Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the ...

Louisiana State University

Targeted molecular imaging with two-photon fluorescence microscopy (2PFM) is a powerful technique for chemical biology and, potentially, for noninvasive diagnosis and treatment of a number of diseases. The synthesis, photophysical studies, and bioimaging are reported for a versatile norbornene-based block copolymer multifunctional scaffold containing biocompatible (PEG), two-photon fluorescent dyes (fluorenyl) and targeting (cyclic-RGD peptide) moieties. The two bioconjugates, containing two different fluorenyl dyes and cRGDfK covalently attached to the polymer probe, formed a spherical micelle and self-assembled structure in water, for which size was analyzed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Cell viability and 2PFM imaging of human epithelial U87MG cell lines that overexpress α(v)β(3) integrin was performed via incubation with the new probes, along with negative control studies using MCF-7 breast cancer cells and blocking experiments. 2PFM microscopy confirmed the high selectivity of the biocompatible probe in the integrin-rich area in the U87MF cells while blocking as well as negative control MCF-7 experiments confirmed the integrin-targeting ability of the new probes.

Integrin-targeting block copolymer probes for two-photon fluorescence bioimaging.

The size evolution of gold nanoparticles in a millifluidic reactor is investigated using spatially resolved transmission electron microscopy (TEM). The experimental data is supported by numerical simulations, carried out to study the residence-time distribution (RTD) of tracers that have the same properties as Au ions. Size and size distribution of the particles within the channels are influenced by the mixing zones as well as the RTD. However, the Au nanoparticles obtained show a broader size distribution even at the shortest investigated residence time of 3.53 s, indicating that in addition to surface growth reaction kinetics also plays an important role. The comparison of time resolved particle growth within the millifluidic channel with flask-based reactions reveals that the particle size can be controlled better within millifluidic channels. Overall, the results indicate potential opportunities to utilize easy to fabricate millifluidic reactors for the synthesis of nanoparticles, as well as as for carrying out time resolved kinetic studies.

Size evolution of gold nanoparticles in a millifluidic reactor.

Supramolecular structures based on organized assemblies of macrocyclic chromophores, particularly porphyrin-based dyes, have attracted widespread interest as components of molecular devices with potential applications in molecular electronics, artificial light harvesting, and pharmacology. We report the formation of J-aggregates of two porphyrin-based dyes, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TSPP, 4) and an amino tris-sulfonate analogue (5) in water using a functionalized norbornene-based homopolymer, synthesized by ring-opening metathesis polymerization (ROMP). Ionic interactions of the cationic side chains (ammonium groups) of the polymer under acidic conditions with the negatively charged sulfonate groups of the porphyrins facilitated polymer template enhanced J-aggregation of the porphyrin dyes. J-Aggregation behavior was investigated photophysically by UV-vis absorption along with steady-state and time-resolved fluorescence studies. Two-photon absorption (2PA) was enhanced by about an order of magnitude for the J-aggregated TSPP relative to its free base. Significantly, the 2PA cross section of the polymer-templated TSPP J-aggregate was up to three times higher than the J-aggregated TSPP in the absence of the polymer template while the 2PA cross section for polymer-templated J-aggregates of 5 increased substantially, up to ca. 10,000 GM, suggesting a prominent role of polymer-templating to facilitate porphyrin aggregation and greatly enhance nonlinear absorption.

Two-photon absorption enhancement of polymer-templated porphyrin-based J-aggregates.

