نانولوله کاغذي بسازيمدر مقاله «نانولوله هاي کربني» خوانديد که ساختار نانولوله هاي کربني مانند يک صفحه گرافيت است که دو سر آن به هم متصل شده و يک استوانه ساخته اند. همانطور که ديديد، دو سر صفحه گرافيت را به سه شکل مختلف مي توان به هم متصل نمود، بنابراين سه نوع نانولوله خواهيم داشت: 1- نوع زيگزاگ اتمهاي متصل به هم در اين نوع شکل زيگزاگ را پديد مي آورند:
2- نوع صندلي در اين نوع، اتم ها طوري به يکديگر اتصال يافته اند که فرم صندلي را براي ما تداعي مي کنند:
3- نوع نامتقارن رديف هاي اتمي در اين نوع نانولوله به صورت اريب قرار مي گيرند، بنابراين اگر اين نانولوله را مقابل آينه قرار دهيد، تصويري متفاوت از اصل را خواهيد ديد و به همين علت هم ، نامتقارن نام گرفته است:
براي انجام بازي «تقارن آينه اي» به آدرس زير سري بزنيد:
براي ساختن نانولوله هاي گفته شده در بالا با کاغذ، صفحات زير را داونلود کنيد. اين صفحات ساختار شش ضلعي هاي منتظم اتمهاي کربن را نشان مي دهد. براي ساختن نانولوله ها، صفحات را طوري به يکديگر بچسبانيد که کلمات «زيگزاگ»، «صندلي» و «نامتقارن» کامل شوند. • نوع صندلي • نوع نامتقارن • نوع زيگزاگ
چرا نانو پودرها
در تعريف نانوپودرها ذكر شد که مهمترين ويژگي آنها، ريزي ذرات تشكيلدهنده است. وقتي ما يك قطعه را چند قسمت ميكنيم، حجم كل ثابت ميماند، يعني حجم قطعهي اوليه دقيقاً برابر است با جمع حجم تكههاي تقسيمشده. اما در طيّ اين فرآيند، مجموع سطح بيرونيِ تكهها چندبرابرِ سطح بيروني قطعهي اوليه خواهد شد.
محدوديت نانوپودرها محدويت نانوپودرها نيز از زياد بودن سطح آزاد آنها ناشي ميشود. در واقع، ذرات مثل برادههاي آهنربا تمايل دارند به همديگر بچسبند تا دوباره شكل اوليهي خود را به دست آورند. وقتي ما اندازهي ذرات پودر را به نانومتر مي رسانيم، اين تمايل بهشدت زياد ميشود، تا جايي كه ممكن است به صورت ناگهاني به هم بچسبند. براي رفع اين مشكل بايد ذرات پودر را از همديگر جدا نگاه داشت تا به هم نچسبند. اين كار از طريق محلولسازي پودرها، مانند حلّ نمك و آهن يا اضافه كردن موادي كه سبب ايجاد بارهاي همنام روي سطح پودرها و ايجاد نيروي دافعه ميشوند، صورت ميگيرد. براي درك بهتر موضوع، مسئلهاي را طرح ميکنيم: فرض كنيد يك قطعه به شكل مكعب با طول ضلع 3 سانتيمتر داريم. در صورتي كه اين مكعب را به 27 مكعب تقسيم كنيم، سطح آزاد چند برابر ميشود؟ جواب:
V1=a13=(3cm)3=27cm3 (حجم مكعب بزرگتر)
براي اينكه مكعب را به 9 مكعب كوچكتر تقسيم كنيم، بايد هريك از اضلاع را به 3 قسمت تقسيم كنيم. در اين حالت:
V2=a32=(1cm)3=1cm3 (حجم هر مكعب)
اگر جمع حجم اين 9 مكعب را در نظر بگيريم:
يعني برابراست با حجم مکعب بزرگ. ولي سطح آزاد مكعب بزرگ برابر است با:
در حالي که مجموع سطح آزاد مكعبهاي كوچك برابر است با:
يعني سطح آزاد در اثر خُرد كردن مكعب بزرگ به 27 مکعب کوچک، 3 برابر شده است.
اهميت سطح آزاد مواد: اهميت سطح آزاد در اين است كه سطح آزاد مواد است که محل انجام واكنش هاي آن ها است. براي مثال ، حتماً ديده ايد كه در زمستان، روي يخ جاده ها نمك طعام مي پاشند تا يخ زودتر ذوب شود، واكنش بين نمك و يخ در سطح ذرات نمك انجام مي شود ، براي درك بهتر فرض كنيد سنگ نمك طعام را روي يخ بيندازند، بهتر يخ را ذوب مي كند يا اينكه اين سنگ را پودر كرده و پودر نمك را روي يخ بپاشيم. مثالي ديگر از اين مطلب ، تفاوت حل كردن شكر و قند در چاي است. در فيلم زير بخوبي ديده مي شود که شكر به دليل سطح آزاد زياد آن ، به مراتب سريعتر از يك حبه قند با حجم يکسان، در آب داغ حل مي شود.
ديدنِ ناديدهها
تلاش براي ديدنِ سطوح بسيار نازك، از مهمترين فعاليتهاي علميِ آزمايشگاههاي جهان است. اين كار، بسيار مشكل و معمولاً غيراقتصادي است. كدام كار؟ ديدنِ مستقيم سطوح بسيار نازك مانند سطح كف دريا يا سطح اتم. روش معمول براي ديدن چنين سطوحي غيرمستقيم است؛ يعني جمعآوري دادههاي دقيق و پردازش آنها توسط رايانهها و تبديلشان به تصاويرِ ديدني. در مقالهاي كه ميخوانيد، شما را با چگونگي كسب اطلاعات از سطوح ناديدني و تبديل آنها به مدلهاي دوبُعدي و سهبُعدي آشنا ميكنيم. اين همان كاري است كه ميكروسكوپ نيروي اتمي انجام ميدهد. شبيهسازي كف دريا كه با استفاده از دادهها صورت ميگيرد، مدتهاست که در تحقيقات و مطالعات اقيانوسشناسي به كار ميرود. اقيانوسشناسانِ اوليه به انتهاي كابلهاي بلند وزنههايي ميآويختند و ته دريا ميفرستادند. اين وزنهها كف دريا را ميپيمودند و ناهمواريها و شيارهاي آن را از طريق كابلها روي كاغذهاي شطرنجي نقش ميكردند.
