2013-09-19 Amphidex A/S Production de cristaux de cyclodextrine de type canal
WO2013135247A2 (fr) * 2012-03-13 2013-09-19 Amphidex A/S Production de cristaux de cyclodextrine de type canal
DE102018200520A1 (de) 2018-01-15 2019-07-18 Robert Bosch Gmbh Verfahren zum Bereitstellen einer Lösung der Substanz in einer mikrofluidischen Vorrichtung

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US5321014A (en) * 1991-06-28 1994-06-14 The United States Of America As Represented By The Department Of Health And Human Services Molecular encapsulation and delivery of alkenes alkynes and long chain alkanes, to living mammalian cells
JP3288149B2 (ja) * 1993-08-05 2002-06-04 日本食品化工株式会社 シクロデキストリンポリマー及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114618266A (zh) * 2020-12-10 2022-06-14 中国石油天然气股份有限公司 一种增溶吸收剂及其制备方法、有机废气的处理方法
CN114618266B (zh) * 2020-12-10 2023-07-25 中国石油天然气股份有限公司 一种增溶吸收剂及其制备方法、有机废气的处理方法

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DE19808063A1 (de) 1998-10-08
WO1998038222A3 (fr) 1998-12-17
AU6820198A (en) 1998-09-18

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