&#x7EB3;&#x7C73;&#x6750;&#x6599;&#x7684;&#x5408;&#x6210;&#x82AF;&#x7247;&#x5B9E;&#x9A8C;&#x5BA4;&#x8BBE;&#x5907;&#x7684;&#x672A;&#x6765;&#x53D6;&#x51B3;&#x4E8E;&#x6210;&#x529F;&#x5F00;&#x53D1;&#x7684;&#x9AD8;&#x541E;&#x5410;&#x91CF;&#x65B9;&#x6CD5;&#x66F4;&#x597D;&#x5730;&#x63A7;&#x5236;&#x5176;&#x5927;&#x5C0F;&#x3002;&#x867D;&#x7136;&#x91CD;&#x5927;&#x52AA;&#x529B;&#x671D;&#x8FD9;&#x4E2A;&#x65B9;&#x5411;&#x4E3B;&#x8981;&#x662F;&#x91CD;&#x70B9;&#x53D1;&#x5C55;&quot;&#x96BE;&#x7F16;&#x9020;&quot;&#x590D;&#x6742;&#x5FAE;&#x6D41;&#x63A7;&#x53CD;&#x5E94;&#x5806;&#xFF0C;&#x5DF2;&#x5F88;&#x5C11;&#x6CE8;&#x610F;&quot;&#x5BB9;&#x6613;&#x7F16;&#x9020;&quot;&#x548C;&#x7B80;&#x5355;&#x7684; millifluidic &#x7CFB;&#x7EDF;&#xFF0C;&#x53EF;&#x63D0;&#x4F9B;&#x6240;&#x9700;&#x7684;&#x63A7;&#x4EF6;&#xFF0C;&#x4EE5;&#x53CA;&#x8F83;&#x9AD8;&#x7684;&#x541E;&#x5410;&#x91CF;&#x3002;&#x901A;&#x8FC7;&#x5229;&#x7528;&#x6D41;&#x4F53;&#x5185;&#x7684; millifluidic &#x7A7A;&#x95F4;&#x7684;&#x4E0D;&#x540C;&#x7684;&#x6D41;&#x7387;&#x7684;&#x6570;&#x503C;&#x6A21;&#x62DF;&#xFF0C;&#x5728;&#x8FD9;&#x91CC;&#x63D0;&#x51FA;&#x7684;&#x7ED3;&#x679C;&#x663E;&#x793A;&#x901F;&#x5EA6;&#x5206;&#x5E03;&#x548C;&#x5C45;&#x4F4F;&#x65F6;&#x95F4;&#x5206;&#x5E03;&#x7C7B;&#x4F3C;&#x4E8E;&#x5FAE;&#x6D41;&#x4F53;&#x7684;&#x60C5;&#x51B5;&#x3002;&#x901A;&#x8FC7;&#x5927;&#x5927;&#x51CF;&#x5C11;&#x7684;&#x505C;&#x7559;&#x65F6;&#x95F4;&#x548C;&#x505C;&#x7559;&#x65F6;&#x95F4;&#x5206;&#x5E03;&#xFF0C;&#x5177;&#x6709;&#x7279;&#x6B8A;&#x7684;&#x80F6;&#x4F53;&#x7A33;&#x5B9A;&#x6027;&#x7684;&#x8D85;&#x5C0F;&#x94DC;&#x7C07; &#xFF08;UCNCs&#xFF09; &#x7684;&#x8FDE;&#x7EED;&#x6D41;&#x52A8;&#x5408;&#x6210;&#x88AB;&#x5B9E;&#x73B0;&#x3002;&#x539F;&#x4F4D;&#x57FA;&#x4E8E;&#x540C;&#x6B65;&#x8F90;&#x5C04;&#x7684; x &#x5C04;&#x7EBF;&#x5438;&#x6536;&#x8C31; &#xFF08;XAS&#xFF09; &#x900F;&#x9732;&#x4F5C;&#x4E3A;&#x7F16;&#x5199;&#x7684;&#x96C6;&#x7FA4;&#x662F;&#x7EA6; 1 nm&#xFF0C;&#x8FDB;&#x4E00;&#x6B65;&#x652F;&#x6301;&#x7684;&#x900F;&#x5C04;&#x7535;&#x955C;&#x548C;&#x7D2B;&#x5916;&#x53EF;&#x89C1;&#x5149;&#x8C31;&#x7814;&#x7A76;&#x3002;&#x7FA4;&#x96C6;&#x62A5;&#x544A;&#x8FD9;&#x91CC;&#x6709;&#x6700;&#x5C0F;&#x7684;&#x4EE5;&#x5F80;&#x4EFB;&#x4F55;&#x65F6;&#x5019;&#x90FD;&#x4F7F;&#x7528;&#x751F;&#x4EA7;&#x82AF;&#x7247;&#x5B9E;&#x9A8C;&#x5BA4;&#x5E73;&#x53F0;&#x3002;&#x5F53;&#x4E8C;&#x6C27;&#x5316;&#x7845;&#x62C5;&#xFF0C;&#x4ED6;&#x4EEC;&#x53D1;&#x73B0;&#x9AD8;&#x6548;&#x50AC;&#x5316; C H &#x6C27;&#x5316;&#x53CD;&#x5E94;&#xFF0C;&#x8FC4;&#x4ECA;&#x672A;&#x77E5;&#xFF0C;&#x5C06;&#x50AC;&#x5316;&#x94DC;&#x3002;&#x8FD9;&#x9879;&#x5DE5;&#x4F5C;&#x8868;&#x660E; millifluidic &#x5E73;&#x53F0;&#x53EF;&#x4EE5;&#x6210;&#x4E3A;&#x4E00;&#x79CD;&#x5EC9;&#x4EF7;&#x3001; &#x591A;&#x624D;&#x591A;&#x827A;&#x3001; &#x6613;&#x4E8E;&#x4F7F;&#x7528;&#x548C;&#x5F3A;&#x5927;&#x7684;&#x5DE5;&#x5177;&#xFF0C;&#x4E00;&#x822C;&#xFF0C;&#x5728;&#x7EB3;&#x7C73;&#x7C92;&#x5B50;&#x5408;&#x6210;&#x548C;&#x66F4;&#x5177;&#x4F53;&#x5730;&#x8BF4;&#xFF0C;&#x662F;&#x8D85;&#x5C0F;&#x7C07; (Unc)&#x3002;

&#x8D85;&#x5C0F;&#x7EB3;&#x7C73;&#x56E2;&#x7C07;&#x7684;&#x5408;&#x6210;&#x7684; Millifluidic &#x5E73;&#x53F0;&#x5F00;&#x53D1;&#xFF1A; &#x8D85;&#x5C0F;&#x94DC;&#x7EB3;&#x7C73;&#x56E2;&#x7C07;&#x4F5C;&#x4E3A;&#x6848;&#x4F8B;&#x7814;&#x7A76;&#x3002;

