JP2007051073A - Dna salt and functional polymer film obtained by forming the same salt into film - Google Patents
Dna salt and functional polymer film obtained by forming the same salt into film Download PDFInfo
- Publication number
- JP2007051073A JP2007051073A JP2005235592A JP2005235592A JP2007051073A JP 2007051073 A JP2007051073 A JP 2007051073A JP 2005235592 A JP2005235592 A JP 2005235592A JP 2005235592 A JP2005235592 A JP 2005235592A JP 2007051073 A JP2007051073 A JP 2007051073A
- Authority
- JP
- Japan
- Prior art keywords
- dna
- salt
- alkyl
- membrane
- benzyl
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Landscapes
- Saccharide Compounds (AREA)
- Filtering Materials (AREA)
Abstract
Description
本発明は、新規な機能性高分子、詳しくはDNAリン酸アニオンと、長鎖アルキルを有する4級アンモニウムカチオンとの塩、およびこの塩から成膜してなる機能性高分子膜に関する。 The present invention relates to a novel functional polymer, specifically, a salt of a DNA phosphate anion and a quaternary ammonium cation having a long-chain alkyl, and a functional polymer film formed from this salt.
DNAはリン酸アニオンを有する巨大分子である。このリン酸アニオンへカチオン性両親媒性分子をイオン結合し、両親媒性DNA塩を製造することが岡畑ら、J.CHEM.SOC.,CHEM.COMMUN.1992,1339−1341および特開平8−239398号公報に発表されている。発表されたDNA塩の両親媒性カチオンは一般に構造が複雑で、その合成に手間がかかる。そこでもっと容易に合成することができるか、又は市場において容易に入手し得る両親媒性分子を使用して製造することができる機能性DNA塩を提供することが望まれる。 DNA is a macromolecule having a phosphate anion. Okabata et al., J., et al., Produced an amphiphilic DNA salt by ion-bonding a cationic amphiphilic molecule to this phosphate anion. CHEM. SOC. , CHEM. COMMUN. 1992, 1339-1341 and JP-A-8-239398. The amphipathic cation of a DNA salt that has been announced generally has a complicated structure and takes time to synthesize. It is therefore desirable to provide functional DNA salts that can be synthesized more easily or can be produced using amphiphilic molecules that are readily available on the market.
本発明は、DNAリン酸アニオンが、
式I:
を有するカチオンとイオン結合してなるDNA塩を提供する。式I中、RはC8〜C20アルキル、C8〜C20アルキル置換基を有するベンジル、またはC8〜C20アルキル置換基を有するフェノキシエトキシエチルから選ばれ、R’,R’’およびR’’’の2つはC1〜C4アルキルであり、残りの2つの両方がC1〜C4アルキルか、一方がC1〜C4アルキルで他方がベンジルか、または一方がベンジルで他方がフェニルであり、あるいはR’,R’’およびR’’’のそれらが結合するN原子と共にピリジン環を表す。
In the present invention, the DNA phosphate anion is
Formula I:
Provided is a DNA salt formed by ion bonding with a cation having In formula I, R is selected from phenoxyethoxyethyl having benzyl, or a C 8 -C 20 alkyl substituents having C 8 -C 20 alkyl, C 8 -C 20 alkyl substituent, R ', R''and Two of R ′ ″ are C 1 -C 4 alkyl, and the other two are both C 1 -C 4 alkyl, one is C 1 -C 4 alkyl and the other is benzyl, or one is benzyl The other is phenyl or represents a pyridine ring with the N atom to which they of R ′, R ″ and R ′ ″ are attached.
本発明は、上記DNA塩を成膜して得られる機能性高分子膜を提供する。この膜は補強用高分子マトリックスを含むことができる。膜は、例えばO2ガスに対して高い選択的透過率を有し、医療用途において有用である。また膜を構成する2本鎖DNA間に多種類の分子をインターカレーションすることにより、多種類の用途において有用である。 The present invention provides a functional polymer film obtained by forming the DNA salt into a film. The membrane can include a reinforcing polymer matrix. The membrane has a high selective permeability for eg O 2 gas and is useful in medical applications. Moreover, it is useful in many kinds of applications by intercalating many kinds of molecules between the double-stranded DNAs constituting the membrane.
DNAは、天然および合成DNAのいずれでも良いが、両親媒性カチオンとの塩を生成させるため、水溶性のDNA塩、例えばナトリウム塩を使用する。 The DNA may be either natural or synthetic DNA, but a water-soluble DNA salt such as a sodium salt is used to form a salt with an amphiphilic cation.
式Iの4級アンモニウムおよびピリジニウムカチオンは、クロライドまたはブロマイドの形で市場において容易に入手することができる。これらは逆性石鹸として知られる殺菌剤である。もし市場において入手できないときは、例えばC8〜C20アルキルアミンやC1〜C4アルキルハライドを用いて4級化するか、またはピリジンをC8〜C20アルキルハライドで4級化すること等によって容易に合成することができる。本発明において好適に使用し得る4級アンモニウム塩またはピリジニウム塩は、例えば
C8〜C20アルキルトリメチルアンモニウムクロライド、
C8〜C20アルキルジメチルエチルアンモニウムクロライド、
メチルC8〜C20アルキルベンジルトリメチルアンモニウムクロライド、
C8〜C20アルキルジメチルベンジルアンモニウムクロライド(ベンズアルコニウムクロライド)、
ジメチルフェニルベンジルアンモニウムクロライド、
C8〜C20アルキルジメチル−3,4−ジクロロベンジルアンモニウムクロライド
4−(1,1,3,3−テトラメチルブチル)フェノキシエトキシエチルジメチルアンモニウムクロライド(ベンゼトニウムクロライド)
4−(1,1,3,3−テトラメチルブチル)クレゾキシエトキシエチル
ジメチルアンモニウムクロライド(メチルベンゼトニウムクロライド)、
C8〜C20アルキルビリジニウムクロライド
およびこれらの対応するブロマイドを含む。
The quaternary ammonium and pyridinium cations of formula I are readily available on the market in the form of chloride or bromide. These are bactericides known as inverse soaps. If time is not available in the market, for example C 8 -C 20 alkylamine or C 1 -C 4 or quaternized with an alkyl halide, or pyridine C 8 -C 20 alkyl halide in the quaternization can be like Can be easily synthesized. Examples of the quaternary ammonium salt or pyridinium salt that can be preferably used in the present invention include C 8 to C 20 alkyltrimethylammonium chloride,
C 8 -C 20 alkyl dimethyl ethyl ammonium chloride,
Methyl C 8 -C 20 alkyl benzyl trimethyl ammonium chloride,
C 8 -C 20 alkyl dimethyl benzyl ammonium chloride (benzalkonium chloride),
Dimethylphenylbenzylammonium chloride,
C 8 -C 20 alkyl dimethyl 3,4-dichlorobenzyl ammonium chloride 4- (1,1,3,3-tetramethylbutyl) phenoxy ethoxyethyl dimethyl ammonium chloride (benzethonium chloride)
4- (1,1,3,3-tetramethylbutyl) cresoxyethoxyethyldimethylammonium chloride (methylbenzethonium chloride),
C 8 -C including 20 alkyl pyridinium chloride and their corresponding bromides.
本発明のDNA塩は、水溶液中において、ナトリウム塩のような水溶性DNA塩と、該DNAに対し少なくとも当量の前記アンモニウム塩またはピリジニウム塩を反応させることによって得られる。この際アンモニウム塩またはピリジニウム塩水溶液中に、攪拌下DNA塩水溶液を徐々に滴下するのが好ましい。生成する本発明のDNA塩は水に不溶なため白色沈澱として析出する。これを吸引濾過して集め、精製水でよく洗った後減圧乾燥することにより目的物が得られる。この塩はDNA2本鎖構造を保持している。 The DNA salt of the present invention is obtained by reacting a water-soluble DNA salt such as a sodium salt with at least an equivalent amount of the ammonium salt or pyridinium salt with respect to the DNA in an aqueous solution. At this time, the aqueous DNA salt solution is preferably gradually dropped into the aqueous ammonium salt or pyridinium salt solution with stirring. The resulting DNA salt of the present invention is insoluble in water and thus precipitates as a white precipitate. This is collected by suction filtration, washed well with purified water, and then dried under reduced pressure to obtain the desired product. This salt retains the DNA double-stranded structure.
