This research was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canada Research Chairs Program, and Simon Fraser University. This work made use of 4D LABS shared facilities supported by the Canada Foundation for Innovation (CFI), British Columbia Knowledge Development Fund (BCKDF) and Simon Fraser University.

NaYF 4 / Yb 3+ / Er 3+ upconverting Nanopartiküller (UCNP) 1. sentezi <ol><li> Olarak takip cihazı ayarlayın: <ol><li> Düzenli karıştırma plaka üzerinde 250 ml&#39;lik bir ısıtma manto yerleştirin ve termal çift üzerine manto takın. </li><li> Uygun olarak tespit ısıtma mantosu üzerine bir manyetik karıştırma çubuğu ile donatılmış bir 250 ml&#39;lik yuvarlak tabanlı bir şişeye koyun. </li><li> Yuvarlak dipli sol boyun hava adaptörünü ve plastik boru ile savurma hattına bu hava adaptörünü bağlayın. </li><li> Yuvarlak dipli sağ boyun cam adaptörünü ve cam adaptör üzerine bir termometre adaptörünü sabitleyin. Termometre adaptörü ile balona sıcaklık probu yerleştirin ve termokupl içine bu takın. </li><li> Yuvarlak tabanlı şişenin orta boynunun bir damıtma kafası takın. Damıtma kafası üzerine bir stoper yerleştirin. Bir vakum distillat ardından bir kondansatör kafa bağlayınİyon adaptörü ve 50 ml&#39;lik yuvarlak tabanlı bir şişeye. Plastik boru aracılığıyla kabarcık Vakum damıtma adaptörünü bağlayın. </li></ol></li><li> Itriyum asetat 1.17 g (3.9 mmol), iterbiyum asetat 0.439 g ve erbiyum asetat 0,0727 g (0.1 mmol) tartılır ve yuvarlak dipli bir deney kabına reaksiyona koyun. </li><li> Oleik asit 30 ml ve bir dereceli silindir kullanarak şişeye -oktadesene 75 ml ekleyin. </li><li> 5 ml metanol herhangi bir oleik asit, ve oktadesen reaksiyon şişesine kenarlarına yapışmış olduğundan emin olmak için, kullanılarak yuvarlak tabanlı reaksiyonun yan durulayın. </li><li> Çift manifoldu Schlenk hattına tepki şişeyi bağlayın ve azot hattına bağlı reaksiyon şişesi tutmak için gelen vanayı çevirin. </li><li> , Termokupl açın 80 ° C sıcaklığı ayarlamak ve yavaş yavaş, bu sıcaklıkta, sistemi ısıtın. Tüm başlangıç ​​materyalleri eritilir sonra 80 ° C&#39;de ve, ısıtma gömleğinin kaldırmak ve reaksiyona olanak vermek30 ° C&#39;ye kadar soğutun. </li><li> Sıcaklık 30 ° C&#39;ye ulaştığında, damıtma kafasını çıkarmak orta boyun sol boyun hava adaptörünü geçiş ve bir tıpa ile sol boyun kapatmaktadır. Yavaşça vakum hattına azot hattından savurma hattında vana çevirerek reaksiyon balonuna vakum tanıtmak. Düşük kaynama noktalı bileşenlerin tümü, bu noktada reaksiyondan üzerinden çekilir. </li><li> Çözelti köpüren durduğunda, 5 ° C / dk bir hızda, 115 ° C sıcaklık yükseltmek. </li><li> Sıcaklık 115 ° C&#39;ye ulaştığında, 15 dakika boyunca bu sıcaklıkta muhafaza daha sonra ısıtma mantosu çıkarın ve 50 ° C&#39;de reaksiyonun soğuması. Daha sonra, hızlı bir şekilde orta boyun ve sol baş hava adaptörü damıtma kafa reattaching geri orijinal formuna kurmak geçin. </li><li> Soğutma işlemi sırasında NaOH 0.74 g (12.5 mmol) ve NH4 F 0.50 g (20.0 mmol) tartılır ve bunları çözmeksonikasyon ile metanol içinde 50 ml. </li><li> Sonikasyon sonrasında, yuvarlak tabanlı reaksiyona girerek çözelti dökün ve 5 ml MeOH ile Şişenin yanlarının yıkayın. </li><li> 30 dakika boyunca 50 ° C de karıştırılarak çözelti bırakın. </li><li> Metanol damıtmak için 75 ° C sıcaklık artırır. </li><li> Gerektiğinde damıtma sırasında, toplama şişesi boşaltın. Damıtma işlemi bittikten sonra, mümkün olduğunca hızlı azot koruması altında 300 ° C&#39;ye tepki ısınır. </li><li> Sıcaklık 300 ° C&#39;ye ulaştığında, 1 saat boyunca bu sıcaklıkta muhafaza. Gerekirse, sıcaklık korumaya yardımcı olmak için alüminyum folyo ile setup kapsamaktadır. Daha