The future of lab-on-a-chip devices for the synthesis of nanomaterials hinges on the successful development of high-throughput methods with better control over their size. While significant effort in this direction mainly focuses on developing "difficult to fabricate" complex microfluidic reactors, scant attention has been paid to the "easy to fabricate" and simple millifluidic systems that could provide the required control as well as high throughput. By utilizing numerical simulation of fluids within the millifluidic space at different flow rates, the results presented here show velocity profiles and residence time distributions similar to the case of microfluidics. By significantly reducing the residence time and residence time distribution, a continuous flow synthesis of ultrasmall copper nanoclusters (UCNCs) with exceptional colloidal stability is achieved. In-situ synchrotron-radiation-based X-ray absorption spectroscopy (XAS) reveal that the as-prepared clusters are about 1 nm, which is further supported by transmission electron microscopy and UV-vis spectroscopy studies. The clusters reported here are the smallest ever produced using a lab-on-a-chip platform. When supported on silica, they are found to efficiently catalyze C-H oxidation reactions, hitherto unknown to be catalyzed by Cu. This work suggests that a millifluidic platform can be an inexpensive, versatile, easy-to-use, and powerful tool for nanoparticle synthesis in general, and more specifically for ultrasmall nanoclusters (UNCs).

Developing a Millifluidic Platform for the Synthesis of Ultrasmall Nanoclusters: Ultrasmall Copper Nanoclusters as a Case Study.

L&#39;avenir des dispositifs lab-on-a-chip pour la synth&egrave;se de nanomat&eacute;riaux d&eacute;pend de la mise au point de m&eacute;thodes de haut d&eacute;bit avec le meilleur contr&ocirc;le sur leur taille. Alors que des efforts consid&eacute;rables dans cette direction se concentre principalement sur le d&eacute;veloppement de &laquo; difficiles &agrave; fabriquer &raquo; r&eacute;acteurs du complexe microfluides, peu d&#39;attention a &eacute;t&eacute; pay&eacute; aux syst&egrave;mes de millifluidic simple qui pourraient servir de contr&ocirc;le requis et le haut d&eacute;bit et &laquo; faciles &agrave; fabriquer &raquo;. En utilisant la simulation num&eacute;rique des fluides dans l&#39;espace millifluidic &agrave; diff&eacute;rents d&eacute;bits, les r&eacute;sultats pr&eacute;sent&eacute;s ici montrent r&eacute;sidence et les profils de vitesse distributions de temps comme dans le cas de la microfluidique. En r&eacute;duisant consid&eacute;rablement le temps de r&eacute;sidence et de la distribution de temps de r&eacute;sidence, une synth&egrave;se de l&#39;&eacute;coulement continu de nanoagr&eacute;gats cuivre ultrapetits (UCNCs) avec une exceptionnelle stabilit&eacute; collo&iuml;dale est atteint. Spectroscopie d&#39;absorption des rayons x synchrotron-radiation-based in situ (XAS) r&eacute;v&egrave;lent que les clusters comme pr&eacute;par&eacute;s sont &agrave; environ 1 nm, ce qui est encore attest&eacute; par microscopie &eacute;lectronique &agrave; transmission et &eacute;tudes de spectroscopie UV-visible. Les clusters rapport&eacute;s ici sont de la plus petite jamais produite &agrave; l&#39;aide d&#39;une plate-forme de lab-on-a-chip. Lorsque pris en charge sur silice, elles se trouvent &agrave; efficacement catalysent les r&eacute;actions d&#39;oxydation de C-H, jusque l&agrave; inconnues &agrave; &ecirc;tre catalys&eacute;e par Cu. Ce travail sugg&egrave;re qu&#39;une plate-forme de millifluidic peut &ecirc;tre un peu co&ucirc;teux, polyvalent, facile &agrave; utiliser et puissant outil pour la synth&egrave;se de nanoparticules en g&eacute;n&eacute;ral et plus particuli&egrave;rement pour les ultrapetits nanoclusters (UNC).

D&eacute;veloppement d&#39;une plateforme de Millifluidic pour la synth&egrave;se de nanoagr&eacute;gats ultrapetits : ultrapetits nanoagr&eacute;gats de cuivre comme &eacute;tude de cas.

Die Zukunft der Lab-on-a-Chip-Ger&auml;te f&uuml;r die Synthese von Nanomaterialien h&auml;ngt von der erfolgreichen Entwicklung von Hochdurchsatz-Methoden mit bessere Kontrolle &uuml;ber ihre Gr&ouml;&szlig;e. W&auml;hrend erhebliche Anstrengungen in diese Richtung konzentriert sich haupts&auml;chlich auf die Entwicklung von &quot;schwer zu fabrizieren&quot; komplexe mikrofluidische Reaktoren, hat kaum Aufmerksamkeit auf die &quot;leicht zu fabrizieren&quot; und einfache Millifluidic-Systeme, die die erforderliche Steuerung sowie hohen Durchsatz bieten k&ouml;nnte. Durch die Verwendung von numerischen Simulation von Fl&uuml;ssigkeiten innerhalb des Millifluidic bei verschiedenen Durchflussmengen, zeigen die Ergebnisse hier vorgestellten Velocity Profile und Wohnort Zeit Distributionen wie im Falle der Mikrofluidik. Durch die deutlich Verringerung der Verweilzeit und Residenz Zeitverteilung, wird eine kontinuierliche Synthese von ultrasmall Kupfer Nanoclustern (UCNCs) mit au&szlig;ergew&ouml;hnlichen kolloidale Stabilit&auml;t erreicht. In-Situ-Synchrotron-Strahlung-basierte x-ray Absorption Spectroscopy (XAS) zeigen, dass die Cluster als vorbereitete etwa 1 nm, die von Transmissionselektronenmikroskopie und UV-Vis Spektroskopie Studien weiter unterst&uuml;tzt wird. Die Cluster gemeldet, hier sind die kleinste jemals produziert mit eine Lab-on-a-Chip-Plattform. Als Kiesels&auml;ure unterst&uuml;tzt, fanden sie sind um C-H-Oxidationsreaktionen, bisher unbekannte, durch Cu katalysiert werden effizient zu katalysieren. Diese Arbeit schl&auml;gt vor, dass eine Millifluidic-Plattform eine kosteng&uuml;nstig, vielseitig, einfach zu bedienende und leistungsf&auml;hige Werkzeug f&uuml;r Nanopartikel-Synthese im allgemeinen und speziell f&uuml;r ultrasmall Nanoclustern (UNCs) sein kann.