امروزه در فارسي به اين قبيل وسايل كه ميتوانند اطلاعاتي را از سطوح ناديدني به ما برسانند، «پيمايشگر» ميگويند. اين عنوان معادل واژة probe در انگليسي است.
اقيانوسشناسان جديد، كابل و وزنه را به كناري نهادهاند و فناوري رادار را به خدمت گرفتهاند. آنها امواج صوتي را از يك كشتي اقيانوسپيما به كف دريا گسيل ميكنند و با ثبت فاصلة كف با منبع گسيلكننده ناهمواريهاي كف را ترسيم مينمايند. ماهوارهها هم به همين روش ميتوانند امواجي را به اعماق ناشناختة فضا بفرستند و با محاسبة زمان رفت و برگشت، فواصل را اندازه بگيرند. در ميكروسكوپ نيروي اتمي نيز از اين روشِ ديدن استفاده ميشود. AFM پيمايشگري را روي سطح ماده حركت ميدهد. همزمان با حركت اين پيمايشگر بر سطح ماده، نيروي مكانيكي بين كاوشگر و ماده محاسبه ميشود. اين دادهها براي به تصوير كشيدن سطح اتم در رايانه مورد استفاده قرار ميگيرند.
در اينجا آزمايشي را به شما معرفي ميكنيم كه شما را با رفتار يك ميكروسكوپ نيروي اتمي آشنا ميكند. با اين آزمايش ميتوانيد بدون ديدنِ مستقيم، دادههايي را از درون يك جعبة دربسته استخراج كنيد و با استفاده از آنها تصاويري دو و سهبُعدي از سطح دروني آن ترسيم نماييد.
يك جعبه كفشِ خالي را برداريد و از دوستتان بخواهيد كه يك وسيلة مجهول درون جعبه درست وسط آن بچسباند و در آن را هم محكم ببندد. حالا كاغذي شطرنجي، مانند تصوير زير، روي آن بچسبانيد. (اگر چاپگر داريد، روي تصوير كليك كنيد و نسخة با كيفيت بالاتر را داونلود كنيد و از آن پرينت بگيريد.)
سپس با يك ميل بافتني صفحه را سوراخ سوراخ كنيد و با كمك همان ميل بافتني ارتفاع شيء مجهول از كفِ جعبه را در نقاط مختلف اندازه بگيريد. حواستان را جمع كنيد كه فقط ارتفاع ميلة بافتنيِ فرورفته داخل جعبه را اندازه نگيريد، بلكه ارتفاع جعبه را هم محاسبه كنيد. مثلاً اگر ارتفاع جعبه 14 سانتيمتر است و ميل بافتني در آن نقطه 7.5 سانتيمتر فرو رفته است. بايد 7.5 را از 14 كم كنيد تا ارتفاع شيء مجهول از كف جعبه به دست آيد.
پس از اينكه ارتفاعهاي نقاط مختلف را اندازه گرفتيد، كافي است تا اين فايل را داونلود كنيد و به كمك آن حدس بزنيد داخل جعبه چه چيزي وجود دارد. خوب، چطور اين حدس را زديد؟ درست است: به كمك شكلي كه از سطح شيء مجهول به دست آورده ايد. فايلي كه براي اين كار در اختيار شما قرار داده شده، يك صفحة گسترده است كه توسط نرمافزار Excel طراحي شده است و شما هم ميتوانيد مشابه آن را توليد كنيد.
شكل بالا نتيجه انجام آزمايش جعبه دربسته براي يك جسم هرم مانند است. جدول 15×15 بالاي صفحه در واقع همان كاغذ مشبكي است كه شما روي جعبه چسباندهايد. حالا كافي است كه ارتفاع شيء مجهول را در هر نقطه به كمك ميل بافتني اندازه بگيريد و آن را در خانة متناظر آن در فايل Excel ذخيره كنيد. همانطور كه اعداد وارد برنامه ميشوند، نقشة سطحِ شيء مجهول كه اصطلاحاً به آن «نقشة توپوگرافي» ميگويند، كاملتر مي شود.
نانوبیوتکنولوژی
دید کلی
فناوری نانو ، چنانکه از نام آن برمیآید با اجسامی به ابعادنانومتر سروکار دارد. فناوری نانو در سه سطح قابل بررسی است: مواد ، ابزارها وسیستمها. در حال حاضر در سطح مواد ، پیشرفتهای بیشتری نسبت به دو سطح دیگر حاصل شدهاست. موادی را که در فناوری نانو بکار میروند، نانو ذره نیز مینامند. برای آنکهتصوری از ریزی نانو ذرهها داشته باشیم بهتر است آن را باابعادسلولمقایسه کنیم. اندازه متوسطسلولیوکاریوتی 10 میکرومتر است. اندازه متوسط یکپروتئین 5 نانومتر است که با ابعاد ریزترین جسم ساخت بشر قابل مقایسه است. بنابراین میتوانبا بکارگیری نانو ذرهها نوعی مامور مخفی به درون سلول فرستاد و به کمک آن از بعضیرازهای نهفته در سلول پرده برداری کرد.
نانوتکنولوژیمجموعهای است از فناوریهایی که به صورت انفرادی یا باهم در جهت بکارگیری و یا درکبهتر علوم مورد استفاده قرار میگیرند. بیوتکنولوژیجزء فناورهای در حال توسعه میباشد که با بکارگیری مفهوم نانو به پیشرفتهای بیشتریدست خواهد یافت. نانوبیوتکنولوژی به عنوان یکی از حوزههای کلیدی قرن 21 شناخته شدهاست که امکان تعامل با سیستمهای زنده را در مقیاس مولکولی فراهم میآورد. بیوتکنولوژی به نانوتکنولوژی مدل ارائه میدهد، در حالی که نانوتکنولوژی با دراختیار گذاشتن ابزار برای بیوتکنولوژی آن را برای رسیدن به اهدافش یاری میرساند.
