fabrication-of-large-area-free-standing-ultrathin-polymer-films

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

Lawrence Livermore National Laboratory

Riportiamo la deposizione di vapore chimico di fotoiniziata (piCVD), un delicato Metodo sintetico per la preparazione delle pellicole ultrasottili (circa 100 nm) della poly(hydroxyethyl methacrylate) hydrogel (pHEMA). piCVD si verifica vicino a temperatura ambiente e richiede solo lievi condizioni di vuoto. Il film depositato gonfiarsi rapidamente e reversibilmente in soluzione tampone, e le propriet&agrave; di gonfiore possono essere controllate attraverso le condizioni di deposizione. Analisi dei dati gonfiori indica che la dimensione delle maglie dell&#39;idrogel crea un rivestimento selettivamente permeabile. La rete &egrave; abbastanza grande per consentire a piccola molecola analiti di permeare il film ma abbastanza piccolo per impedire il trasporto di grandi biomolecole come proteine. Spettacoli spettroscopia (XPS) della fotoemissione di raggi x che il film diminuire aspecifico adesione di proteine albumina da quasi ad nel silicio nuda. Un processo a secco, piCVD &egrave; adatto per le particelle di rivestimento con diametri piccoli come 5 microm. L&#39;assenza di solventi e plasmi in piCVD permette di film ad essere sintetizzato direttamente su optode sensori senza degradazione di sensibilit&agrave; o di tempo di risposta.

Protezione di sensori per applicazioni biologiche di deposizione di vapore chimico fotoiniziata di pellicole sottili di idrogel.

&#x6211;&#x4EEC;&#x62A5;&#x544A;&#x5149;&#x5F15;&#x53D1;&#x5316;&#x5B66;&#x6C14;&#x76F8;&#x6C89;&#x79EF; (piCVD)&#xFF0C;&#x6E29;&#x67D4;&#x7684;&#x8D85;&#x8584;&#x8584;&#x819C;&#x5236;&#x5907;&#x5408;&#x6210;&#x65B9;&#x6CD5; &#xFF08;&#x5927;&#x7EA6; 100 nm&#xFF09; &#x7684;&#x6C34;&#x51DD;&#x80F6; poly(hydroxyethyl methacrylate) (pHEMA)&#x3002;piCVD &#x5BA4;&#x6E29;&#x9644;&#x8FD1;&#x53D1;&#x751F;&#xFF0C;&#x5E76;&#x8981;&#x6C42;&#x53EA;&#x6709;&#x6E29;&#x548C;&#x7684;&#x771F;&#x7A7A;&#x6761;&#x4EF6;&#x3002;&#x8584;&#x819C;&#x81A8;&#x80C0;&#x8FC5;&#x901F;&#x53CA;&#x53EF;&#x9006;&#x7684;&#x7F13;&#x51B2;&#x6EB6;&#x6DB2;&#x548C;&#x80BF;&#x80C0;&#x7279;&#x6027;&#x53EF;&#x4EE5;&#x901A;&#x8FC7;&#x6C89;&#x79EF;&#x6761;&#x4EF6;&#x63A7;&#x5236;&#x3002;&#x4E0D;&#x65AD;&#x81A8;&#x80C0;&#x7684;&#x6570;&#x636E;&#x7684;&#x5206;&#x6790;&#x8868;&#x660E;&#x6C34;&#x51DD;&#x80F6;&#x7684;&#x7F51;&#x683C;&#x5927;&#x5C0F;&#x521B;&#x5EFA;&#x4E00;&#x79CD;&#x9009;&#x62E9;&#x6027;&#x6E17;&#x900F;&#x6D82;&#x5C42;&#x3002;&#x7F51;&#x683C;&#x662F;&#x8DB3;&#x591F;&#x5927;&#xFF0C;&#x4EE5;&#x5141;&#x8BB8;&#x5C0F;&#x5206;&#x5B50;&#x5206;&#x6790;&#x7269;&#x6E17;&#x900F;&#x4F46;&#x8DB3;&#x591F;&#x5C0F;&#xFF0C;&#x4EE5;&#x9632;&#x6B62;&#x8FD0;&#x8F93;&#x86CB;&#x767D;&#x8D28;&#x7B49;&#x751F;&#x7269;&#x5927;&#x5206;&#x5B50;&#x7684;&#x7535;&#x5F71;&#x3002;X &#x5C04;&#x7EBF;&#x5149;&#x7535;&#x5B50;&#x80FD;&#x8C31; (XPS) &#x663E;&#x793A;&#xFF0C;&#x7535;&#x5F71;&#x51CF;&#x5C11;&#x975E;&#x7279;&#x5F02;&#x6027;&#x9ECF;&#x9644;&#x86CB;&#x767D;&#x767D;&#x86CB;&#x767D;&#x7684;&#x8FD1; 8-fold &#x88F8;&#x7845;&#x3002;&#x5E72;&#x7684;&#x8FC7;&#x7A0B;&#x4E2D;&#xFF0C;piCVD &#x662F;&#x9002;&#x5408;&#x6D82;&#x6599;&#x7C92;&#x5B50;&#x7684;&#x76F4;&#x5F84;&#x5C0F;&#x81F3; 5 microm&#x3002;&#x6EB6;&#x5242;&#x548C;&#x7B49;&#x79BB;&#x5B50;&#x4F53;&#x5728; piCVD &#x4E2D;&#x7684;&#x6CA1;&#x6709;&#x5141;&#x8BB8;&#x7535;&#x5F71;&#x4E0A;&#x5149;&#x6781;&#x4F20;&#x611F;&#x5668;&#x4E0D;&#x9000;&#x5316;&#x7684;&#x654F;&#x611F;&#x6027;&#x6216;&#x54CD;&#x5E94;&#x65F6;&#x95F4;&#x7684;&#x60C5;&#x51B5;&#x4E0B;&#x76F4;&#x63A5;&#x5408;&#x6210;&#x3002;