Entwicklung einer Millifluidic-Plattform f&uuml;r die Synthese von Ultrasmall Nanoclustern: Ultrasmall Kupfer Nanoclustern als Fallstudie.

Il futuro dei dispositivi lab-on-a-chip per la sintesi dei nanomateriali cerniere sullo sviluppo di metodi di alto-rendimento con migliore controllo sulle loro dimensioni. Mentre lo sforzo significativo in questa direzione si concentra principalmente sullo sviluppo di reattori di microfluidica complesso &quot;difficile fabbricare&quot;, scarsa attenzione alla &quot;facile da fabbricare&quot; e sistemi di millifluidic semplice che potrebbero fornire il controllo richiesto come pure ad alto rendimento. Utilizzando la simulazione numerica dei fluidi all&#39;interno dello spazio millifluidic a diverse portate, i risultati presentati qui visualizza residence e profili di velocit&agrave; distribuzioni tempo simile al caso di microfluidica. Riducendo significativamente il tempo di permanenza e la distribuzione del tempo di residenza, una sintesi di flusso continuo di nanocluster rame ultracorte (UCNCs) con eccezionale stabilit&agrave; colloidale &egrave; raggiunto. In-situ basata su radiazioni di sincrotrone a raggi x spettroscopia di assorbimento (XAS) rivelano che i cluster come preparato sono circa 1 nm, che &egrave; ulteriormente sostenuto da microscopia elettronica di trasmissione e gli studi di Spettroscopia UV-vis. I cluster riportati qui sono la pi&ugrave; piccola mai prodotta utilizzando una piattaforma lab-on-a-chip. Quando supportato su silice, si trovano in modo efficiente catalizzano reazioni di ossidazione di C-H, fino ad allora sconosciute a essere catalizzata da Cu. Questo lavoro suggerisce che una piattaforma di millifluidic pu&ograve; essere uno strumento poco costoso, versatile, facile da usare e potente per la sintesi di nanoparticelle in generale e pi&ugrave; specificamente per questo nanocluster (UNC).

Lo sviluppo di una piattaforma di Millifluidic per la sintesi di nanocluster ultracorte: ultracorte nanocluster di rame come un caso di studio.