نشانگرهای زیستی
از آنجا که انداه نانو ذرات ، در محدوده اندازهپروتئینهاست، میتوان از آنها برای نشاندار کردن نمونههای زیستی استفاده کرد. برایاین کار ، باید نانو ذره بتواند به نمونه زیستی هدف متصل شود و نیز راهی برای دنبالکردن و شناسایی نانو ذره وجود داشته باشد. به منظور ایجاد میان کنش بین نانو ونمونه زیستی ، نانو ذره را با پوشش بیولوژیکی مانندآنتیبادیها، بیوپلیمرهایی مانندکلاژنهاکه نانو ذره ها را از نظر زیستی سازگار میکند، میپوشانند. میتوان نانو ذرهها رافلورسنت کرده یا خواص نوری آنها تغییر داد.
سطحاستخواناز ترکیباتی تشکیل شده است که حدودا 100 نانومتر عرض دارند. اگر سطح یک عضو مصنوعیبه استخوان طبیعی پیوند بخورد بدن آن را پس میزند. دلیل امر تولید بافت مصنوعی درمحل استخوان طبیعی و سطح مصنوعی میباشد. استئوبلاستهادربافتپیوندیاستخوان وجود دارند و بخصوص در استخوانهای در حال رشد دارای فعالیتچشمگیری هستند. با ایجاد ذراتی در اندازه نانو در سطح مفاصل و استخوانهای مصنوعیاحتمال دفع عضو جایگزین به دلیل تحریک سلولهای استئوبلاست کمتر میشود. ایجاد اینذرات با ترکیبمواد پلیمری، سرامیکی و فلزی چندی پیش توسطدانشمندان به اثبات رسید.
معالجهسرطانبا استفاده از روش فتودینامیک بر اساس نابودی سلولهای سرطانی بوسیله لیزری است کهتولیداکسیژناتمیمیکند. به این طریق که اکسیژن اتمی رنگ خاصی را تولید میکند و سلولهایسرطانی بیش از سلولهاهای دیگر آن را جذب میکنند. در نتیجه فقط سلولهای سرطانی توسطاشعه لیزرنابود میشوند. البته یکی ازمعایب این روش آن است که به دلیل آب گریز بودن مواد رنگی ، این مواد به سمتپوستوچشمهاحرکت میکند و در صورتی که شخص در معرض نور خورشید قرار گیرد باعث حساسیت در پوست وچشمها میشود.
اکسید تیتانیوم (Tio2) می تواند بهعنوان کاتالیزور نوری عمل نماید. هنگام تابش نور جذبفوتونهابا انرژی بالا ، باعث برانگیختگیالکترونهاو ایجاد رسانایی در مولکول میگردد. شکاف ایجاد شده بین دو جفت الکترون به مشابه یکجریان الکتروپوزیتیو در طولمولکول DNAباعث باز شدن دو رشته DNA از یکدیگر میگردد. در واقع تغییرات ایجاد شدهبوسیله فوتونهای نور در مولکول Tio2باعث میشود که این مولکول به شکلیک آنزیم آندونوکلئاز عمل نماید. این تواناییها در آینده میتواند تغییرات زیادی رادر استفاده از داروها وژندرمانیایجاد نماید و توانایی پیوند Tio2با بیومولکولهای مختلف راهرا در ژن درمانی هموار خواهد نمود.
یکیازبزرگتریناشکالاتدستکاریداخلسلولبوسیلهاینریزابزارایناستکهاینذراتبهاندازهکافیتواناییکنترلمادهژنتیکیداخلهستهراندارند. ترکیبمولکول DNA با Tio2درمحیطخارجسلولنشاندهندهاینمشکلاست. بهازایاتصال Tio2بههر60 - 50 جفتبازفقطیکناحیهژنیدرسلولپستاندارانتحتپوششقرارمیگیردکهدانشمندانامیدوارنداینمشکلنیزدرآیندهنزدیکحلشود. همچنینتحقیقاتیدرزمینهاستفادهازاینذراتبهعنوانجایگزینیدرتوقفسنتز RNA بهعنوانبازدارندههایسنتز RNA بامکانیزمایجادشکافدر RNA صورتگرفتهکهمیتوانددرصورتتکمیلشدن،امکاناستفادهازاینذراترادرتوقفسنتز RNA درسلولهایسرطانیفراهمنماید.
چشم انداز بحث
با توجه به پیشرفت سریع و دامنه گسترده بیوتکنولوژیزمینههای بروز انقالاب بیوتکنولوژی عصر جدیدی در علوم مختلف مانند بیولوژی ، پزشکی،فارماکولوژیومهندسیژنتیکفراهم گردیده است. به علاوه حوزههای دیگری مانند اقتصاد و سیاست نیز ازآن تاثیر بسزایی پذیرفته است. هم اکنون از دیدگاه اخلاق زیستی در این رابطه سوالاتمهم و اساسی مطرح شده است که علاوه بر اثرات بسزایی که بر پیشرفتهای علمی و سایرزمینههای علوم زیستی دارد، نسلهای آینده بشر را نیز به صورت گستردهای تحتالشعاعقرار میدهد. در این باره مشارکت مداوم دانشمندان کنجکاو و خردمندی میتواند راهگشا بوده و بایستی با در نظر گرفتن این منابع و پیشرفتهای جدید و با امید به حلچنین مشکلات و مسائلی با فائق آمدن بر همه محدودیتها در جهت گسترش این دانش فعالیتنمود.
New technique takes a big step in examination of small structures
Shown is an image of bacteriophage Epsilon15 studied by Wen Jiang, an assistant professor of biological sciences at Purdue. The bacteriophage is shown at a resolution of 4.5 angstrom - the highest resolution achieved for a living organism of this size. (Graphic/Wen Jiang lab)
A team led by a Purdue University researcher has achieved images of a virus in detail two times greater than had previously been achieved. Wen Jiang, an assistant professor of biological sciences at Purdue, led a research team that used the emerging technique of single-particle electron cryomicroscopy to capture a three-dimensional image of a virus at a resolution of 4.5 angstroms.