sonra ısı kaynağı çıkarın ve reaksiyon, oda sıcaklığına kadar soğumaya bırakın. </li><li> Bu sırada oda sıcaklığına kadar soğutuldu sonra üç santrifüj tüpleri (50 mi borular, her bir tüp başına yaklaşık 35 ml solüsyon) içinde eşit bir şekilde çözelti ayrıldı ve 50 ml üst borusunu, susuz etanol kullanılarak ölçek. Santrifüj tüm tO 15 dakika 3400 xg&#39;de borular. Santrifüj işleminden sonra, beyaz bir çökelti UCNPs tüplerin tarafında gözlenmelidir. </li><li> Süpernatant atılır ve heksan (her tüp için heksan 7.5 ml) &#39;de UCNPs pelet yeniden disperse, daha sonra 50 ml ölçekli etanol ile tüp doldurun. Santrifüj tüpleri tekrar 15 dakika 3400 xg&#39;de. </li><li> Santrifüj işlemi tamamlandıktan sonra, süpernatan atılır ve daha sonra kullanılmak üzere CHCI3 30 ml bir katı UCNPs yeniden disperse. </li></ol> Organik boya molekülünü ve upconverting Nanopartiküller İçeren 2. Montaj suda dağılabilir Nanoassemblies <ol><li> Bir manyetik karıştırma çubuğu ile donatılmış bir ışıldama şişesine boşaltıldı CHCI3 3 ml poli (stiren-alt -maleik anhidrid), 25 mg (0,0147 mmol), (PSMA) içinde çözülür. Bu miktar birden denemeden sonra optimize edilmiş miktardır. </li><li> Upconverting 250 ul (47 mg / ml) ilave edilir taraması yapmak üzere kloroform stok solüsyonu nanopartiküllerillation şişe. </li><li> Kapatılır ve manyetik bir karıştırma levhasının üzerine yerleştirin ve 2 saat boyunca oda sıcaklığında çözelti karıştırılır. </li><li> 2070 amin polieter 160 mg (0,0773 mmol) tartılır ve CHCI3 1 ml içinde çözülür. Daha sonra, bir pipet kullanılarak, bir kısım halinde sintilasyon şişesine, bu çözüm ekleyin. Çözelti PSMA üzerinde anhidrit grupları ile 2070 amin polieter tepkisini gösteren sarı soluk dönecek. </li><li> Gece boyunca oda sıcaklığında çözelti karıştırılmaya devam edin. </li><li> 1 saat süre ile karıştırıldı, elde edilen çözeltinin, daha sonra organik boya moleküllerinin uygun miktarda ölçün bir kısım halinde sintilasyon şişesine içine dağıtın. <ol><li> Örnek TPP-NP (nanoassembly polimer kabuk, tetrafenil porfirin ve upconverting nanopartikülleri içeren) için, doğrudan olarak ışıldama şişesine tetrafenil porfirinin 1 mg ekleyin. Örnek DAE-UCNP (nanoassembly için polimer kabuk, diarylethene molekülleri ve upconverting nanoparçacık içerens), her bir diarylethene moleküllerinin miktarı 2 x 10 -7 mol. Reaksiyon çözeltisi içine, iki diarylethene molekülleri ekleyin. İki diarylethene moleküller için hacimleri: DAE-1o (1.8 mM), 111 ul ve DAE-2O (1.6 mM), 125 ul. </li></ol></li><li> Bir döner buharlaştırıcı kullanılarak indirgenmiş basınç altında çözücüyü çıkarın CHCI3, sonra sütümsü süspansiyon meydana getirilinceye kadar, sonra flakon sonikasyon, sintilasyon şişesine 3 mL (11 pH ≈) M sulu NaOH 0,001 ekleyin. </li><li> Geri dönüşlü buharlaştırıcı ile şişe yerleştirin ve süspansiyon daha berrak bir solüsyona dönüştü kadar dikkatlice geri kalan CHCl3 çıkarın. </li><li> Daha sonra 25 dakika boyunca 20.600 xg&#39;de çözüm santrifüj, iki adet 1,5 ml&#39;lik konik santrifüj tüplerine sintilasyon şişeden çözüm aktarın. </li><li> Süpernatant atılır, daha sonra, iki tüp (tüp başına 1,5 mi) içine deiyonize H2O 3 ml toplam eklemek peletler yeniden dağıtmak için tüpler sonikasyondeiyonize H 2 O. </li><li> 25 dakika boyunca 20.600 x g hızında tekrar santrifüj iki boruyu. </li><li> Süpernatant atılır, daha sonra iki tüp (tüp başına 1.5 mi) içinde deiyonize H2O 3 ml toplam ekleyin. Deiyonize H2O pelet yeniden dağıtmak için tüpler sonikasyon </li><li> Ileri testler için son örneği elde etmek için bir 0.2 mikron bir şırınga filtreden geçirilmiştir sulu bir dispersiyon örneği nanopartiküller filtre. </li></ol>