&#x30E9;&#x30DC; &#x30AA;&#x30F3;&#x30C1;&#x30C3;&#x30D7; &#x30C7;&#x30D0;&#x30A4;&#x30B9;&#x306E;&#x672A;&#x6765;&#x306E;&#x305F;&#x3081;&#x306E;&#x30CA;&#x30CE;&#x6750;&#x6599;&#x306E;&#x5408;&#x6210;&#x306F;&#x3001;&#x5F7C;&#x3089;&#x306E;&#x30B5;&#x30A4;&#x30BA;&#x3092;&#x5236;&#x5FA1;&#x9AD8;&#x30B9;&#x30EB;&#x30FC;&#x30D7;&#x30C3;&#x30C8;&#x65B9;&#x6CD5;&#x306E;&#x958B;&#x767A;&#x306B;&#x6210;&#x529F;&#x306B;&#x304B;&#x304B;&#x3063;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002;&#x3053;&#x306E;&#x65B9;&#x5411;&#x306B;&#x304B;&#x306A;&#x308A;&#x306E;&#x52B4;&#x529B;&#x306F;&#x4E3B;&#x306B;&#x300C;&#x96E3;&#x3057;&#x3044;&#x300D;&#x4F5C;&#x88FD;&#x3059;&#x308B;&#x8907;&#x96D1;&#x306A;&#x5FAE;&#x7D30;&#x6D41;&#x4F53;&#x30EA;&#x30A2;&#x30AF;&#x30BF;&#x30FC;&#x306E;&#x958B;&#x767A;&#x306B;&#x7126;&#x70B9;&#x3092;&#x5F53;&#x3066;&#x306A;&#x304C;&#x3089;&#x3001;&#x308F;&#x305A;&#x304B;&#x306A;&#x300C;&#x7C21;&#x5358;&#x4F5C;&#x88FD;&#x3059;&#x308B;&#x300D;&#x3068;&#x9AD8;&#x30B9;&#x30EB;&#x30FC;&#x30D7;&#x30C3;&#x30C8;&#x3060;&#x3051;&#x3067;&#x306A;&#x304F;&#x3001;&#x5FC5;&#x8981;&#x306A;&#x30B3;&#x30F3;&#x30C8;&#x30ED;&#x30FC;&#x30EB;&#x3092;&#x63D0;&#x4F9B;&#x3059;&#x308B;&#x3053;&#x3068;&#x304C;&#x3067;&#x304D;&#x308B;&#x30B7;&#x30F3;&#x30D7;&#x30EB;&#x306A; millifluidic &#x30B7;&#x30B9;&#x30C6;&#x30E0;&#x306B;&#x6CE8;&#x76EE;&#x3055;&#x308C;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002;&#x7570;&#x306A;&#x308B;&#x30D5;&#x30ED;&#x30FC; &#x30EC;&#x30FC;&#x30C8;&#x3067; millifluidic &#x30B9;&#x30DA;&#x30FC;&#x30B9;&#x5185;&#x306E;&#x6D41;&#x4F53;&#x306E;&#x6570;&#x5024;&#x30B7;&#x30DF;&#x30E5;&#x30EC;&#x30FC;&#x30B7;&#x30E7;&#x30F3;&#x3092;&#x6D3B;&#x7528;&#x3057;&#x3066;&#x3001;&#x3053;&#x3053;&#x306B;&#x63D0;&#x793A;&#x7D50;&#x679C;&#x6D41;&#x901F;&#x5206;&#x5E03;&#x3068;&#x30EC;&#x30B8;&#x30C7;&#x30F3;&#x30B9;&#x6642;&#x9593;&#x5206;&#x5E03;&#x30DE;&#x30A4;&#x30AF;&#x30ED;&#x6D41;&#x4F53;&#x306E;&#x5834;&#x5408;&#x3068;&#x540C;&#x69D8;&#x306B;. &#x3057;&#x307E;&#x3059;&#x3002;&#x5927;&#x5E45;&#x306B;&#x6EDE;&#x7559;&#x6642;&#x9593;&#x3068;&#x6EDE;&#x7559;&#x6642;&#x9593;&#x5206;&#x5E03;&#x3092;&#x6E1B;&#x3089;&#x3059;&#x3053;&#x3068;&#x306B;&#x3088;&#x3063;&#x3066;&#x3001;&#x4F8B;&#x5916;&#x7684;&#x306A;&#x30B3;&#x30ED;&#x30A4;&#x30C9;&#x5B89;&#x5B9A;&#x6027;&#x3068;&#x6975;&#x7D30;&#x9285;&#x30CA;&#x30CE;&#x30AF;&#x30E9; &#x30B9;&#x30BF;&#x30FC; (UCNCs) &#x306E;&#x9023;&#x7D9A;&#x30D5;&#x30ED;&#x30FC;&#x5408;&#x6210;&#x3092;&#x5B9F;&#x73FE;&#x3057;&#x307E;&#x3059;&#x3002;In-situ &#x30B7;&#x30F3;&#x30AF;&#x30ED;&#x30C8;&#x30ED;&#x30F3;&#x7167;&#x5C04;&#x3092;&#x7528;&#x3044;&#x305F; x &#x7DDA;&#x5438;&#x53CE;&#x5206;&#x5149; (XAS) &#x3092;&#x660E;&#x3089;&#x304B;&#x306B;&#x6E96;&#x5099;&#x3068;&#x3057;&#x3066;&#x30AF;&#x30E9;&#x30B9;&#x30BF;&#x30FC;&#x7D04; 1 &#x3067;&#x3042;&#x308B;&#x3053;&#x3068; nm &#x306F;&#x3001;&#x3055;&#x3089;&#x306B;&#x900F;&#x904E;&#x578B;&#x96FB;&#x5B50;&#x9855;&#x5FAE;&#x93E1;&#x3068;&#x7D2B;&#x5916;&#x53EF;&#x8996;&#x5206;&#x5149;&#x7814;&#x7A76;&#x306B;&#x3088;&#x3063;&#x3066;&#x30B5;&#x30DD;&#x30FC;&#x30C8;&#x3055;&#x308C;&#x3066;&#x3044;&#x307E;&#x3059;&#x3002;&#x3053;&#x3053;&#x3067;&#x306F;&#x3001;&#x6700;&#x5C0F;&#x307E;&#x3067;&#x30E9;&#x30DC;-&#x30AA;&#x30F3;-&#x30C1;&#x30C3;&#x30D7; &#x30D7;&#x30E9;&#x30C3;&#x30C8;&#x30D5;&#x30A9;&#x30FC;&#x30E0;&#x3092;&#x4F7F;&#x7528;&#x3057;&#x3066;&#x751F;&#x7523;&#x30AF;&#x30E9;&#x30B9;&#x30BF;&#x30FC;&#x3092;&#x5831;&#x544A;&#x3057;&#x307E;&#x3057;&#x305F;&#x3002;&#x30B7;&#x30EA;&#x30AB;&#x306B;&#x62C5;&#x3055;&#x308C;&#x308B;&#x3068;&#x304D;&#x3001;&#x5F7C;&#x3089;&#x306F;&#x52B9;&#x7387;&#x7684;&#x306B; Cu &#x306B;&#x3088;&#x3063;&#x3066;&#x89E6;&#x5A92;&#x3055;&#x308C;&#x308B;&#x672A;&#x77E5; C-H &#x9178;&#x5316;&#x53CD;&#x5FDC;&#x306E;&#x89E6;&#x5A92;&#x306B;&#x767A;&#x898B;&#x3055;&#x308C;&#x307E;&#x3059;&#x3002;&#x3053;&#x306E;&#x4F5C;&#x696D;&#x3067;&#x306F;&#x3001;millifluidic &#x30D7;&#x30E9;&#x30C3;&#x30C8;&#x30D5;&#x30A9;&#x30FC;&#x30E0;&#x4E00;&#x822C;&#x7684;&#x306B;&#x3001;&#x30CA;&#x30CE;&#x7C92;&#x5B50;&#x5408;&#x6210;&#x3068;&#x6975;&#x5C0F;&#x30CA;&#x30CE;&#x30AF;&#x30E9; &#x30B9;&#x30BF;&#x30FC; (Unc) &#x3092;&#x3088;&#x308A;&#x5177;&#x4F53;&#x7684;&#x306B;&#x306F;&#x3001;&#x5B89;&#x4FA1;&#x306A;&#x6C4E;&#x7528;&#x6027;&#x306E;&#x9AD8;&#x3044;&#x3001;&#x4F7F;&#x3044;&#x3084;&#x3059;&#x3044;&#x3001;&#x5F37;&#x529B;&#x306A;&#x30C4;&#x30FC;&#x30EB;&#x3067;&#x3042;&#x308B;&#x3053;&#x3068;&#x304C;&#x793A;&#x5506;&#x3055;&#x308C;&#x307E;&#x3057;&#x305F;&#x3002;