&#x4F20;&#x611F;&#x5668;&#x7684;&#x751F;&#x7269;&#x5B66;&#x5E94;&#x7528;&#x6C34;&#x51DD;&#x80F6;&#x8584;&#x819C;&#x7684;&#x5149;&#x5F15;&#x53D1;&#x5316;&#x5B66;&#x6C14;&#x76F8;&#x6C89;&#x79EF;&#x6CD5;&#x7684;&#x4FDD;&#x62A4;&#x3002;

We report photoinitiated chemical vapor deposition (piCVD), a gentle synthetic method for the preparation of ultrathin films (approximately 100 nm) of the hydrogel poly(hydroxyethyl methacrylate) (pHEMA). piCVD occurs near room temperature and requires only mild vacuum conditions. The deposited films swell rapidly and reversibly in buffer solution, and the swelling properties can be controlled via the deposition conditions. Analysis of the swelling data indicates that the mesh size of the hydrogel creates a selectively permeable coating. The mesh is large enough to allow small molecule analytes to permeate the film but small enough to prevent the transport of large biomolecules such as proteins. X-ray photoelectron spectroscopy (XPS) shows that the films decrease nonspecific adhesion of the protein albumin by nearly 8-fold over bare silicon. A dry process, piCVD is suitable for coating particles with diameters as small as 5 microm. The absence of solvents and plasmas in piCVD allows films to be directly synthesized on optode sensors without degradation of sensitivity or response time.

Protection of sensors for biological applications by photoinitiated chemical vapor deposition of hydrogel thin films.

On rapport photoiniti&#xE9;e d&#xE9;p&#xF4;t chimique en phase vapeur (PICVD), un proc&#xE9;d&#xE9; synth&#xE9;tique doux pour la pr&#xE9;paration de films ultraminces (environ 100 nm) de l&#x26;#39;hydrogel de poly (m&#xE9;thacrylate d&#x26;#39;hydroxy&#xE9;thyle) (PHEMA). PICVD se trouve pr&#xE8;s de la temp&#xE9;rature ambiante et ne n&#xE9;cessite que des conditions de vide doux. Les films d&#xE9;pos&#xE9;s gonflent rapidement et de mani&#xE8;re r&#xE9;versible dans une solution tampon, et les propri&#xE9;t&#xE9;s de gonflement peut &#xEA;tre contr&#xF4;l&#xE9; via les conditions de d&#xE9;p&#xF4;t. L&#x26;#39;analyse des donn&#xE9;es indique que l&#x26;#39;enflure de la taille de maille de l&#x26;#39;hydrogel cr&#xE9;e un rev&#xEA;tement perm&#xE9;able de mani&#xE8;re s&#xE9;lective. Le maillage est suffisamment grande pour permettre &#xE0; de petites mol&#xE9;cules d&#x26;#39;analytes perm&#xE9;at du film mais suffisamment petite pour emp&#xEA;cher le transport de grandes biomol&#xE9;cules telles que des prot&#xE9;ines. X-spectroscopie de photo&#xE9;lectrons (XPS) montre que les films de diminuer l&#x26;#39;adh&#xE9;rence non sp&#xE9;cifique de l&#x26;#39;albumine prot&#xE9;ines de pr&#xE8;s de 8 fois par rapport au silicium &#xE0; nu. Un proc&#xE9;d&#xE9; par voie s&#xE8;che, PICVD est appropri&#xE9; pour l&#x26;#39;enrobage de particules avec des diam&#xE8;tres aussi petits que 5 microm. L&#x26;#39;absence de solvants et des plasmas dans PICVD permet films &#xE0; synth&#xE8;se directe sur les capteurs optode sans d&#xE9;gradation de la sensibilit&#xE9; ou le temps de r&#xE9;ponse.