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The authors have nothing to disclose.

Bu protokole uygun olarak sentez nanopartiküller Bir α-NaYF 4 ev sahibi kafes yapısı ile küresel parçacıklar olarak sınıflandırılabilir yaklaşık 22,5 nm. 26,27 merkezli 20 25 nm arasında bir boyut dağılımına sahiptir. Bu protokolde iki kritik adımlar vardır. UCNP sentezinde, bu parçacık boyutunun dar bir dağılımı sağlamak için mümkün olduğu kadar kesin bir ısıtma sıcaklığı ve zamanı sağlamak için çok önemlidir. Iyi dağıtılmış boyut ve iyi bir morfoloji...

Bugün biyo-görüntüleme ajanları yeni türleri geliştirmek için acil ihtiyaç duyulmaktadır. Birçok roman floresan probları iyi belgelenmiştir. 1-6 Ancak, görüntü çözünürlüğü önemli gelişmeler bir sorun olmaya devam etmektedir. 7 Tek pratik yöntem, doğrudan bir &#39;hafif&#39; yayan devlet ve &#39;karanlık&#39; söndürüldü devlet arasındaki floresan probları modüle etmektir. 8-12 Bu özel yöntem, uyarılmış emisyon tükenmesi gibi teknolojileri geliştirmek için uygulanmıştır (STED) mikroskopi 13 ve stokastik optik rekonstrüksiyon mikroskobu (FIRTINA). 14 Floresan modüle için başka bir yaklaşım, floresan probları ile birlikte bir çift ışığa cevap kromoforlar etmektir. 15,16 izomerlerden sadece birisinin etkin bir enerji aktarma alıcısı olarak hareket edebilen iki izomer arasındaki ışığa cevap kromofor geçiş yapılması, th flüoresanının söndürülmesi üzerinde kontrole olanak sağlamaktadırFörster Rezonans Enerji Transferi (FRET) ve diğer mekanizmalar aracılığıyla e prob. Sonuç bir emisyonlu devleti oluşturma ve ışığın farklı dalga boylarında ışığa cevap kromoforun maruz kalarak dönüşümlü edilebilir söndürüldü devlettir. Işığa diarylethene kromoforlar tersine çevrilebilir renksiz halka açık izomeri ve UV ve görünür ışık ile ışınlama üzerine renkli halka kapalı izomeri arasında geçiş yapılabilir. 17-19 halka kapalı izomer make iki izomer ve ayarlanabilir emme spektrumları termal stabilitesi diarylethenes çok iyi aday kontrol FRET alıcıları olarak. 20-23 lantanid katkılı NaYF 4 upconverting nanopartiküller biyo-görüntüleme için faydalıdır. 24 Bu nanopartiküller yakın kızılötesi ışık emer ve görünür spektrum çeşitli bölgelerinde ışık yayar. Işığa cevap diarylethene kromoforları ve nano-parçacıkları birleştirerek floresans modülasyon örnekleri önceden edilmiştirbir önce grubumuz tarafından rapor edilmiştir. 25-27 Bununla birlikte, her örnek için tarif sistemler daha çeşitli sistemlerin geliştirilmesini zorlaştırmaktadır nanopartiküllerin yüzeyine diarylethenes takmak için bir ek sentetik modifikasyon gerekli. Bu yazıda kendi kendine montaj stratejisi kullanılarak suda dağılabilir organik boya molekülleri ve ışığa cevap upconverting nanopartiküller hazırlamak için basit bir &#39;tak-çalıştır&#39; yöntemini göstermektedir. Polimerlerin seçimi; 2070 amin poli (stiren-alt -maleik anhidrid) ve polieter hidrofobik ve hidrofilik bir ortam hem de sağlar. Polimerin hidrofilik bölgesi suda çözünürlüğe muhafaza edilmesi için önemli ise, polimer yardımıyla hidrofobik bölümler, birbirine normal suda çözünür olmayan organik moleküller ve upconverting nanopartikülleri tutun. Biz ilk termal çekirdeklenme yöntemiyle upconverting nanopartiküllerin sentezi gösterecektir. Sonra, biz ho ispat edecektirOrganik moleküller ve upconverting nanopartiküller polimer kabuk hidrofobik bölgeler içinde kapsüllenmiş ve basit uygun bir çalışma prosedüreüne ardından upconverting nanopartiküller, polimer ve farklı organik boya molekülleri ihtiva eden bir çözelti, co-karıştırılarak sulu ortam içinde sabit kalması w. Biz de dış ışık ışıması kullanılarak meclislerinin floresan emisyonunu modüle nasıl gösterilmektedir. Biz suda dağılabilir nanoassemblies genişletmeye devam edeceğiz yapmak için bu &#39;tak-çalıştır&#39; yöntemini kullanarak kapsamını tahmin.