本発明のDNA塩はクロロホルム/エタノール混液のような有機溶媒に可溶である。そのためこの溶液をガラス板のような基板にキャストし、乾燥して成膜することができる。膜の用途によって機械的強度が要求される場合には補強材と複合化することができる。そのような補強材を含む補強膜を作製する第1の方法は、布、不織布、多孔質フィルムのような補強支持材に溶液を塗布し、乾燥して異方性膜を作製する方法である。塗布の代りに補強支持材をDNA塩溶液で含浸してもよい。第2の方法は、DNA塩と補強用高分子を両者の共通有機溶媒に溶かし、ガラス板の上に溶液をキャストし、乾燥後剥離する方法である。例えば補強用高分子がポリアミドイミドの場合、溶媒としてジメチルホルムアミド(DMF)を用いることができる。 The DNA salt of the present invention is soluble in an organic solvent such as a chloroform / ethanol mixture. Therefore, this solution can be cast on a substrate such as a glass plate and dried to form a film. When mechanical strength is required depending on the use of the membrane, it can be combined with a reinforcing material. A first method for producing a reinforcing membrane containing such a reinforcing material is a method of producing an anisotropic membrane by applying a solution to a reinforcing support material such as a cloth, a nonwoven fabric, or a porous film and drying it. . Instead of coating, the reinforcing support may be impregnated with a DNA salt solution. The second method is a method in which a DNA salt and a reinforcing polymer are dissolved in a common organic solvent of both, a solution is cast on a glass plate, and dried and peeled off. For example, when the reinforcing polymer is polyamideimide, dimethylformamide (DMF) can be used as a solvent.
このようにして得られた本発明のDNA塩膜は、O2ガスに対して選択的に高い透過率を有することがわかった。このため膜は気体分離膜として、または高いO2透過性を要求する医療用途において有用である。また、成膜前のDNA塩に機能性分子をインターカレーションすることにより、インターカレーションした分子の性質を利用する機能性高分子膜として有用である。 It was found that the thus obtained DNA salt film of the present invention has a selectively high transmittance with respect to O 2 gas. Thus, the membrane is useful as a gas separation membrane or in medical applications that require high O 2 permeability. In addition, it is useful as a functional polymer film that utilizes the properties of intercalated molecules by intercalating functional molecules with DNA salts before film formation.
以下の実施例は本発明を例証する目的で与えられ限定を意図しない。なお、すべての実施例においてDNAとしてサケ精子DNAナトリウム塩(日本化学飼料社製)を用いた。 The following examples are given for the purpose of illustrating the invention and are not intended to be limiting. In all examples, salmon sperm DNA sodium salt (manufactured by Nippon Chemical Feed Co., Ltd.) was used as DNA.
実施例1 DNA/CTMAの合成
2Lビーカーに超純水1100mlを入れ、これにDNA−Na 4g(4.57×10−3mol)を加え、マグネチックスターラーで攪拌して溶解した。別の2Lビーカーに超純水1100mlを入れ、セチルトリメチルアンモニウムクロライド(CTMACl)3.42g(1.07×10−2mol)を加えて溶解した。DNA−Na溶液を滴下ロートに移し、CTMACl溶液中に攪拌下ゆっくり滴下した。滴下するとすぐ白色の沈澱が生成した。滴下終了後3時間攪拌を継続し、反応液を冷蔵庫で12時間静置した。その後白色沈澱物を吸引濾過し、超純水で2〜3回洗浄し、シャーレに生成物を移し、40℃で1日減圧乾燥した。収率94%であった。
Example 1 Synthesis of DNA / CTMA 1100 ml of ultrapure water was placed in a 2 L beaker, 4 g (4.57 × 10 −3 mol) of DNA-Na was added thereto, and the mixture was dissolved by stirring with a magnetic stirrer. In another 2 L beaker, 1100 ml of ultrapure water was added, and 3.42 g (1.07 × 10 −2 mol) of cetyltrimethylammonium chloride (CTMACl) was added and dissolved. The DNA-Na solution was transferred to a dropping funnel and slowly dropped into the CTMACl solution with stirring. A white precipitate formed immediately after the addition. Stirring was continued for 3 hours after completion of dropping, and the reaction solution was allowed to stand in a refrigerator for 12 hours. Thereafter, the white precipitate was filtered by suction, washed with ultrapure water 2-3 times, transferred to a petri dish, and dried under reduced pressure at 40 ° C. for 1 day. The yield was 94%.