Protection des capteurs pour des applications biologiques par photoiniti&#xE9;e Chemical Vapor Deposition de films d&#x26;#39;hydrogel minces

Wir berichten Photoinitiated chemische Gasphasenabscheidung (PiCVD), synthetische schonende Methode f&uuml;r die Vorbereitung der ultrad&uuml;nne Schichten (ca. 100 nm) von der Hydrogel-Poly(hydroxyethyl methacrylate) (pHEMA). PiCVD erfolgt bei Raumtemperatur und erfordert nur milde Vakuumbedingungen. Die hinterlegten Filme Schwellen schnell und reversibel in Pufferl&ouml;sung und die Schwellungen Eigenschaften k&ouml;nnen &uuml;ber die Absetzung Bedingungen kontrolliert werden. Analyse der Schwellungen Daten bedeutet, dass die Maschenweite der Hydrogel selektiv durchl&auml;ssige Beschichtung erstellt. Das Netz ist gro&szlig; genug, um niedermolekulare Analyte zu erm&ouml;glichen, den Film aber klein genug, um zu verhindern, dass den Transport von gro&szlig;en Molek&uuml;len wie Proteinen zu durchdringen. X-ray Photoelektronenspektroskopie Spektroskopie (XPS) zeigt die Filme unspezifische Adh&auml;sion der Protein Albumin durch fast 8-fach nackten Silizium sinken. Ein Trockenverfahren, eignet sich PiCVD f&uuml;r Beschichtung Teilchen mit Durchmessern 5 Microm m&ouml;glichst klein. Das Fehlen von L&ouml;sungsmitteln und Plasmen in PiCVD erlaubt Filme direkt auf Optoden Sensoren ohne Verschlechterung der Sensitivit&auml;t oder Reaktionszeiten synthetisiert werden.

Schutz von Sensoren f&uuml;r biologische Anwendungen von Photoinitiated chemische Gasphasenabscheidung Hydrogel d&uuml;nner Schichten.