<table><tbody><tr><td>Yttrium acetate</td><td>Sigma</td><td>326046</td><td>Yttrium(III) acetate hydrate</td></tr><tr><td>Ytterbium acetate</td><td>Sigma</td><td>544973</td><td>Ytterbium(III) acetate hydrate</td></tr><tr><td>Erbium acetate</td><td>Sigma</td><td>325570</td><td>Erbium(III) acetate hydrate</td></tr><tr><td>Oleic acid</td><td>Sigma</td><td>75096</td><td>analytical standard</td></tr><tr><td>Octadecene</td><td>Sigma</td><td>O806</td><td>Technical grade</td></tr><tr><td>NaOH</td><td>Sigma</td><td>S5881</td><td>reagent grade</td></tr><tr><td>NH&lt;sub&gt;4&lt;/sub&gt;F</td><td>Sigma</td><td>216011</td><td>ACS reagent</td></tr><tr><td>Poly(styrene-co-maleic anhydride)</td><td>Sigma</td><td>442399</td><td>Average Mn = 1700</td></tr><tr><td>JeffAmine 2070</td><td>Huntsman</td><td>M-2070</td><td></td></tr><tr><td>Varian Carry 300</td><td>Agilent</td><td></td><td></td></tr><tr><td>JDSU NIR laser</td><td>JSDU</td><td>L4-9897510-100M</td><td>980 nm diode laser</td></tr></tbody></table>

a 'plug and play' method to create water-dispersible nanoassemblies containing an amphiphilic polymer, organic dyes and upconverting nanoparticles

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate amphiphilic polymers in situ, and describe a protocol to encapsulate the prepared UCNPs and different organic dye molecules (porphyrins and diarylethenes) using polymer shells to form stable water-dispersible nanoassemblies. The nanoassembly samples containing both the UCNPs and the diarylethene organic dyes have interesting photochemical and photophysical properties. Upon 365 nm UV irradiation, the diarylethene group undergoes a visual color change. When the samples are irradiated with visible light of another specific wavelength, the color fades and the samples return to the initial colorless state. The samples also emit visible light from the UCNPs upon irradiation with 980 nm near-infrared light. The emission intensity of the samples can be tuned through alternate irradiation with UV and visible light. Modulation of fluorescence can be performed for many cycles without observable degradation of the samples. This versatile encapsulation procedure allows for the transfer of hydrophobic molecules and nanoparticles from an organic solvent to an aqueous medium. The polymer helps to maintain a lipid-like microenvironment for the organic molecules to aid in preservation of their photochemical behavior in water. Thus this method is ideal to prepare water-dispersible photoresponsive systems. The use of near-infrared light to activate upconverting nanoparticles allows for lower energy light to be used to activate photoreactions instead of more harmful ultraviolet light.