&#x6975;&#x5C0F;&#x30CA;&#x30CE;&#x30AF;&#x30E9; &#x30B9;&#x30BF;&#x30FC;&#x306E;&#x5408;&#x6210;&#x306E;&#x305F;&#x3081;&#x306E; Millifluidic &#x30D7;&#x30E9;&#x30C3;&#x30C8;&#x30D5;&#x30A9;&#x30FC;&#x30E0;&#x306E;&#x958B;&#x767A;: &#x6975;&#x7D30;&#x9285;&#x30CA;&#x30CE;&#x30AF;&#x30E9; &#x30B9;&#x30BF;&#x30FC;&#x3092;&#x30B1;&#x30FC;&#x30B9;&#x30B9;&#x30BF;&#x30C7;&#x30A3;&#x3068;&#x3057;&#x3066;&#x3002;

&#xB098;&#xB178; &#xC18C;&#xC7AC; &#xD569;&#xC131;&#xC744; &#xC704;&#xD55C; &#xB7A9; &#xC628; &#xCE69; &#xB514;&#xBC14;&#xC774;&#xC2A4;&#xC758; &#xBBF8;&#xB798;&#xB294; &#xADF8;&#xB4E4;&#xC758; &#xD06C;&#xAE30;&#xC5D0; &#xB354; &#xB098;&#xC740; &#xD1B5;&#xC81C;&#xC640; &#xB192;&#xC740; &#xCC98;&#xB9AC;&#xB7C9; &#xBC29;&#xBC95;&#xC758; &#xC131;&#xACF5;&#xC801;&#xC778; &#xAC1C;&#xBC1C;&#xC5D0; &#xACBD;&#xCCA9;. &#xC0C1;&#xB2F9;&#xD55C; &#xB178;&#xB825;&#xC744;&#xC774; &#xBC29;&#xD5A5;&#xC73C;&#xB85C; &#xC8FC;&#xB85C; &quot;&#xC870;&#xC791; &#xD558;&#xAE30; &#xC5B4;&#xB824;&#xC6B4;&quot; &#xBCF5;&#xC7A1; &#xD55C; &#xBBF8;&#xC138; &#xC6D0;&#xC790;&#xB85C; &#xAC1C;&#xBC1C;&#xC5D0; &#xCD08;&#xC810;&#xC744; &#xB9DE;&#xCD94;&#xACE0;, &#xD558;&#xB294; &#xB3D9;&#xC548; &#xBD80;&#xC871; &#xD55C; &#xAD00;&#xC2EC; &quot;&#xC744; &#xC870;&#xC791; &#xD558;&#xAE30; &#xC26C;&#xC6B4;&quot; &#xD558; &#xACE0; &#xD544;&#xC694;&#xD55C; &#xC81C;&#xC5B4; &#xBFD0;&#xB9CC; &#xC544;&#xB2C8;&#xB77C; &#xB192;&#xC740; &#xCC98;&#xB9AC;&#xB7C9;&#xC744; &#xC81C;&#xACF5;&#xD560; &#xC218; &#xC788;&#xB294; &#xAC04;&#xB2E8;&#xD55C; millifluidic &#xC2DC;&#xC2A4;&#xD15C; &#xC9C0;&#xAE09; &#xB418;&#xC5C8;&#xC2B5;&#xB2C8;&#xB2E4;. &#xB2E4;&#xB978; &#xD750;&#xB984; &#xC18D;&#xB3C4;&#xC5D0;&#xC11C; millifluidic &#xACF5;&#xAC04; &#xB0B4;&#xC5D0;&#xC11C; &#xCCB4;&#xC561;&#xC758; &#xC2DC;&#xBBAC;&#xB808;&#xC774;&#xC158;&#xC744; &#xC774;&#xC6A9; &#xD558; &#xC5EC; &#xC5EC;&#xAE30;&#xC5D0; &#xC81C;&#xC2DC; &#xB41C; &#xACB0;&#xACFC; &#xD45C;&#xC2DC; &#xC18D;&#xB3C4; &#xD504;&#xB85C;&#xD544; &#xBC0F; &#xCCB4;&#xB958; &#xC2DC;&#xAC04; &#xBC30;&#xD3EC;&#xD310; microfluidics&#xC758; &#xACBD;&#xC6B0;&#xC640; &#xBE44;&#xC2B7;&#xD569;&#xB2C8;&#xB2E4;. &#xCCB4;&#xB958; &#xC2DC;&#xAC04; &#xBC0F; &#xCCB4;&#xB958; &#xC2DC;&#xAC04; &#xBD84;&#xD3EC;&#xB97C; &#xD06C;&#xAC8C; &#xAC10;&#xC18C; &#xC2DC;&#xD0A4;&#xB294; &#xB6F0;&#xC5B4;&#xB09C; &#xCF5C; &#xB85C;&#xC774;&#xB4DC; &#xC548;&#xC815;&#xC131;&#xACFC; ultrasmall &#xAD6C;&#xB9AC; nanoclusters (UCNCs)&#xC758; &#xC5F0;&#xC18D; &#xD750;&#xB984; &#xD569;&#xC131;&#xC774; &#xC774;&#xB8E8;&#xC5B4;&#xC9D1;&#xB2C8;&#xB2E4;. -&#xD574; &#xB77C; synchrotron &#xBC29;&#xC0AC;&#xC120; &#xAE30;&#xBC18; x-&#xC120; &#xD761;&#xC218; &#xBD84;&#xAD11;&#xD559; (XAS) &#xACF5;&#xAC1C;&#xB85C; &#xC900;&#xBE44; &#xB41C; &#xD074;&#xB7EC;&#xC2A4;&#xD130;&#xB294; &#xC57D; 1 nm, &#xC804;&#xC1A1; &#xC804;&#xC790; &#xD604;&#xBBF8;&#xACBD; &#xAC80;&#xC0AC; &#xBC95; &#xBC0F; UV-&#xB9C8;&#xC8FC; &#xBD84;&#xAD11;&#xD559; &#xC5F0;&#xAD6C; &#xC9C0;&#xC6D0; &#xCD94;&#xAC00;. &#xD074;&#xB7EC;&#xC2A4;&#xD130; &#xBCF4;&#xACE0; &#xC5EC;&#xAE30; &#xC791;&#xC740; &#xC801; &#xB7A9; &#xC628; &#xCE69; &#xD50C;&#xB7AB;&#xD3FC;&#xC744; &#xC0AC;&#xC6A9; &#xD558; &#xC5EC; &#xC0DD;&#xC131; &#xB429;&#xB2C8;&#xB2E4;. &#xC2E4;&#xB9AC; &#xCE74;&#xC5D0; &#xC9C0;&#xC6D0;, &#xADF8;&#xB4E4;&#xC740; &#xD6A8;&#xC728;&#xC801;&#xC73C;&#xB85C; Cu&#xC5D0; &#xC758;&#xD574; &#xCD09;&#xB9E4;&#xC5D0; &#xC9C0;&#xAE08;&#xAE4C;&#xC9C0; &#xC54C;&#xB824;&#xC9C0;&#xC9C0; &#xC54A;&#xC740; C H &#xC0B0;&#xD654; &#xBC18;&#xC751; &#xCD09;&#xB9E4;&#xB97C; &#xCC3E;&#xC744; &#xC218; &#xC788;&#xC2B5;&#xB2C8;&#xB2E4;. &#xC774; &#xC791;&#xD488; &#xC81C;&#xC548; millifluidic &#xD50C;&#xB7AB;&#xD3FC; ultrasmall nanoclusters (Unc) &#xC880; &#xB354; &#xAD6C;&#xCCB4;&#xC801;&#xC73C;&#xB85C; &#xC77C;&#xBC18;&#xC801;&#xC73C;&#xB85C; &#xB098;&#xB178; &#xC785;&#xC790; &#xD569;&#xC131; &#xBC0F; &#xC800;&#xB834; &#xD55C;, &#xB2E4;&#xC7AC; &#xB2E4;&#xB2A5; &#xD55C;, &#xC0AC;&#xC6A9; &#xD558;&#xAE30; &#xC26C;&#xC6B4;, &#xADF8;&#xB9AC;&#xACE0; &#xAC15;&#xB825;&#xD55C; &#xB3C4;&#xAD6C;&#xB97C; &#xC218; &#xC788;&#xC2B5;&#xB2C8;&#xB2E4;.

Ultrasmall Nanoclusters&#xC758; &#xD569;&#xC131;&#xC744; &#xC704;&#xD55C; Millifluidic &#xD50C;&#xB7AB;&#xD3FC; &#xAC1C;&#xBC1C;: &#xC0AC;&#xB840; &#xC5F0;&#xAD6C;&#xB85C; Ultrasmall &#xAD6C;&#xB9AC; Nanoclusters.