&#x6211;&#x3005;&#x306F;&#x3001;&#x5149;&#x958B;&#x59CB;&#x5316;&#x5B66;&#x84B8;&#x7740;&#xFF08;piCVD&#xFF09;&#x3001;&#xFF08;PHEMA&#xFF09;&#xFF08;&#x30D2;&#x30C9;&#x30ED;&#x30AD;&#x30B7;&#x30A8;&#x30C1;&#x30EB;&#x30E1;&#x30BF;&#x30AF;&#x30EA;&#x30EC;&#x30FC;&#x30C8;&#xFF09;&#x3001;&#x30DD;&#x30EA;&#x30CF;&#x30A4;&#x30C9;&#x30ED;&#x30B2;&#x30EB;&#x306E;&#x8D85;&#x8584;&#x819C;&#xFF08;100nm&#x7A0B;&#x5EA6;&#xFF09;&#x306E;&#x6E96;&#x5099;&#x306E;&#x305F;&#x3081;&#x306E;&#x7A4F;&#x3084;&#x304B;&#x306A;&#x5408;&#x6210;&#x6CD5;&#x3092;&#x5831;&#x544A;&#x3057;&#x307E;&#x3059;&#x3002; piCVD&#x306F;&#x5BA4;&#x6E29;&#x4ED8;&#x8FD1;&#x3067;&#x767A;&#x751F;&#x3057;&#x3001;&#x8EFD;&#x5EA6;&#x306E;&#x771F;&#x7A7A;&#x72B6;&#x614B;&#x3092;&#x5FC5;&#x8981;&#x3068;&#x3057;&#x307E;&#x3059;&#x3002;&#x5806;&#x7A4D;&#x819C;&#x306F;&#x7DE9;&#x885D;&#x6DB2;&#x4E2D;&#x3067;&#x8FC5;&#x901F;&#x304B;&#x3064;&#x53EF;&#x9006;&#x7684;&#x306B;&#x81A8;&#x6F64;&#x3057;&#x3001;&#x81A8;&#x6F64;&#x6027;&#x306F;&#x3001;&#x6210;&#x819C;&#x6761;&#x4EF6;&#x3092;&#x4ECB;&#x3057;&#x3066;&#x5236;&#x5FA1;&#x3059;&#x308B;&#x3053;&#x3068;&#x304C;&#x3067;&#x304D;&#x307E;&#x3059;&#x3002;&#x816B;&#x308C;&#x30C7;&#x30FC;&#x30BF;&#x306E;&#x5206;&#x6790;&#x3067;&#x306F;&#x3001;&#x30CF;&#x30A4;&#x30C9;&#x30ED;&#x30B2;&#x30EB;&#x306E;&#x30E1;&#x30C3;&#x30B7;&#x30E5;&#x30B5;&#x30A4;&#x30BA;&#x306F;&#x9078;&#x629E;&#x900F;&#x904E;&#x30B3;&#x30FC;&#x30C6;&#x30A3;&#x30F3;&#x30B0;&#x3092;&#x4F5C;&#x6210;&#x3059;&#x308B;&#x3053;&#x3068;&#x3092;&#x793A;&#x3057;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002;&#x30E1;&#x30C3;&#x30B7;&#x30E5;&#x306F;&#x3001;&#x30D5;&#x30A3;&#x30EB;&#x30E0;&#x3092;&#x900F;&#x904E;&#x3059;&#x308B;&#x5C0F;&#x5206;&#x5B50;&#x691C;&#x4F53;&#x3092;&#x8A31;&#x53EF;&#x3059;&#x308B;&#x306E;&#x306B;&#x5341;&#x5206;&#x306A;&#x5927;&#x304D;&#x3055;&#x304C;&#x3001;&#x305D;&#x306E;&#x3088;&#x3046;&#x306A;&#x30BF;&#x30F3;&#x30D1;&#x30AF;&#x8CEA;&#x306A;&#x3069;&#x306E;&#x5927;&#x304D;&#x306A;&#x751F;&#x4F53;&#x5206;&#x5B50;&#x306E;&#x8F38;&#x9001;&#x3092;&#x9632;&#x3050;&#x305F;&#x3081;&#x306B;&#x5341;&#x5206;&#x306B;&#x5C0F;&#x3055;&#x3044;&#x3002; X&#x7DDA;&#x5149;&#x96FB;&#x5B50;&#x5206;&#x5149;&#x6CD5;&#xFF08;XPS&#xFF09;&#x306F;&#x3001;&#x30D5;&#x30A3;&#x30EB;&#x30E0;&#x306F;&#x7D04;8&#x500D;&#x306E;&#x30D9;&#x30A2;&#x30B7;&#x30EA;&#x30B3;&#x30F3;&#x4E0A;&#x3067;&#x306E;&#x30BF;&#x30F3;&#x30D1;&#x30AF;&#x8CEA;&#x30A2;&#x30EB;&#x30D6;&#x30DF;&#x30F3;&#x306E;&#x975E;&#x7279;&#x7570;&#x7684;&#x306A;&#x63A5;&#x7740;&#x3092;&#x6E1B;&#x5C11;&#x3055;&#x305B;&#x308B;&#x3053;&#x3068;&#x3092;&#x793A;&#x3057;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002;&#x30C9;&#x30E9;&#x30A4;&#x30D7;&#x30ED;&#x30BB;&#x30B9;&#x306F;&#x3001;piCVD&#x306F;5&#x30DE;&#x30A4;&#x30AF;&#x30ED;&#x30E2;&#x30EB;&#x306E;&#x3088;&#x3046;&#x306A;&#x5C0F;&#x3055;&#x306A;&#x76F4;&#x5F84;&#x3092;&#x6709;&#x3059;&#x308B;&#x30B3;&#x30FC;&#x30C6;&#x30A3;&#x30F3;&#x30B0;&#x7C92;&#x5B50;&#x306B;&#x9069;&#x3057;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002; piCVD&#x306E;&#x6EB6;&#x5A92;&#x3068;&#x30D7;&#x30E9;&#x30BA;&#x30DE;&#x306E;&#x4E0D;&#x5728;&#x306F;&#x3001;&#x30D5;&#x30A3;&#x30EB;&#x30E0;&#x304C;&#x76F4;&#x63A5;&#x611F;&#x5EA6;&#x3084;&#x5FDC;&#x7B54;&#x6642;&#x9593;&#x306E;&#x52A3;&#x5316;&#x3055;&#x305B;&#x305A;&#x306B;&#x30AA;&#x30D7;&#x30C8;&#x30FC;&#x30C9;&#x30BB;&#x30F3;&#x30B5;&#x30FC;&#x4E0A;&#x306B;&#x5408;&#x6210;&#x3059;&#x308B;&#x3053;&#x3068;&#x304C;&#x3067;&#x304D;&#x307E;&#x3059;&#x3002;