Absorpsiyon spektrumları ve fotoluminesans spektrumları numune DAE-UCNP için toplanmıştır. Emme spektrumları kapalı diarylethene kromoforlar ve upconverting nano-tanecikleri arasındaki spektral örtüşme karşılaştırılması için kullanılır. Örneklerde (TPP-UCNP hem de DAE-UCNP) fotoğrafları, sulu faz içinde amfifilik polimer kabukları içinde bulunan organik boya molekülleri ile upconverting nanopartiküller, başarılı bir şekilde kapsülleme göstermek için dahil edilmiştir. Fotokimyada ve f...

Watch this Scientific Journal Video about A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles at JoVE.com

A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

Organic dye molecules and oleic acid coated upconverting nanoparticles are not water-soluble. This protocol describes a &#8216;plug and play&#8217; method that enables the transfer of organic dye molecules and upconverting particles from their initial hydrophobic solvent to water.

A &#39;Tak ve&#39; Yöntem, bir Amfifilik Polimer, Organik maddeler ve upconverting Nanopartiküller İçeren Su dağılabilir Nanoassemblies oluşturma

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate ...

a-plug-play-method-to-create-water-dispersible-nanoassemblies

Research

JoVE Journal

Chemistry

9.8K Görüntüleme.  Simon Fraser University. Organic dye molecules and oleic acid coated upconverting nanoparticles are not water-soluble. This protocol describes a ‘plug and play’ method that enables the transfer of organic dye molecules and upconverting particles from their initial hydrophobic solvent to water. 

Video: A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do so is highly important in view of a number of applications in functional soft matter including electronics, biomedical engineering, and sensors. In the past, successful strategies to control the size and shape of supramolecular polymers typically focused on the use of templates2,3, end cappers4 or selective solvent techniques5. 
Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing electrostatic repulsive interactions on the hydrophilic rim and attractive non-covalent forces within the hydrophobic core of the polymerizing building block, we manage to create small and discrete spherical objects6,7. Increasing the salt concentration to screen the charges induces a sphere-to-rod transition. Intriguingly, this transition is expressed in an increase of cooperativity in the temperature-dependent self-assembly mechanism, and more stable aggregates are obtained. 
For our study we select a benzene-1,3,5-tricarboxamide (BTA) core connected to a hydrophilic metal chelate via a hydrophobic, fluorinated L-phenylalanine based spacer (Scheme 1). The metal chelate selected is a Gd(III)-DTPA complex that contains two overall remaining charges per complex and necessarily two counter ions. The one-dimensional growth of the aggregate is directed by &pi;-&pi; stacking and intermolecular hydrogen bonding. However, the electrostatic, repulsive forces that arise from the charges on the Gd(III)-DTPA complex start limiting the one-dimensional growth of the BTA-based discotic once a certain size is reached. At millimolar concentrations the formed aggregate has a spherical shape and a diameter of around 5 nm as inferred from 1H-NMR spectroscopy, small angle X-ray scattering, and cryogenic transmission electron microscopy (cryo-TEM). The strength of the electrostatic repulsive interactions between molecules can be reduced by increasing the salt concentration of the buffered solutions. This screening of the charges induces a transition from spherical aggregates into elongated rods with a length &gt; 25 nm. Cryo-TEM allows to visualise the changes in shape and size. In addition, CD spectroscopy permits to derive the mechanistic details of the self-assembly processes before and after the addition of salt. Importantly, the cooperativity -a key feature that dictates the physical properties of the produced supramolecular polymers- increases dramatically upon screening the electrostatic interactions. This increase in cooperativity results in a significant increase in the molecular weight of the formed supramolecular polymers in water.

The goal of this experiment is to determine and control the size, shape and stability of self-assembled discotic amphiphiles in water. For aqueous based supramolecular polymers such level of control is very difficult. We apply a strategy using both repulsive and attractive interactions. The experimental techniques applied to characterize this system are broadly applicable.

Su Supramoleküler Polimerlerin Boyut, Şekil ve Stabilite Kontrolü

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do ...