"This is one of the first projects to refine the technique to the point of near atomic-level resolution," said Jiang, who also is a member of Purdue's structural biology group. "This breaks a threshold and allows us to now see a whole new level of detail in the structure. This is the highest resolution ever achieved for a living organism of this size."
Details of the structure of a virus provide valuable information for development of disease treatments, he said.
"If we understand the system - how the virus particles assemble and how they infect a host cell - it will greatly improve our ability to design a treatment," Jiang said. "Structural biologists perform the basic science and provide information to help those working on the clinical aspects."
A paper detailing the work was published in the Feb. 28 issue of Nature.
Roger Hendrix, a professor of biological sciences at the University of Pittsburgh, said what is learned about viruses can be applied to many other biological systems.
"Understanding the proteins that create the structure of a virus gives us insight into the tiny biological machines found throughout our bodies," he said. "Getting to 4.5 angstrom using this technique is a watershed of sorts because it is the first time we can actually trace the polypeptide chain - the backbone of proteins. Now we can see the tiny gears and levers that allow the proteins to move and interact as they carry out their intricate biological roles."
The imaging technique, called cryo-EM, has the added benefit of maintaining the sample being studied in a state very similar to its natural environment. Other imaging techniques used regularly, such as X-ray crystallography, require the sample be manipulated.
"This method offers a new approach for modeling the structure of proteins in other macromolecular assemblies, such as DNA, at near-native states," Jiang said. "The sample is purified in a solution that is very similar to the environment that would be found in a host cell. It is as if the virus is frozen in glass and it is alive and infectious while we examine it."
In addition to Jiang, Matthew L. Baker, Joanita Jakana and Wah Chiu from Baylor College of Medicine, and Peter R. Weigele and Jonathan King from Massachusetts Institute of Technology worked on the project, which was funded by the National Institutes of Health and the National Science Foundation.
The team obtained a three-dimensional map of the capsid, or protein shell, of the epsilon15 bacteriophage, a virus that infects bacteria and is a member of a family of viruses that are the most abundant life forms on Earth, Jiang said.
Other methods of determining the structure could not be used for this family of virus. None had been successfully crystallized, and the complexity of members of this family had prevented evaluation through the genome sequence alone.
This demonstration shows that cryo-EM is doable and is a major step in reaching the full potential of this technique," he said. "The goal is to have it reach a 3 to 4 angstrom resolution, which would allow us to clearly see the amino acids that make up a protein."
In electron microscopy, a beam of electrons takes the place of the light beam used in a conventional microscope. The use of electrons instead of light allows the microscope to "see" in much greater detail.
Cryo-EM cools specimens to temperatures well below the freezing point of water. This decreases damage from the electron beam and allows the specimens to be examined for a longer period of time. Longer exposure time allows for sharper, more detailed images.
Researchers using cryo-EM had obtained images at a resolution of 6-9 angstroms but could not differentiate between smaller elements of the structure spaced only 4.5 angstroms apart.
"There are different elements that make up the protein building blocks of the virus," Jiang said. "It is like examining a striped blanket. From a distance, the stripes blur together and the blanket appears to be one solid color. As you get closer you can see the different stripes, and if you use a magnifying glass you can see the strands of string that make up the material. The resolution needs to be smaller than the distance between the strands of thread in order to see two separate strands.
"By being able to zoom in, researchers were able to see components that blurred together at the earlier achieved resolution."
Cryo-EM requires high-end electron microscopes and powerful computing resources. The research team used the Baylor College of Medicine's cryoelectron microscope. It is expected that Purdue will install a state-of-the-art cryoelectron microscope in 2009.
In 2006 Purdue received a $2 million grant from the National Institute of Health to purchase the microscope. It will be installed in Hockmeyer Hall of Structural Biology, expected to open in 2009.
Computer programs are used to extract the signal from the microscope and to combine thousands of two-dimensional images into an accurate three-dimensional image that maps the structure of the virus. This requires use of a large data set and could not have been done without the resources of Purdue's Office of Information Technology, or ItaP, Jiang said.
Jiang used Purdue's Condor program - which links computers including desktop machines and large, powerful research computers - to create the largest distributed computing network at a university.
"ITaP provided us with computational power at the supercomputer scale that was necessary for this work," he said. "Purdue's Condor program allowed us to take advantage of the power of 7,000 computers. This was a critical element to our success."
Jiang plans to continue to refine every step of the process to improve the capabilities of the technique and to examine more medically relevant virus species.
Purdue's structural biology group studies a diverse group of problems, including cellular signaling pathways, RNA catalysis, bioremediation, molecular evolution, viral entry, viral replication and viral pathogenesis. Researchers use a combination of X-ray crystallography, electron cryomicroscopy, NMR spectroscopy, and advanced computational and modeling tools to study these problems.
Ultrafast electron microscopy reveals switchable nanochannels in materials
Microscopic fissures in a tiny crystal open and close—on command. Researchers led by Ahmed H. Zewail successfully used ultrafast electron microscopy (UEM) to observe nanoscopic structures at their “exercises”, as they report in the journal Angewandte Chemie. Such switchable nanochannels could be useful for future nanoelectronics and nanoscopic “machines”.
Zewail and his team at the California Institute of Technology (Pasadena, USA) are renowned for their work in ultrafast science and technology. Zewail received the Nobel Prize in Chemistry in 1999 for the development of ultrafast laser techniques that are capable of revealing the motions of individual atoms within a molecule during a reaction.
The most recent development to spring from Zewail’s Laboratory is ultrafast electron microscopy. This technique is a combination of a femtosecond optical system (a femtosecond equals 10-15 seconds) with a high-resolution electron microscope; the result is a new tool with extremely high resolution in time as well as in space.
Zewail and his team have now discovered that needle-shaped microcrystals of copper and the organic compound TCNQ (7,7,8,8-tetracyanoquinodimethane, C12H4N4 ), a crystalline, quasi-one-dimensional semiconductor, exhibit optomechanical phenomena that could be of use in nanoelectronic applications.