&#x30CF;&#x30A4;&#x30C9;&#x30ED;&#x30B2;&#x30EB;&#x8584;&#x819C;&#x306E;&#x5149;&#x958B;&#x59CB;CVD&#x6CD5;&#x306B;&#x3088;&#x308B;&#x751F;&#x7269;&#x5B66;&#x7684;&#x30A2;&#x30D7;&#x30EA;&#x30B1;&#x30FC;&#x30B7;&#x30E7;&#x30F3;&#x306E;&#x305F;&#x3081;&#x306E;&#x30BB;&#x30F3;&#x30B5;&#x306E;&#x4FDD;&#x8B77;

Photoinitiated &#xD654;&#xD559; &#xAE30;&#xC0C1; &#xC99D; &#xCC29; (piCVD), ultrathin &#xC601;&#xD654; &#xC900;&#xBE44;&#xC5D0; &#xB300; &#xD55C; &#xBD80;&#xB4DC;&#xB7EC;&#xC6B4; &#xD569;&#xC131; &#xBC29;&#xBC95;&#xC744; &#xC54C;&#xB824;&#xB4DC;&#xB9BD;&#xB2C8;&#xB2E4; (&#xC57D; 100 nm) hydrogel poly(hydroxyethyl methacrylate) (pHEMA)&#xC758;. piCVD &#xC2E4;&#xB0B4; &#xC628;&#xB3C4; &#xAC00;&#xAE4C;&#xC774; &#xBC1C;&#xC0DD; &#xD558; &#xACE0;&#xB9CC; &#xAC00;&#xBCBC;&#xC6B4; &#xC9C4;&#xACF5; &#xC870;&#xAC74;&#xC774; &#xD544;&#xC694; &#xD569;&#xB2C8;&#xB2E4;. &#xC608;&#xCE58; &#xC601;&#xD654; &#xBC84;&#xD37C; &#xC194;&#xB8E8;&#xC158;&#xC5D0; &#xBE60;&#xB974;&#xAC8C; &#xACE0; &#xC5ED; &#xD30C;&#xB3C4; &#xC99D; &#xCC29; &#xC870;&#xAC74;&#xC744; &#xD1B5;&#xD574; &#xBD93;&#xAE30; &#xC18D;&#xC131;&#xC744; &#xC81C;&#xC5B4;&#xD560; &#xC218; &#xC788;&#xC2B5;&#xB2C8;&#xB2E4;. &#xBD93;&#xAE30;&#xAC00; &#xB370;&#xC774;&#xD130;&#xC758; &#xBD84;&#xC11D;&#xC5D0;&#xC11C; hydrogel&#xC758; &#xBA54;&#xC26C; &#xD06C;&#xAE30; &#xC120;&#xD0DD;&#xC801;&#xC73C;&#xB85C; &#xD22C;&#xACFC; &#xCF54;&#xD305; &#xB9CC;&#xB4ED;&#xB2C8;&#xB2E4; &#xB098;&#xD0C0;&#xB0C5;&#xB2C8;&#xB2E4;. &#xBA54;&#xC26C; &#xCE68;&#xD22C; &#xD558;&#xC9C0;&#xB9CC; &#xB2E8;&#xBC31;&#xC9C8; &#xAC19;&#xC740; &#xD070; biomolecules &#xC804;&#xC1A1; &#xBC29;&#xC9C0; &#xD558;&#xAE30; &#xC704;&#xD574; &#xCDA9;&#xBD84;&#xD788; &#xC791;&#xC740; &#xC601;&#xD654;&#xB97C; &#xC791;&#xC740; &#xBD84;&#xC790; analytes &#xC218; &#xC788;&#xB3C4;&#xB85D; &#xCDA9;&#xBD84;&#xD788; &#xD07D;&#xB2C8;&#xB2E4;. &#xC601;&#xD654; &#xAC10;&#xC18C; &#xD558; &#xC5EC; &#xB2E8;&#xBC31;&#xC9C8; &#xC54C; &#xBD80; &#xBBFC;&#xC758; &#xC77C;&#xBC18; &#xC811;&#xCC29; &#xBCA0;&#xC5B4; &#xC2E4;&#xB9AC;&#xCF58; &#xAC70;&#xC758; 8-fold&#xB294; x-&#xC120; &#xAD11;&#xC804;&#xC790; &#xBD84; &#xAD11; &#xBC95; (XPS) &#xC1FC;. &#xAC74;&#xC870; &#xACFC;&#xC815; Picvd&#xB294; &#xC9C1;&#xACBD; 5 microm &#xC791;&#xC740; &#xC785;&#xC790; &#xCF54;&#xD305;&#xC5D0; &#xC801;&#xD569; &#xD569;&#xB2C8;&#xB2E4;. &#xC6A9; &#xC81C; &#xBC0F; Picvd&#xC5D0;&#xC11C; &#xD50C;&#xB77C;&#xC988;&#xB9C8;&#xC758; &#xBD80;&#xC7AC; &#xC601;&#xD654;&#xB97C; optode &#xC13C;&#xC11C;&#xC758; &#xAC10;&#xB3C4; &#xB098; &#xC751;&#xB2F5; &#xC2DC;&#xAC04; &#xC800;&#xD558; &#xC5C6;&#xC774; &#xC9C1;&#xC811; &#xD569;&#xC131; &#xC218; &#xC788;&#xC2B5;&#xB2C8;&#xB2E4;.