実施例2 DNA/CTMA膜の製造
実施例1で得たDNA/CTMA0.3gをクロロホルム:エタノール(4:1)22gに溶解し、これをガラス板上にキャストし、40℃で30分減圧乾燥し、フィルムを得た。
Example 2 Production of DNA / CTMA membrane 0.3 g of DNA / CTMA obtained in Example 1 was dissolved in 22 g of chloroform: ethanol (4: 1), cast on a glass plate, and dried under reduced pressure at 40 ° C. for 30 minutes. And a film was obtained.
実施例3 DNA/DTMAの合成
CTMACl 3.42gに代えて、ドデシルトリメチルアンモニウムクロライド(DTMACl)2.8g(1.07×10−2mol)を用いること以外は実施例1と同様にしてDNA/DTMAを得た。収率は96%であった。
Example 3 Synthesis of DNA / DTMA DNA / DTMA was synthesized in the same manner as in Example 1 except that 2.8 g (1.07 × 10 −2 mol) of dodecyltrimethylammonium chloride (DTMACl) was used instead of 3.42 g of CTMAC1. DTMA was obtained. The yield was 96%.
実施例4 DNA/DTMA膜の製造
DNA/CTMAの代りに実施例3で得たDNA/DTMAを使用する以外は実施例2と同様にしてDNA/DTMA膜を製造した。
Example 4 Production of DNA / DTMA Membrane A DNA / DTMA membrane was produced in the same manner as in Example 2 except that DNA / DTMA obtained in Example 3 was used instead of DNA / CTMA.
実施例5 DNA/TDTMAの合成
CTMACl 3.42gに代えて、テトラデシルトリメチルアンモニウムクロライド(TDTMACl)3.59g(1.07×10−2mol)を用いること以外は実施例1に同様にしてDNA/TDTMAを得た。収率は94.5%であった。
Example 5 Synthesis of DNA / TDTMA DNA was replaced in the same manner as in Example 1 except that 3.59 g (1.07 × 10 −2 mol) of tetradecyltrimethylammonium chloride (TDTMACl) was used instead of 3.42 g of CTMAC1. / TDTMA was obtained. The yield was 94.5%.
実施例6 DNA/TDTMA膜の製造
DNA/CTMAの代りに実施例5で得たDNA/TDTMAを使用する以外は実施例2と同様にしてDNA/TDTMA膜を製造した。
Example 6 Production of DNA / TDTMA Membrane A DNA / TDTMA membrane was produced in the same manner as in Example 2, except that DNA / TDTMA obtained in Example 5 was used instead of DNA / CTMA.
実施例7 DNA/STMAの合成
CTMACl 3.42gに代えて、ステアリルトリメチルアンモニウムクロライド(STMACl)3.70g(1.07×10−2mol)を用いること以外は実施例1と同様にしてDNA/STMAを得た。収率93%であった。
Example 7 Synthesis of DNA / STMA DNA / STMA was replaced with DNA / STMA in the same manner as in Example 1 except that 3.70 g (1.07 × 10 −2 mol) of stearyltrimethylammonium chloride (STMACl) was used instead of 3.42 g. Obtained STMA. The yield was 93%.
実施例8 DNA/STMA膜の製造
DNA/CTMAの代りに実施例7で得たDNA/STMAを使用する以外は実施例2と同様にしてDNA/STMA膜を製造した。
Example 8 Production of DNA / STMA Membrane A DNA / STMA membrane was produced in the same manner as in Example 2 except that DNA / STMA obtained in Example 7 was used instead of DNA / CTMA.
実施例9 DNA/BDMTDAの合成
CTMACl 3.42gに代えて、ベンジルジメチルテトラデシルアンモニウムクロライド(BDMTDACl)3.93g(1.07×10−2mol)を用いる以外は実施例1と同様にしてDNA/BDMTDAを得た。収率96%であった。
Example 9 Synthesis of DNA / BDMTDA DNA was replaced in the same manner as in Example 1 except that 3.93 g (1.07 × 10 −2 mol) of benzyldimethyltetradecylammonium chloride (BDMTDACl) was used instead of 3.42 g of CTMAC1. / BDMTDA was obtained. The yield was 96%.