Mühendislik

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

Şablon-ücretsiz Substratlarm üzerine makroskobik Nanoparçacık-ligand tabakalı Filmler işlevselleştirmek ve Öz-montajı A Tekniği

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

Kimya

Formulation of Diblock Polymeric Nanoparticles through Nanoprecipitation Technique

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale (nanoparticles). Nanoparticles can be engineered in a precise fashion where their size, composition and surface chemistry can be carefully controlled. This enables unprecedented freedom to modify some of the fundamental properties of their cargo, such as solubility, diffusivity, biodistribution, release characteristics and immunogenicity. Since their inception, nanoparticles have been utilized in many areas of science and medicine, including drug delivery, imaging, and cell biology1-4. However, it has not been fully utilized outside of "nanotechnology laboratories" due to perceived technical barrier. In this article, we describe a simple method to synthesize a polymer based nanoparticle platform that has a wide range of potential applications. 
The first step is to synthesize a diblock co-polymer that has both a hydrophobic domain and hydrophilic domain. Using PLGA and PEG as model polymers, we described a conjugation reaction using EDC/NHS chemistry5 (Fig 1). We also discuss the polymer purification process. The synthesized diblock co-polymer can self-assemble into nanoparticles in the nanoprecipitation process through hydrophobic-hydrophilic interactions.
The described polymer nanoparticle is very versatile. The hydrophobic core of the nanoparticle can be utilized to carry poorly soluble drugs for drug delivery experiments6. Furthermore, the nanoparticles can overcome the problem of toxic solvents for poorly soluble molecular biology reagents, such as wortmannin, which requires a solvent like DMSO. However, DMSO can be toxic to cells and interfere with the experiment. These poorly soluble drugs and reagents can be effectively delivered using polymer nanoparticles with minimal toxicity. Polymer nanoparticles can also be loaded with fluorescent dye and utilized for intracellular trafficking studies. Lastly, these polymer nanoparticles can be conjugated to targeting ligands through surface PEG. Such targeted nanoparticles can be utilized to label specific epitopes on or in cells7-10.

This article describes a nanoprecipitation method to synthesize polymer-based nanoparticles using diblock co-polymers. We will discuss the synthesis of diblock co-polymers, the nanoprecipitation technique, and potential applications.

Nanoprecipitation Tekniği Diblock Polimerik Nanopartiküller formülasyonu

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale ...

Biyomühendislik

Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are encapsulated in polystyrene-block-poly(acrylic acid) (PSPAA) shells and then used as monomers for their self-assembly. Spherical PSPAA micelles upon acid treatment are known to assemble into cylindrical micelles. Exploiting this tendency, the core-shell nanoparticles are induced to aggregate, coalesce, and then transform into long chains. When more than one type of nanoparticles are used, random and block &#8220;copolymers&#8221; of nanoparticles can be obtained. Detailed procedures are reported for the PSPAA encapsulation of nanoparticles, homo- and co-polymerization of the core-shell nanoparticles, separation and purification of the resulting nanoparticle chains. Transformations of single-line chains into double- and triple-line chains are also presented. The synergy between the polymer shell and the embedded nanoparticles leads to an unusual chain-growth polymerization mode, giving long nanoparticle chains that are distinct from the products of the traditional step-growth aggregation process.

Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We report protocols for &#8220;polymerizing&#8221; various types of polymer-encapsulated metal nanoparticles into long chains of &#8220;homo-&#8220; and &#8220;co-polymers&#8221;.

Polistiren kullanma<em&gt; Bloğu</em&gt; -poli (Akrilik asit) Bunların homo- ve ko-polimerizasyon için monomer olarak metal Nanopartiküller -kaplı

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox Katalizörü kullanarak görünür ışık aracılığı ile dispersiyon polimerleştirilmesi ile solucan gibi miseller Facile sentezi

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Fabrication of Spherical and Worm-shaped Micellar Nanocrystals by Combining Electrospray, Self-assembly, and Solvent-based Structure Control

Micellar nanocrystals (micelles with encapsulated nanocrystals) have become an emerging major class of nanobiomaterials. We describe a method of fabricating micellar nanocrystals based on combining top-down electrospray, bottom-up self-assembly, and solvent-based structure control. This method involves first using electrospray to generate uniform ultrafine liquid droplets, each of which functions as a micro-reactor in which self-assembly reaction occurs forming micellar nanocrystals, with the structures (micelle shape and nanocrystal encapsulation) controlled by the organic solvent used. This method is largely continuous and produces high quality micellar nanocrystal products with an inexpensive structure control approach. By using a water-miscible organic solvent tetrahydrofuran (THF), worm-shaped micellar nanocrystals can be produced due to solvent-induced/facilitated micelle fusion. Compared with the common spherical micellar nanocrystals, worm-shaped micellar nanocrystals can offer minimized non-specific cellular uptake, thus enhancing biological targeting. By co-encapsulating multiple nanocrystals into each micelle, multifunctional or synergistic effects can be achieved. Current limitations of this fabrication method, which will be part of the future work, primarily include imperfect encapsulation in the micellar nanocrystal product and the incompletely continuous nature of the process.