Hydrogel &#xBC15;&#xB9C9;&#xC758; photoinitiated &#xD654;&#xD559; &#xAE30;&#xC0C1; &#xC99D; &#xCC29;&#xC5D0; &#xC758;&#xD574; &#xC0DD;&#xBB3C; &#xD559;&#xC801; &#xC751;&#xC6A9; &#xD504;&#xB85C;&#xADF8;&#xB7A8;&#xC5D0; &#xB300; &#xD55C; &#xC13C;&#xC11C;&#xC758; &#xBCF4;&#xD638;.

Se presenta qu&#xED;mica fotoiniciada deposici&#xF3;n de vapor (PICVD), un m&#xE9;todo suave sint&#xE9;tico para la preparaci&#xF3;n de pel&#xED;culas ultrafinas (aproximadamente 100 nm) del hidrogel de poli (metacrilato de hidroxietilo) (PHEMA). PICVD se produce a temperatura ambiente y s&#xF3;lo requiere condiciones de vac&#xED;o leves. Las pel&#xED;culas depositadas se hinchan r&#xE1;pidamente y de forma reversible en soluci&#xF3;n tamp&#xF3;n, y las propiedades de hinchamiento puede ser controlado a trav&#xE9;s de las condiciones de deposici&#xF3;n. El an&#xE1;lisis de los datos de hinchamiento indica que el tama&#xF1;o de malla del hidrogel crea una capa selectivamente permeable. La malla es lo suficientemente grande para permitir que los analitos de mol&#xE9;culas peque&#xF1;as a impregnar la pel&#xED;cula, pero lo suficientemente peque&#xF1;o para evitar el transporte de biomol&#xE9;culas grandes, tales como prote&#xED;nas. Espectroscop&#xED;a de rayos X (XPS), muestra que las pel&#xED;culas disminuir la adherencia no espec&#xED;fica de la alb&#xFA;mina prote&#xED;na por casi 8-veces sobre silicio al descubierto. Un proceso en seco, PICVD es adecuado para recubrir part&#xED;culas con di&#xE1;metros tan peque&#xF1;os como 5 micras. La ausencia de disolventes y plasmas en PICVD permite pel&#xED;culas que se sintetizan directamente en los sensores optode sin degradaci&#xF3;n de la sensibilidad o tiempo de respuesta.

Protecci&#xF3;n de los sensores para aplicaciones biol&#xF3;gicas por fotoiniciados deposici&#xF3;n de vapor qu&#xED;mico de pel&#xED;culas delgadas de hidrogel

simple method to fabricate a multifunctional patterned platform on the nanometer scale is demonstrated. The platform contains two reactive functional groups on the surface: one is an acetylene group which can be functionalized via click chemistry, and the other is an amine group which can also be functionalized by classic carbodiimide chemistry with N-hydroxysuccinimide (NHS). The click-active and amine surface could be obtained from polymer coating of poly(propargyl methacrylate) (PPMA) via initiated chemical vapor deposition (iCVD) and poly(allylamine) (PAAm) via a plasma polymerization process, respectively, utilizing commercially available monomers. A capillary force lithography (CFL) process was applied on a stacked film of a PPMA layer on PAAm, and CFL could selectively pattern PPMA maintaining the bottom PAAm layer intact, which completes the multifunctional nanopatterns. The minimum feature size of this nanopattern was 110 nm. The entire fabrication process is solventless and low temperature, which can minimize the loss of functionalities. The click and NHS reactions are highly orthogonal to each other so that nonspecific immobilization can be minimized. These advantageous characteristics enable the covalent functionalization of two independent components in a one-pot functionalization process in self-recognized way. The one-pot orthogonal functionalization was performed in an aqueous solution at room temperature, which is biocompatible. Considering the versatility and generality of the reactions used here, we believe this platform can be easily extended to various biodevice applications.

Patterning nanodomains with orthogonal functionalities: solventless synthesis of self-sorting surfaces.