The investigation showed that these crystals stretch out to become longer (but not wider) when they are irradiated with laser pulses in the microscope. If the irradiation is switched off, they contract back to their original size. This effect was most obvious when one of these needles was broken by the shock of a short, strong laser pulse: A small crack of some ten to one hundred nanometers forms at the break. When the crystal is stretched out under irradiation, the nanoscale channel closes up; upon contraction, it reappears. The phenomenon is reversible, as confirmed by UEM. Why do these micromaterials stretch under light? Within the crystal, the negatively charged TCNQ ions are arranged so that their central, flat, six-membered rings are piled up on top of each other in the long direction of the needle. The energy of a laser pulse excites electrons; part of this energy is transferred, resulting in uncharged TCNQ molecules. For the uncharged TCNQ, the stacked arrangement is no longer favorable, they now require more space and cause the crystal to grow longer. The degree of stretching depends on the strength of the energy absorbed.
“Our fundamental in situ UEM observations, which reveal the behavior of nanoscopic matter in space and time, opens up new areas to explore, especially in materials science, nanotechnology, and biology,” says Zewail.
Citation: Ahmed H. Zewail, Controlled Nanoscale Mechanical Phenomena Discovered with Ultrafast Electron Microscopy, Angewandte Chemie International Edition 2007, 46, No. 48, 9206–9210, doi: 10.1002/anie.200704147
Nanoscale tool allows scientists to study membrane proteins one at a time
Isolation chamber. A new tool developed at Rockefeller allows scientists to study membrane proteins individually, or in pairs, to see how they interact with other molecules. The scientists use an electron microscope to take images of isolated NABBs and categorize the orientation of the receptors they contain as either antiparallel (top) or parallel (bottom). Credit: Rockefeller University
In biology, as in construction, it’s all about having tools that fit the job. Researchers at Rockefeller University have now created a tiny tool, more than 10,000 times smaller than the diameter of a human hair, capable of encasing single membrane proteins from living cells. The new system, which resembles a nanoscale sushi roll, will allow investigators to individually stimulate these key proteins with specific molecules and signals in order to precisely define the biological reactions that result.
The Nanoscale Apolipoprotein Bound Bilayers (NABBs), developed by scientists in Rockefeller’s Laboratory of Molecular Biology and Biochemistry and reported in the Journal of Molecular Biology, is a versatile device that can likely be adapted to any of the myriad transmembrane receptors that direct cell activity by reacting to molecules outside the cell and activating signals inside the cell.
“Today it is impossible to know exactly what a single protein on the surface of a cell that has thousands of other proteins is doing. It might be acting on its own or binding to one or more other proteins,” says Thomas Sakmar, Richard M. and Isabel P. Furlaud Professor and head of the laboratory and the study’s senior investigator. “With this tool, we can control the receptor’s membrane environment and test all possibilities of interaction with ligands, other receptors or other proteins. It’s one way to figure out how a complex system works.”
Previously, researchers studied the functions of such proteins by investigating literally millions of them floating together in a soup created when cell membranes are broken apart and solubilized chemically. But this method of studying proteins is problematic, the researchers say: The membrane protein mixtures tend to be inhomogeneous and it is difficult — partially due to poor stability of the isolated proteins — to purify them in their active state in order to understand what the receptors are doing individually. The solution, devised by Sakmar, first author Sourabh Banerjee, a graduate student in the Tri-Institutional Chemical Biology Program, and Thomas Huber, a postdoc, arose as the team searched for a way to exquisitely catalogue the functions of individual G-protein-coupled receptors (GPCRs), a large family of transmembrane proteins that are involved in many diseases and are often the target of medicinal agents. The structure they built was developed using a hard-working human transport particle, the high-density lipoprotein (HDL), as a model system. This flat, circular structure is essentially a complex of phospholipids belted together by apolipoprotein A-I (apo A-I) to carry cholesterol and lipids through blood to the liver.
Assuming that evolutionary forces might have already optimized a biological solution to an engineering problem, Huber suggested using apo A-I from zebrafish. “Based on the sequence of zebrafish apo A-I, we thought that it may yield structurally homogeneous discs,” Banerjee says. So in their NABB, zebrafish apo A-I (known as zap1) forms a belt that makes two layers of lipids stick together — like the seaweed that keeps sticky rice together in sushi.
They then devised a method to trigger rapid self-assembly of these disc-like nanoparticles from mixtures of zap1, lipids and extracted cellular membrane proteins. “We have made it fairly straightforward to make these structures and they form in less than an hour,” says Banerjee, who coined the term NABBs.
The team visualized individual antibody fragments bound to the receptors with an electron microscope. And, as a proof of principle, they experimented with rhodopsin, a prototypical GPCR. They found that rhodopsin was remarkably stable in NABBs — as stable as in its native membranes. They also found that it doesn’t require a “dimer,” or union of two rhodopsin receptors, to produce a response — as many scientists had argued — but that rhodopsin can be activated in its monomeric form.
“Each protein is very happy inside its own disc and the beauty is that both sides of these receptors, the part that is inside the cell and the part that is outside, are exposed to whatever you want to test it with,” Sakmar says. “That way we can use it to monitor what happens on both sides of the cell membrane.”
“This tool can be used for a wide variety of membrane proteins,” Banerjee says. “We think it will be important for high-throughput screening for new drugs that can bind to membrane proteins involved in disease.”
Ultrafast electron microscopy reveals switchable nanochannels in materials
Microscopic fissures in a tiny crystal open and close—on command. Researchers led by Ahmed H. Zewail successfully used ultrafast electron microscopy (UEM) to observe nanoscopic structures at their “exercises”, as they report in the journal Angewandte Chemie. Such switchable nanochannels could be useful for future nanoelectronics and nanoscopic “machines”.
Zewail and his team at the California Institute of Technology (Pasadena, USA) are renowned for their work in ultrafast science and technology. Zewail received the Nobel Prize in Chemistry in 1999 for the development of ultrafast laser techniques that are capable of revealing the motions of individual atoms within a molecule during a reaction.