The present work describes a method to fabricate micellar nanocrystals, an emerging major class of nanobiomaterials. This method combines top-down electrospray, bottom-up self-assembly, and solvent-based structure control. The fabrication method is largely continuous, can produce high quality products, and possesses an inexpensive means of structure control.

Küresel ve solucan şeklinde Micellar Nanocrystals Electrospray, kendinden montajlı birleştirerek ve Solvent Bazlı Yapı Denetim imalatı

Micellar nanocrystals (micelles with encapsulated nanocrystals) have become an emerging major class of nanobiomaterials. We describe a method of ...

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock copolymers are produced by one of three techniques: thin film rehydration, solvent switching or polymerization-induced self-assembly, and produce only flexible, polydisperse cylinders. Crystallization-driven self-assembly (CDSA) is a method which can produce cylinders with these properties, by stabilizing structures of a lower curvature due to the formation of a crystalline core. However, the living polymerization techniques by which most core-forming blocks are formed are not trivial processes and the CDSA process may yield unsatisfactory results if carried out incorrectly. Here, the synthesis of cylindrical nanoparticles from simple reagents is shown. The drying and purification of reagents prior to a ring-opening polymerization of &#949;-caprolactone catalyzed by diphenyl phosphate is described. This polymer is then chain extended by methyl methacrylate (MMA) followed by N,N-dimethyl acrylamide (DMA) using reversible addition&#8722;fragmentation chain-transfer (RAFT) polymerization, affording a triblock copolymer that can undergo CDSA in ethanol. The living CDSA process is outlined, the results of which yield cylindrical nanoparticles up to 500 nm in length and a length dispersity as low as 1.05. It is anticipated that these protocols will allow others to produce cylindrical nanostructures and elevate the field of CDSA in the future.

Crystallization-driven self-assembly (CDSA) displays the unique ability to fabricate cylindrical nanostructures of narrow length distributions. The organocatalyzed ring-opening polymerization of &#949;-caprolactone and subsequent chain extensions of methyl methacrylate and N,N-dimethyl acrylamide are demonstrated. A living CDSA protocol that produces monodisperse cylinders up to 500 nm in length is outlined.

Biodegradable blok kopolimerlerin kristalizasyon Driven kendinden montajı ile Monodisperse silindirik Nanopartiküllerin sentezini

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock ...

Rapid, Scalable Assembly and Loading of Bioactive Proteins and Immunostimulants into Diverse Synthetic Nanocarriers Via Flash Nanoprecipitation

Nanomaterials present a wide range of options to customize the controlled delivery of single and combined molecular payloads for therapeutic and imaging applications. This increased specificity can have significant clinical implications, including decreased side effects and lower dosages with higher potency. Furthermore, the in situ targeting and controlled modulation of specific cell subsets can enhance in vitro and in vivo investigations of basic biological phenomena and probe cell function. Unfortunately, the required expertise in nanoscale science, chemistry and engineering often prohibit laboratories without experience in these fields from fabricating and customizing nanomaterials as tools for their investigations or vehicles for their therapeutic strategies. Here, we provide protocols for the synthesis and scalable assembly of a versatile non-toxic block copolymer system amenable to the facile formation and loading of nanoscale vehicles for biomedical applications. Flash nanoprecipitation is presented as a methodology for rapid fabrication of diverse nanocarriers from poly(ethylene glycol)-bl-poly(propylene sulfide) copolymers. These protocols will allow laboratories with a wide range of expertise and resources to easily and reproducibly fabricate advanced nanocarrier delivery systems for their applications. The design and construction of an automated instrument that employs a high-speed syringe pump to facilitate the flash nanoprecipitation process and to allow enhanced control over the homogeneity, size, morphology and loading of polymersome nanocarriers is described.