Novel nanoporous poly(3,4-ethylenedioxythiophene) (PEDOT) films with basalt-like surface morphology are successfully obtained via a one-step, vapor phase process of oxidative chemical vapor deposition (oCVD) by introducing a new oxidant, CuCl(2). The substrate temperature of the oCVD process is a crucial process parameter for controlling electrical conductivity and conjugation length. Moreover, the surface morphology is also systemically tunable through variations in substrate temperature, a unique advantage of the oCVD process. By increasing the substrate temperature, the surface morphology becomes more porous, with the textured structure on the nanometer scale. The size of nanopores and fibrils appears uniformly over 25 mm x 25 mm areas on the Si wafer substrates. Conformal coverage of PEDOT films grown with the CuCl(2) oxidant (C-PEDOT) is observed on both standard trench structures with high aspect ratio and fragile surfaces with complex topology, such as paper, results which are extremely difficult to achieve with liquid phase based processes. The tunable nanoporosity and its conformal coverage on various complex geometries are highly desirable for many device applications requiring controlled, high interfacial area, such as supercapacitors, Li ion battery electrodes, and sensors. For example, a highly hydrophilic surface with the static water contact angle down to less than 10 degrees is obtained solely by changing surface morphology. By applying fluorinated polymer film onto the nanoporous C-PEDOT via initiative chemical vapor deposition (iCVD), the C-PEDOT surface also shows the contact angle higher than 150 degrees . The hierarchical porous structure of fluorinated polymer coated C-PEDOT on a paper mat shows superhydrophobicity and oil repellency.

Conformal coverage of poly(3,4-ethylenedioxythiophene) films with tunable nanoporosity via oxidative chemical vapor deposition.

Chemical vapor deposition (CVD) is a widely-used technology for the preparation of conformal and defect-free inorganic thin films with systematically tunable properties. Polymers are a desirable class of materials for surface modification because of their low cost, wide array of chemical and physical functionality and mechanical flexibility. Initiated and oxidative chemical vapor deposition (iCVD and oCVD) are polymer CVD methods that combine the benefits of CVD processing with the possibilities of polymeric materials. Using these technologies, our laboratory has synthesized a number of functional, biocompatible and electrically conducting polymers as thin films on micro- and nano-structured surfaces. This Perspective will review recent advances in these areas and highlight devices and applications that utilize iCVD and oCVD polymers.

Initiated and oxidative chemical vapor deposition: a scalable method for conformal and functional polymer films on real substrates.

Chemical vapor deposition (CVD) polymerization utilizes the delivery of vapor-phase monomers to form chemically well-defined polymeric films directly on the surface of a substrate. CVD polymers are desirable as conformal surface modification layers exhibiting strong retention of organic functional groups, and, in some cases, are responsive to external stimuli. Traditional wet-chemical chain- and step-growth mechanisms guide the development of new heterogeneous CVD polymerization techniques. Commonality with inorganic CVD methods facilitates the fabrication of hybrid devices. CVD polymers bridge microfabrication technology with chemical, biological, and nanoparticle systems and assembly. Robust interfaces can be achieved through covalent grafting enabling high-resolution (60 nm) patterning, even on flexible substrates. Utilizing only low-energy input to drive selective chemistry, modest vacuum, and room-temperature substrates, CVD polymerization is compatible with thermally sensitive substrates, such as paper, textiles, and plastics. CVD methods are particularly valuable for insoluble and infusible films, including fluoropolymers, electrically conductive polymers, and controllably crosslinked networks and for the potential to reduce environmental, health, and safety impacts associated with solvents. Quantitative models aid the development of large-area and roll-to-roll CVD polymer reactors. Relevant background, fundamental principles, and selected applications are reviewed.

Chemical vapor deposition of conformal, functional, and responsive polymer films.

Gold nanorods (GNRs) stabilized with cetyltrimethylammonium bromide (CTAB) and GNR functionalized via a ligand exchange method with either thiolated polyethylene glycol (PEG(5000)) or mercaptohexadecanoic acid (MHDA) were investigated for their stability in biological media and subsequent toxicological effects to HaCaT cells. GNR-PEG and GNR-MHDA exhibited minimal effects on cell proliferation, whereas GNR-CTAB reduced cell proliferation significantly due to the inherent toxicity of the cationic surfactant to cells. Cell uptake studies indicated relatively low uptake for GNR-PEG and high uptake for GNR-MHDA. Reverse transcriptase polymerase chain reaction (RT-PCR) revealed that GNR-PEG induced less significant and unique changes in the transcription levels of 84 genes related to stress and toxicity compared to GNR-MHDA. The results demonstrate that, although cell proliferation was not affected by both particles, there is a significant difference in gene expression in GNR-MHDA exposed cells, suggesting long-term implications for chronic exposure.