実施例10 DNA/BDMTDA膜の製造
DNA/CTMAの代りに実施例9で得たDNA/BDMTDAを使用する以外は実施例2と同様にしてDNA/BDMTDA膜を製造した。
Example 10 Production of DNA / BDMTDA Membrane A DNA / BDMTDA membrane was produced in the same manner as in Example 2 except that DNA / BDMTDA obtained in Example 9 was used instead of DNA / CTMA.
実施例11 DNA/BCDMAの合成
CTMACl 3.4gに代えて、ベンジルセチルジメチルアンモニウムクロライド(BCDMACl)4.23g(1.07×10−2mol)を用いる以外は実施例1と同様にしてDNA/BCDMAを得た。収率94%であった。
Example 11 Synthesis of DNA / BCDMA DNA / BCDMA was prepared in the same manner as in Example 1 except that 4.23 g (1.07 × 10 −2 mol) of benzylcetyldimethylammonium chloride (BCDMACl) was used instead of 3.4 g of CTMAC1. BCDMA was obtained. The yield was 94%.
実施例12 DNA/BCDMA膜の製造
DNA/CTMAの代りに実施例11で得たDNA/BCDMAを使用する以外は実施例2と同様にしてDNA/BCDMA膜を製造した。
Example 12 Production of DNA / BCDMA Membrane A DNA / BCDMA membrane was produced in the same manner as in Example 2 except that DNA / BCDMA obtained in Example 11 was used instead of DNA / CTMA.
実施例13 DNA/BDMSAの合成
CTMACl 3.4gに代えて、ベンジルジメチルステアリルアンモニウムクロライド(BDMSACl)4.5g(1.07×10−2mol)を用いる以外は実施例1と同様にしてDNA/BDMSAを得た。収率96.5%であった。
Example 13 Synthesis of DNA / BDMSA DNA / BDMSA was replaced in the same manner as in Example 1 except that 4.5 g (1.07 × 10 -2 mol) of benzyldimethylstearylammonium chloride (BDMSACl) was used instead of 3.4 g. BDMSA was obtained. The yield was 96.5%.
実施例14 DNA/BDMSAの製造
DNA/CTMAの代りに、実施例13で得たDNA/BDMSAを使用する以外は実施例2と同様にしてDNA/BDMSA膜を製造した。
Example 14 Production of DNA / BDMSA A DNA / BDMSA membrane was produced in the same manner as in Example 2 except that DNA / BDMSA obtained in Example 13 was used instead of DNA / CTMA.
実施例15 DNA/CPの合成
CTMACl 3.4gに代えて、セチルピリジニウムクロライド(CPCl)3.6g(1.07×10−2mol)を用いる以外は実施例1と同様にしてDNA/CPを得た。収率は殆んど定量的であった。
Example 15 Synthesis of DNA / CP DNA / CP was prepared in the same manner as in Example 1 except that 3.6 g (1.07 × 10 −2 mol) of cetylpyridinium chloride (CPCl) was used instead of 3.4 g of CTMAC1. Obtained. The yield was almost quantitative.
実施例16 DNA/CP膜の製造
DNA/CTMAの代りに、実施例15で得たDNA/CPを使用する以外は実施例2と同様にしてDNA/CP膜を製造した。
Example 16 Production of DNA / CP Membrane A DNA / CP membrane was produced in the same manner as in Example 2 except that DNA / CP obtained in Example 15 was used instead of DNA / CTMA.
実施例17 DNA/ベンゼトニウム塩の合成
CTMACl 3.4gに代えて、塩化ベンゼトニウム(4−(1,1,3,3−テトラメチルブチル)フェノキシエトキシエチルジメチルアンニウムクロライド)4.8g(1.07×10−2mol)を用いる以外は実施例1と同様にしてDNA/ベンゼトニウム塩を得た。収率は殆んど定量的であった。
Example 17 Synthesis of DNA / Benzetonium Salt Instead of CTMACl 3.4 g, 4.8 g (1.07) of benzethonium chloride (4- (1,1,3,3-tetramethylbutyl) phenoxyethoxyethyldimethylanium chloride) A DNA / benzethonium salt was obtained in the same manner as in Example 1 except that × 10 −2 mol) was used. The yield was almost quantitative.