Nanomaterials provide versatile mechanisms of controlled therapeutic delivery for both basic science and translational applications, but their fabrication often requires expertise that is unavailable in most biomedical laboratories. Here, we present protocols for the scalable fabrication and therapeutic loading of diverse self-assembled nanocarriers using flash nanoprecipitation.

Ölçeklenebilir, Hızlı montaj ve biyoaktif proteinler ve Immunostimulants yükleme yolu ile birden parlamak Nanoprecipitation çeşitli sentetik Nanocarriers içine

Nanomaterials present a wide range of options to customize the controlled delivery of single and combined molecular payloads for therapeutic and imaging ...

Flash NanoPrecipitation for the Encapsulation of Hydrophobic and Hydrophilic Compounds in Polymeric Nanoparticles

The formulation of a therapeutic compound into nanoparticles (NPs) can impart unique properties. For poorly water-soluble drugs, NP formulations can improve bioavailability and modify drug distribution within the body. For hydrophilic drugs like peptides or proteins, encapsulation within NPs can also provide protection from natural clearance mechanisms. There are few techniques for the production of polymeric NPs that are scalable. Flash NanoPrecipitation (FNP) is a process that uses engineered mixing geometries to produce NPs with narrow size distributions and tunable sizes between 30 and 400 nm. This protocol provides instructions on the laboratory-scale production of core-shell polymeric nanoparticles of a target size using FNP. The protocol can be implemented to encapsulate either hydrophilic or hydrophobic compounds with only minor modifications. The technique can be readily employed in the laboratory at milligram scale to screen formulations. Lead hits can directly be scaled up to gram- and kilogram-scale. As a continuous process, scale-up involves longer mixing process run time rather than translation to new process vessels. NPs produced by FNP are highly loaded with therapeutic, feature a dense stabilizing polymer brush, and have a size reproducibility of &#177; 6%.

Flash NanoPrecipitation (FNP) is a scalable approach to produce polymeric core-shell nanoparticles. Lab-scale formulations for the encapsulation of hydrophobic or hydrophilic therapeutics are described.

Hidrofobik ve hidrofilik bileşikler polimer nano tanecikleri Kapsülleme için NanoPrecipitation flash

The formulation of a therapeutic compound into nanoparticles (NPs) can impart unique properties. For poorly water-soluble drugs, NP formulations can ...

Facile Preparation and Photoactivation of Prodrug-Dye Nanoassemblies

Self-assembly is a simple yet reliable method for constructing nanoscale drug delivery systems. Photoactivatable prodrugs enable controllable drug release from nanocarriers at target sites modulated by light irradiation. In this protocol, a facile method for fabricating photoactivatable prodrug-dye nanoparticles via molecular self-assembly is presented. The procedures for prodrug synthesis, nanoparticle fabrication, physical characterization of the nanoassembly, photocleavage demonstration, and in vitro cytotoxicity verification are described in detail. A photocleavable boron-dipyrromethene-chlorambucil (BC) prodrug was first synthesized. BC and a near-infrared dye, IR-783, at an optimized ratio, could self-assemble into nanoparticles (IR783/BC NPs). The synthesized nanoparticles had an average size of 87.22 nm and a surface charge of -29.8 mV. The nanoparticles disassembled upon light irradiation, which could be observed by transmission electronic microscopy. The photocleavage of BC was completed within 10 min, with a 22% recovery efficiency for chlorambucil. The nanoparticles displayed enhanced cytotoxicity under light irradiation at 530 nm compared with the non-irradiated nanoparticles and irradiated free BC prodrug. This protocol provides a reference&#160;for the construction and evaluation of photoresponsive drug delivery systems.

This protocol describes the fabrication and characterization of a photoresponsive prodrug-dye nanoassembly. The methodology for drug release from the nanoparticles by light-triggered disassembly, including the light irradiation setup, is explicitly described. The drugs released from the nanoparticles following light irradiation exhibited excellent anti-proliferation effects on human colorectal tumor cells.

Prodrug-Boya Nanoassment'lerinin Kolay Hazırlanması ve Fotoaktivasyonu

Self-assembly is a simple yet reliable method for constructing nanoscale drug delivery systems. Photoactivatable prodrugs enable controllable drug release ...

A 'Tak ve' Yöntem, bir Amfifilik Polimer, Organik maddeler ve upconverting Nanopartiküller İçeren Su dağılabilir Nanoassemblies oluşturma

Özet

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