The most recent development to spring from Zewail’s Laboratory is ultrafast electron microscopy. This technique is a combination of a femtosecond optical system (a femtosecond equals 10-15 seconds) with a high-resolution electron microscope; the result is a new tool with extremely high resolution in time as well as in space.
Zewail and his team have now discovered that needle-shaped microcrystals of copper and the organic compound TCNQ (7,7,8,8-tetracyanoquinodimethane, C12H4N4 ), a crystalline, quasi-one-dimensional semiconductor, exhibit optomechanical phenomena that could be of use in nanoelectronic applications.
The investigation showed that these crystals stretch out to become longer (but not wider) when they are irradiated with laser pulses in the microscope. If the irradiation is switched off, they contract back to their original size. This effect was most obvious when one of these needles was broken by the shock of a short, strong laser pulse: A small crack of some ten to one hundred nanometers forms at the break. When the crystal is stretched out under irradiation, the nanoscale channel closes up; upon contraction, it reappears. The phenomenon is reversible, as confirmed by UEM. Why do these micromaterials stretch under light? Within the crystal, the negatively charged TCNQ ions are arranged so that their central, flat, six-membered rings are piled up on top of each other in the long direction of the needle. The energy of a laser pulse excites electrons; part of this energy is transferred, resulting in uncharged TCNQ molecules. For the uncharged TCNQ, the stacked arrangement is no longer favorable, they now require more space and cause the crystal to grow longer. The degree of stretching depends on the strength of the energy absorbed.
“Our fundamental in situ UEM observations, which reveal the behavior of nanoscopic matter in space and time, opens up new areas to explore, especially in materials science, nanotechnology, and biology,” says Zewail.
Citation: Ahmed H. Zewail, Controlled Nanoscale Mechanical Phenomena Discovered with Ultrafast Electron Microscopy, Angewandte Chemie International Edition 2007, 46, No. 48, 9206–9210, doi: 10.1002/anie.200704147
Introduction to Nanotechnology and our Nanomaterials
Nanostructured materials have dimensions typically ranging from 1 to 100 nm (where 10 angstrom = 1 nm =1/1000 micrometer). They can be classified into the following dimensional types:
Zero dimensional (0D): nanospherical particles.
One dimensional (1D): nanorods, nanowires and nanotubes.
Two dimensional (2D): nanoflakes, nanodiscs and nanofilms.
Three dimensional (3D): bulk nanostructured materials, consisting of nanometer-sized grains or nanoporous particles.
In nanostructured materials, the proportion of atoms in the grain boundaries or particle surfaces can be equivalent to those inside the grain or particle interiors, these novel types of nanomaterials exhibit properties and performance such as larger specific surface area and dangling bonds or excessive surface energy level or chemical and physic activities that can be very different than those of conventional microsize materials with larger particle or grain sizes. Such dimension is near to some of critical points of magnetic, optical, superconductivity, etc.. These unique properties and performance benefits include, but are not limited to:
Better radiation absorption or shielding.
Better interface connection or binding (in filler/polymer nanocomposites).
High sensitivity for sensor devices.
Transparent pigments (when the filler size is less than 1/4 to 1/2 of the wavelength of the radiation light)
Higher storage capacity of energy such as electrons, solar light, and hydrogen gas.
High density and high speed information storage and transport.
Conductive Carbon Nanofibe or Oxides,
High hardness and good conductive such as Ag-based and Cu-based nanocrystalline alloys.
High strength and high-ductility nanocrystalline ceramics parts, which can be used for cutting, grinding and more.
High reaction rates, especially useful for catalysts and waste treatment.
Sintering additives.
Low melting packaging materials.
High dielectronic ceramic oxides...
Because of these unique properties, nanostructured materials can have a wide variety of applications in Composites, Coating, Particle Film devices, Catalyst, Biomedical, Electronic, Optical, Magnetic and Energy Industries.
About Our Product Catalogue
Currently, our company is able to provide our customers with nanostructured (1 nm to 100 nm) and ultrafine-structured (0.1 um to 5 um) powder materials in the form of:
Carbon Nanotubes: single-, double- and multi-walled; short length or networks; bare or functionalized, high surface area Carbon particles/tubes (1,000 m2/g, 2,000 m2/g, & 3,000 m2/g).
Compounds: carbides, nitrides, borides, and fluorides.
Oxides: single-metal, multi-metal, rare-earth, & doped or shelled.
It is sometimes the case that you may not find your desired product in listed amongst the hundreds of items in our catalogue, or anyone else's catalogue. Not to worry: we will work together with you to custom-manufacture a nanostructured material for your specific needs and application. Just contact our sales department, by phone or e-mail, for an individual consultation. Remember:
- When you have a new idea, we can custom-manufacture new nanomaterials for you. -
- When your demand reaches industrial scale, our price can meet your needs
Researchers Create 'Invisibility Cloak' For Colloidal Nanoparticles
Carnegie Mellon University’s Michael Bockstaller and Krzysztof Matyjaszewski have created a version of Harry Potter’s famed “invisibility cloak” for nanoparticles.
Through a collaborative effort, researchers from the departments of Materials Science and Engineering and Chemistry have developed a new design paradigm that makes particles invisible.
In a recent edition of Advanced Materials Magazine, the researchers demonstrate that controlling the structure of nanoparticles can “shrink” their visible size by a factor of thousands without affecting a particle’s actual physical dimension.
“What we are doing is creating a novel technique to control the architecture of nanoparticles that will remedy many of the problems associated with the application of nanomaterials that are so essential to business sectors such as the aerospace and cosmetics industry,” said Bockstaller, an assistant professor of materials science and engineering.
Colloidal particles are omnipresent as additives in current material technologies in order to enhance strength and wear resistance and other attributes. Light scattering that is associated with the presence of particles often results in an undesirable whitish, or milky, appearance of nanoparticles, which presents a tremendous challenge to current material technologies. Carnegie Mellon researchers have successfully created a way to prevent this problem by grafting polymers onto the particles’ surface. Essentially, what we learned how to do was to control the density, composition and size of polymers attached to inorganic materials which in turn improves the optical transparency of polymer composites. In a sense, light can flow freely through the particle by putting ‘grease’ onto its surface,” said Matyjaszewski, the J.C. Warner University Professor of Natural Sciences in the Department of Chemistry.