実施例18 多孔質PTFE補強DNA/CP膜
実施例16で合成したDNA/CP 0.3gをクロロホルム:エタノール(4:1)22gに溶解し、この溶液でポリテトラフルオロエチレン多孔質フィルムを含浸し、40℃で1日乾燥して補強DNA/CP膜を製造した。
Example 18 Porous PTFE-reinforced DNA / CP membrane 0.3 g of DNA / CP synthesized in Example 16 was dissolved in 22 g of chloroform: ethanol (4: 1), and this solution was impregnated with a polytetrafluoroethylene porous film. The reinforced DNA / CP membrane was produced by drying at 40 ° C. for 1 day.
実施例19 ポリアミドイミドブレンドDNA/CTMA膜
実施例1で合成したDNA/CTMAと、ポリアミドイミド(Solvay Advanced Polymer社製TORLON)とを1対1の割合でDMFに溶解し、ガラス板上にキャストし、150℃で乾燥後剥離してポリアミドイミドブレンドDNA/CTMA膜を製造した。
Example 19 Polyamideimide blend DNA / CTMA membrane DNA / CTMA synthesized in Example 1 and polyamideimide (TORLON manufactured by Solvay Advanced Polymer) were dissolved in DMF at a ratio of 1: 1 and cast on a glass plate. After drying at 150 ° C., peeling was performed to produce a polyamideimide blend DNA / CTMA film.
ガス透過性試験
実施例で製造した膜のいくつかについて、JIS K71261987に準じてO2およびN2について気体透過率を測定した。ツクバリカセイキ(株)製気体透過率測定装置を使用し、温度および供給(上流側)圧力条件は、それぞれ25℃および106kPaに設定した。またO2およびN2の透過係数からP(O2)/P(N2)の比を求め、他のガスに対するO2ガス選択透過性の指標とした。結果を表1に示す。
For some of the membranes produced in the gas permeability test example, gas permeability was measured for O 2 and N 2 according to JIS K71261987. Using a gas permeability measuring device manufactured by Tsukubarika Seiki Co., Ltd., temperature and supply (upstream side) pressure conditions were set to 25 ° C. and 106 kPa, respectively. The calculated ratio of P (O 2) / P ( N 2) from the transmission coefficient of O 2 and N 2, was O 2 gas permselective indicator for other gases. The results are shown in Table 1.
水蒸気透過性試験
実施例で製造したいくつかについて水蒸気透過率を測定した。密閉可能なガラス製サンプルホルダーにDNA脂質膜を装着し、サンプルホルダー内に入れた水を55℃に加温し、一定時間内に透過した水蒸気量をサンプルホルダー内に残存した水重量から算出した。なお、水温55℃の飽和水蒸気圧は約157hPaである。結果を表2に示す。
Water vapor permeability test The water vapor permeability was measured for some of the examples produced in the examples. A DNA lipid membrane was attached to a sealable glass sample holder, the water in the sample holder was heated to 55 ° C., and the amount of water vapor permeated within a certain time was calculated from the weight of water remaining in the sample holder. . The saturated water vapor pressure at a water temperature of 55 ° C. is about 157 hPa. The results are shown in Table 2.
上で実施した水蒸気透過試験方法を採用して汎用的なフィルムの水蒸気透過性試験を実施した。汎用的なフィルムと比較すると実施例で製造した膜は水蒸気透過率が極めて高い特徴を示した。結果を表3に示す。 A water vapor permeability test of a general-purpose film was performed by adopting the water vapor permeability test method performed above. Compared with a general-purpose film, the membrane produced in the example showed the feature of extremely high water vapor permeability. The results are shown in Table 3.