Effect of gold nanorod surface chemistry on cellular response.

Bifunctional surfaces are micropatterned using a self-aligned, dual-purpose lithographic mask and pairs of conformally deposited iCVD polymers. A first layer is deposited, then physically masked and etched in oxygen plasma. A second layer is deposited with the mask still in place. Lift-off reveals the micropatterned surface. The thicknesses of the two layers are independently controlled so that the resultant surface displays both chemical and topographical contrast. The patterning scheme is independent of the polymers used and order of deposition. We use this scheme to create surfaces that spatially confine microcondensation, as well as chemical functionality. We also demonstrate microwells whose depth can be altered in response to a water stimulus.

Self-aligned micropatterns of bifunctional polymer surfaces with independent chemical and topographical contrast.

A study is presented of the nanomechanical phenomena experienced by nanoparticle-conjugated biomolecules. A thermodynamic framework is developed to describe the binding of thrombin-binding aptamer (TBA) to thrombin when the TBA is conjugated to nanorods. Binding results in nanorod aggregation (viz. directed self-assembly), which is detectable by absorption spectroscopy. The analysis introduces the energy of aggregation, separating it into TBA-thrombin recognition and surface-work contributions. Consequently, it is demonstrated that self-assembly is driven by the interplay of surface work and thrombin-TBA recognition. It is shown that the work at the surface is about -10 kJ mol(-1) and results from the accumulation of in-plane molecular forces of pN magnitude and with a lifetime of <1 s, which arises from TBA nanoscale rearrangements fuelled by thrombin-directed nanorod aggregation. The obtained surface work can map aggregation regimes as a function of different nanoparticle surface conditions. Also, the thermodynamic treatment can be used to obtain quantitative information on surface effects impacting biomolecules on nanoparticle surfaces.

Quantifying the nanomachinery of the nanoparticle-biomolecule interface.

Blood clotting is a precise cascade engineered to form a clot with temporal and spatial control. Current control of blood clotting is achieved predominantly by anticoagulants and thus inherently one-sided. Here we use a pair of nanorods (NRs) to provide a two-way switch for the blood clotting cascade by utilizing their ability to selectively release species on their surface under two different laser excitations. We selectively trigger release of a thrombin binding aptamer from one nanorod, inhibiting blood clotting and resulting in increased clotting time. We then release the complementary DNA as an antidote from the other NR, reversing the effect of the aptamer and restoring blood clotting. Thus, the nanorod pair acts as an on/off switch. One challenge for nanobiotechnology is the bio-nano interface, where coronas of weakly adsorbed proteins can obscure biomolecular function. We exploit these adsorbed proteins to increase aptamer and antidote loading on the nanorods.

Selective light-triggered release of DNA from gold nanorods switches blood clotting on and off.

Free-standing polymer thin films are typically fabricated using a sacrificial underlayer (between the film and its deposition substrate) or overlayer (on top of the film to assist peeling) in order to facilitate removal of the thin film from its deposition substrate. We show the direct delamination of extraordinarily thin (as thin as 8 nm) films of poly(vinyl formal) (PVF), polystyrene, and poly(methyl methacrylate). Large (up to 13 cm diameter) films of PVF could be captured on wire supports to produce free-standing films. By modifying the substrate to lower the interfacial energy resisting film-substrate separation, the conditions for spontaneous delamination are satisfied even for very thin films. The substrate modification is based on the electrostatic adsorption of a cationic polyelectrolyte. Eliminating the use of sacrificial materials and instead relying on naturally self-limiting adsorption makes this method suitable for large areas. We have observed delamination of films with aspect ratios (ratio of lateral dimension between supports to thickness) of 10(7) and have captured dry, free-standing films with aspect ratios >10(6). Films with an aspect ratio of 10(5) can bear loads up to 10(6) times the mass of the film itself. The presence of the adsorbed layer can be observed using X-ray photoelectron spectroscopy, and this layer is persistent through multiple uses. In the system studied, elimination of sacrificial materials leads to an enhancement in the failure strength of the free-standing thin film. The robustness, persistence, and the self-optimizing nature distinguish this method from various fabrication methods utilizing sacrificial materials and make it a potentially scalable process for the fabrication of ultrathin free-standing or transferrable films for filtration, MEMS, or tissue engineering applications.

Salmaan H. Baxamusa

Physical and Life Sciences Directorate

Lawrence Livermore National Laboratory

Fabrication of Large-area Free-standing Ultrathin Polymer Films

Salmaan H. Baxamusa

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Lawrence Livermore National Laboratory

Fabrication of Large-area Free-standing Ultrathin Polymer Films

Physical and Life Sciences Directorate