El futuro de los dispositivos de lab-on-a-chip para la s&iacute;ntesis de nanomateriales se basa en el desarrollo de m&eacute;todos de alto rendimiento con un mayor control sobre su tama&ntilde;o. Mientras que un esfuerzo importante en esta direcci&oacute;n se centra principalmente en el desarrollo de reactores de microfluidos complejo &quot;dif&iacute;cil de fabricar&quot;, se ha prestado poca atenci&oacute;n a la &quot;f&aacute;cil fabricar&quot; y sistemas de millifluidic simple que podr&iacute;an proporcionar el control necesario as&iacute; como alto rendimiento. Mediante la utilizaci&oacute;n de simulaci&oacute;n num&eacute;rica de fluidos dentro del espacio de millifluidic en caudales diferentes, los resultados aqu&iacute; presentados muestran residencia y perfiles de velocidad distribuciones de tiempo similar al caso de la microflu&iacute;dica. Reduciendo significativamente el tiempo de permanencia y distribuci&oacute;n del tiempo de residencia, se logra una s&iacute;ntesis de flujo continuo de nanoclusters cobre peque&ntilde;o (UCNCs) con una excepcional estabilidad coloidal. &quot;In-situ&quot; basadas en radiaci&oacute;n sincrotr&oacute;n radiograf&iacute;a espectroscopia de absorci&oacute;n (XAS) revelan que los clusters como preparados son aproximadamente 1 nm, que es apoyado por microscop&iacute;a electr&oacute;nica de transmisi&oacute;n y estudios de espectroscopia UV-vis. Los grupos registrados aqu&iacute; son el m&aacute;s peque&ntilde;o jam&aacute;s fabricado utilizando una plataforma de lab-on-a-chip. Cuando est&aacute; apoyado en s&iacute;lice, se encuentran eficientemente catalizar reacciones de oxidaci&oacute;n del C-H, hasta ahora desconocidas a ser catalizadas por Cu. Este trabajo sugiere que una plataforma de millifluidic puede ser una herramienta barata, vers&aacute;til, f&aacute;cil de usar y potente para la s&iacute;ntesis de nanopart&iacute;culas en general y m&aacute;s espec&iacute;ficamente para ultrapeque&ntilde;o nanoclusters (UNC).

Desarrollo de una plataforma de Millifluidic para la s&iacute;ntesis de Nanoclusters ultrapeque&ntilde;o: peque&ntilde;o Nanoclusters cobre como caso de estudio.

We report the use of small molecule and block copolymer RGD peptide conjugates for deep ex vivo imaging of tumor vasculature in "whole" excised tumors using two-photon fluorescence microscopy (2PFM). The fluorescent probes were administered to mice via tail-vein injection, after which the tumors were excised, fixed, and imaged without further sample preparation. Both RGD conjugates demonstrated specific targeting to tumor blood vessels, and this selectivity imparted excellent contrast in 2PFM micrographs that captured high-resolution 3-D images of the tumor vasculature up to depths of 830 μm in Lewis Lung Carcinoma (LLC) tumors. 2PFM ex vivo fluorescence micrographs clearly revealed tumor vessels, while differences in the sensitivity of tumor vessel imaging were apparent between the small molecule and block copolymer conjugates. Both the small molecule and polymer-based two-photon absorbing probe conjugate are valuable for deep tissue tumor microvasculature imaging.

Small molecule fluorophore and copolymer RGD peptide conjugates for ex vivo two-photon fluorescence tumor vasculature imaging.

Innovative in situ characterization tools are essential for understanding the reaction mechanisms leading to the growth of nanoscale materials. Though techniques, such as in situ transmission X-ray microscopy, fast single-particle spectroscopy, small-angle X-ray scattering, etc., are currently being developed, these tools are complex, not easily accessible, and do not necessarily provide the temporal resolution required to follow the formation of nanomaterials in real time. Here, we demonstrate for the first time the utility of a simple millifluidic chip for an in situ real time analysis of morphology and dimension-controlled growth of gold nano- and microstructures with a time resolution of 5 ms. The structures formed were characterized using synchrotron radiation-based in situ X-ray absorption spectroscopy, 3-D X-ray tomography, and high-resolution electron microscopy. These gold nanostructures were found to be catalytically active for conversion of 4-nitrophenol into 4-aminophenol, providing an example of the potential opportunities for time-resolved analysis of catalytic reactions. While the investigations reported here are focused on gold nanostructures, the technique can be applied to analyze the time-resolved growth of other types of nanostructured metals and metal oxides. With the ability to probe at least a 10-fold higher concentrations, in comparison with traditional microfluidics, the tool has potential to revolutionize a broad range of fields from catalysis, molecular analysis, biodefense, and molecular biology.

Sanchita Biswas

Center for Advanced Microstructures and Devices (CAMD),
Center for Atomic-Level Catalyst Design,
Cain Department of Chemical Engineering,
Center for Atomic-Level Catalyst Design, Cain Department of Chemical Engineering

Louisiana State University

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Sanchita Biswas

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Center for Advanced Microstructures and Devices (CAMD),Center for Atomic-Level Catalyst Design,Cain Department of Chemical Engineering,Center for Atomic-Level Catalyst Design, Cain Department of Chemical Engineering

Louisiana State University

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Center for Advanced Microstructures and Devices (CAMD),
Center for Atomic-Level Catalyst Design,
Cain Department of Chemical Engineering,
Center for Atomic-Level Catalyst Design, Cain Department of Chemical Engineering