Claims (3)
The functional polymer membrane according to claim 2, comprising a reinforcing polymer matrix.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005235592A JP5157002B2 (en) | 2005-08-16 | 2005-08-16 | DNA salt and functional polymer film formed by forming the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005235592A JP5157002B2 (en) | 2005-08-16 | 2005-08-16 | DNA salt and functional polymer film formed by forming the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007051073A true JP2007051073A (en) | 2007-03-01 |
JP5157002B2 JP5157002B2 (en) | 2013-03-06 |
Family
ID=37915772
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005235592A Expired - Fee Related JP5157002B2 (en) | 2005-08-16 | 2005-08-16 | DNA salt and functional polymer film formed by forming the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5157002B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007091647A (en) * | 2005-09-29 | 2007-04-12 | Trekion Co Ltd | Antimicrobial dna salt composition |
JP2009084225A (en) * | 2007-09-28 | 2009-04-23 | Dainippon Printing Co Ltd | Porous material, cell culture membrane, method for producing porous material and method for producing cell culture membrane |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08239398A (en) * | 1995-03-03 | 1996-09-17 | Sogo Yatsukou Kk | Water-insoluble, self-supporting transparent dna/lipid complex film and its production |
JP2001294597A (en) * | 2000-04-12 | 2001-10-23 | Asahi Denka Kogyo Kk | Complex |
-
2005
- 2005-08-16 JP JP2005235592A patent/JP5157002B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08239398A (en) * | 1995-03-03 | 1996-09-17 | Sogo Yatsukou Kk | Water-insoluble, self-supporting transparent dna/lipid complex film and its production |
JP2001294597A (en) * | 2000-04-12 | 2001-10-23 | Asahi Denka Kogyo Kk | Complex |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007091647A (en) * | 2005-09-29 | 2007-04-12 | Trekion Co Ltd | Antimicrobial dna salt composition |
JP2009084225A (en) * | 2007-09-28 | 2009-04-23 | Dainippon Printing Co Ltd | Porous material, cell culture membrane, method for producing porous material and method for producing cell culture membrane |
Also Published As
Publication number | Publication date |
---|---|
JP5157002B2 (en) | 2013-03-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gu et al. | Chiral chemistry of metal–camphorate frameworks | |
Maly et al. | Engineering hydrogen-bonded molecular crystals built from derivatives of hexaphenylbenzene and related compounds | |
Kim et al. | Microwave-assisted cyanation of an aryl bromide directly on a metal− organic framework | |
HUE029738T2 (en) | 4-[2-[[5-methyl-1-(2-naphthalenyl)-1h-pyrazol-3-yl]oxy]ethyl]morpholine hydrochloride and solvates | |
TW200811082A (en) | Process for the preparation of cinacalcet base | |
JP5110564B2 (en) | Ionic organic compound and method for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound | |
TW200524848A (en) | Process of preparing O-carbamoyl compounds in the presence of active amine group | |
Malviya et al. | Self-healable lanthanoid-based metallogels: dye removal and crystallization in the confined gel state | |
JP5157002B2 (en) | DNA salt and functional polymer film formed by forming the same | |
Zhao et al. | Optically active helical polyacetylene self-assembled into chiral micelles used as nanoreactor for helix-sense-selective polymerization | |
Hawes et al. | A resilient and luminescent stimuli-responsive hydrogel from a heterotopic 1, 8-naphthalimide-derived ligand | |
Yeung et al. | Phase selection during the crystallization of metal–organic frameworks; thermodynamic and kinetic factors in the lithium tartrate system | |
JP2007045816A5 (en) | Carbazole derivative, preparation method of anthracene derivative used as material for light emitting device | |
JP5813238B2 (en) | Dendritic starch-based dextrin adhesive | |
Pan et al. | Supramolecular assemblies of novel aminonucleoside phospholipids and their bonding to nucleic acids | |
Zhao et al. | Self-assembled copper metallogel bearing terpyridine and its application as a catalyst for the click reaction in water | |
Feng et al. | Gelation of luminescent supramolecular cages and transformation to crystals with trace-doped-enhancement luminescence | |
JP4836144B2 (en) | Ionic organic compound and process for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound | |
Franke et al. | Effects of chirality on the aggregation properties of amide-bonded pyridinium gemini surfactants | |
Khavasi et al. | Is Gelation Behavior Predictable through a Crystal Engineering Approach? A Case Study in Four Similar Coordination Compounds | |
US4469621A (en) | Molecular aggregate having an ordered structure | |
Shen et al. | A mixed matrix Eu-4, 4′-biphenyldicarboxylate coordination polymer film as a fluorescence turn-off sensor to aniline vapor | |
Wang et al. | Study on the surface properties and aggregation behavior of quaternary ammonium surfactants with amide bonds | |
Price et al. | Maize 1: A trimorphic azo pigment | |
CN110372533B (en) | Cationic linear chloramine antibacterial agent and synthetic method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080805 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20101013 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111129 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120126 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120327 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120510 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121030 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121122 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5157002 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151221 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
LAPS | Cancellation because of no payment of annual fees |