The new “particle invisibility cloak” will help create a vast array of new material technologies that combine unknown property combinations such as strength and durability with optical transparency.
Switchable nanovalves: pH-sensitive pseudorotaxane as reversible gate for drug nanotransporter
We encounter valves every day, whether in the water faucet, the carburetor in our car, or our bicycle tire tube. Valves are also present in the world of nanotechnology.
A team of researchers headed by J. Fraser Stoddart and Jeffrey I. Zink at the University of California, Los Angeles, has now developed a new nanovalve. In the journal Angewandte Chemie, the scientists reveal what is special about it: In contrast to prior versions, which only function in organic solvents, this valve operates in an aqueous environment and under physiological conditions—prerequisites for any application as a gate for nanoscopic drug-transport agents, which need to set their cargo free at the right place and time.
In order for pharmaceuticals to affect only the target diseased organ, suitable nanopackaging is required to bring the drug to the target area and release it only there. One example of a good nanoscopic packaging agent is a tiny sphere of porous silica. Its pores can be filled with the drug and closed with tiny controllable valves.
The scientists attached stem-shaped molecules onto the surface of the porous spheres and filled the pores with guest molecules. At neutral to acidic pH values, they stacked cucurbituril molecules onto these “stems”. Cucurbituril is a fat, ring-shaped molecule reminiscent of a pumpkin that has both ends hollowed out. The resulting supramolecular structure, which resembles a skewered pumpkin and is known to chemists as a pseudorotaxane, blocks the pores, so that the guest molecules cannot exit. The nanovalve is closed.
If the pH value is raised into the basic range, however, the interaction between the “pumpkins” and the “skewers” is weakened, and the pumpkins come off, opening the pores. Now the valves are open and the guest molecules can exit.
At this point the molecular details of the individual components still need to be tweaked. The goal: very small differences in pH values between healthy and diseased tissue should be sufficient to switch the valves and release the drug only in diseased cells.
Citation: Jeffrey I. Zink, pH-Responsive Supramolecular Nanovalves Based on Cucurbit[6]uril Pseudorotaxanes, Angewandte Chemie International
On a 'roll': Researchers devise new cell-sorting system
Capitalizing on a cell’s ability to roll along a surface, MIT researchers have developed a simple, inexpensive system to sort different kinds of cells — a process that could result in low-cost tools to test for diseases such as cancer, even in remote locations.
Rohit Karnik, an MIT assistant professor of mechanical engineering and lead author of a paper on the new finding appearing this week in the journal Nano Letters, said the cell-sorting method was minimally invasive and highly innovative.
“It’s a new discovery,” Karnik said. “Nobody has ever done anything like this before.”
The method relies on the way cells sometimes interact with a surface (such as the wall of a blood vessel) by rolling along it. In the new device, a surface is coated with lines of a material that interacts with the cells, making it seem sticky to specific types of cells. The sticky lines are oriented diagonally to the flow of cell-containing fluid passing over the surface, so as certain kinds of cells respond to the coating they are nudged to one side, allowing them to be separated out.
Cancer cells, for example, can be separated from normal cells by this method, which could ultimately lead to a simple device for cancer screening. Stem cells also exhibit the same kind of selective response, so such devices could eventually be used in research labs to concentrate these cells for further study. Normally, it takes an array of lab equipment and several separate steps to achieve this kind of separation of cells. This can make such methods impractical for widespread screening of blood samples in the field, especially in remote areas. “Our system is tailor-made for analysis of blood,” Karnik says. In addition, some kinds of cells, including stem cells, are very sensitive to external conditions, so this system could allow them to be concentrated with much less damage than with conventional multi-stage lab techniques.
“If you’re out in the field and you want to diagnose something, you don’t want to have to do several steps,” Karnik says. With the new system, “you can sort cells in a very simple way, without processing.”
Now that the basic principle has been harnessed in the lab, Karnik estimates it may take up to two years to develop into a standard device that could be used for laboratory research purposes. Because of the need for extensive testing, development of a device for clinical use could take about five years, he estimates.
Fluorescent organic nanoparticles help illuminate cellular proteins
Like a smart highlighter, immunofluorescent labeling can zero in on a specific protein, helping scientists understand the structure of a cell and how diseases affect that structure. Current techniques have disadvantages, though.
University of Michigan scientists developed a non-toxic, organic nanoparticle for immunofluorescent labeling that makes a bright, longer-lasting glow without the drawbacks of today's popular methods. A paper on the research will be published in the March 18 edition of the journal Advanced Materials.
"We've demonstrated the promising application of organic nanoparticles for immunofluorescent labeling," said Jinsang Kim, assistant professor of materials science and engineering who is the principal investigator of this research.
"Our molecules show unique properties. When they clump together, they get brighter, which is the opposite of what normally happens. Normally, when fluorescent molecules clump together, they become much dimmer, which is called self-quenching. Self-quenching is not a problem for our molecules."
Immunofluorescent labeling works like this: Scientists join fluorescent particles with protein-seeking molecules and let the companions loose in cells to bind to the protein they want to locate and study. The scientists then radiate the mixture with ultraviolet light. The light causes the fluorescent particles to glow, giving away the location of the protein the scientists were looking for.
Certain diseases can change the amount of particular proteins in cells. Prostate tumors, for example, can increase the level of prostate-specific antigen, or PSA, which is a cellular protein.
For fluorescent particles, scientists can currently choose between organic fluorescent dyes and inorganic quantum dots, both of which have shortcomings. Organic fluorescent dyes wear out easily from the ultraviolet light and inorganic quantum dots are toxic. Kim's nanoparticles bridge the gap between these methods. They're non-toxic, and the researchers' novel way of making the nanoparticles causes them to shine brightly without deteriorating as easily as organic dyes.
Kim and his colleagues started by directing the self-assembly of a new kind of green fluorescent organic molecule called DBO. They mixed the fluorescent organic molecules in water together with a molecule called diacetylene that formed multi-layered bubbles around the fluorescent molecules and formed polymers. The fluorescent molecules glowed more than 12 times brighter in the multi-layered bubbles than they did in plain solution because of a unique arrangement of the molecules inside the bubbles.
The researchers tested their new nanoparticles by attaching them to biotin, a molecule that binds readily with the protein avidin. The researchers released the nanoparticles with biotin on a glass slide containing spots of avidin. The biotin found the avidin and Kim's nanoparticles glowed.
"More interestingly," Kim said, "the pressure-sensitive polydiacetylene bilayer surrounding the fluorescent nanoparticles also produced its own red fluorescence induced by the pressure the nanoparticles experienced when they attached to the target area. Green can't be seen through skin, but red can. This suggests additional applications for these nanoparticles."
The paper is called "Highly Emissive Self-assembled Organic Nanoparticles having Dual Color Capacity for Targeted Immunofluorescent Labeling."
Nanopartz patent pending gold nanorods combine the revolutionary optical, photothermal, and mechanical properties inherent in the gold nanorod structure with a well characterized highly customizable surface for directing the bioactivity of gold nanorods or for conjugating them to a wide range of molecules of interest. Nanopartz gold nanorods represent a truly enabling "nanotechnology" - the many benefits they bring to optical, photothermal, and material methodology include:
Inherently non-toxic, ideal for in-vivo and in-vitro applications
Coatings that provide half-life in-vivo circulation greater than twenty hours
Absorption and scattering cross sections that are two orders of magnitude greater than Nanoshells at one-fifth the size
Intense absorption and scattering bands in the near infrared, orders of magnitude greater than spherical gold nanoparticles or QDs at advantageous wavelengths not available to either
Two photon fluorescence equal to QDs
High photothermal conversion rate
Optical properties that benefit the use as subcomponents in polarizers, filters, and negative refractive index materials
SERS Labels for In-Vivo and In-Vitro imaging utilizing Surface Enhanced Raman, Resonance Light Scattering
Sensors
X-ray Contrast Enhancement
Optical polarizers, filters, negative index refraction materials
Micro-Antennas
Applications on the Web
THERAPEUTICS
Gold Nanorods Mediate Tumor Cell Death by Compromising Membrane Integrity
Folate-conjugated gold nanorods targeted to tumor cell surfaces produced severe membrane damage upon near-infrared irradiation. Photoinduced injury to the plasma membrane resulted in a rapid increase in intracellular calcium with subsequent disruption of the actin network, featured prominently by the formation of membrane blebs.
L. Tong, Y. Zhao, T. B. Huff, M. N. Hansen, A. Wei, J.-X. Cheng
Hyperthermic effects of gold nanorods on tumor cells
Plasmon-resonant gold nanorods, which have large absorption cross sections at near-infrared frequencies, are excellent candidates as multifunctional agents for image-guided therapies based on localized hyperthermia. The controlled modification of the surface chemistry of the nanorods is of critical importance, as issues of cell-specific targeting and nonspecific uptake must be addressed prior to clinical evaluation. Nanorods coated with cetyltrimethylammonium bromide (a cationic surfactant used in nanorod synthesis) are internalized within hours into KB cells by a nonspecific uptake pathway, whereas the careful removal of cetyltrimethylammonium bromide from nanorods functionalized with folate results in their accumulation on the cell surface over the same time interval. In either case, the nanorods render the tumor cells highly susceptible to photothermal damage when irradiated at the nanorods' longitudinal plasmon resonance, generating extensive blebbing of the cell membrane at laser fluences as low as 30 J/cm2.
Huff, Terry B; Tong, Ling; Zhao, Yan; Hansen, Matthew N; Cheng, Ji-Xin; Wei, Alexander
Nanomedicine, Volume 2, Number 1, February 2007 , pp. 125-132(8)
Nanoparticles with unique optical properties, facile surface chemistry, and appropriate size scale are generating much enthusiasm in molecular biology and medicine. Noble metal, especially Au, nanoparticles have immense potential for cancer diagnosis and therapy on account of their surface plasmon resonance (SPR) enhanced light scattering and absorption. Conjugation of Au nanoparticles to ligands specifically targeted to biomarkers on cancer cells allows molecular-specific imaging and detection of cancer. Additionally, Au nanoparticles efficiently convert the strongly absorbed light into localized heat, which can be exploited for the selective laser photothermal therapy of cancer. We discuss recent advances in the study and use of selectively targeted Au nanospheres in cancer photodiagnostics and photothermal therapy. By changing the shape or composition of Au nanoparticles, the SPR can be tuned to the near-infrared region, allowing in vivo imaging and photothermal therapy of cancer. The use of Au nanorods and silica-Au core-shell nanoparticles for in vivo cancer detection and therapy is discussed.
Prashant K. Jain, Ivan H. El-Sayed, and Mostafa A. El-Sayed
Photothermal reshaping of gold nanorods prevents further cell death
The combined use of phosphatidylcholine passivated gold nanorods (PC-NRs) and pulsed near-infrared (near-IR) irradiation resulted in cell death. Pulsed near-IR laser irradiation also induced reshaping of PC-NRs into spherical nanoparticles. Since reshaped particles showed no absorption in the near-IR region, successive laser irradiation did not affect cells. Photo-reshaping of PC-NRs is expected to be advantageous in preventing unwanted cell damage following destruction of target cells.
Hironobu Takahashi et al
2006 Nanotechnology 17 4431-4435
Biomedical applications of plasmon resonant metal nanoparticles
The strong optical absorption and scattering of noble metal nanoparticles is due to an effect called localized surface plasmon resonance, which enables the development of novel biomedical applications. The resonant extinction, which can be tuned to the near-infrared, allows the nanoparticles to act as molecular contrast agents in a spectral region where tissue is relatively transparent. The localized heating due to resonant absorption, also tunable into the near-infared, enables new thermal ablation therapies and drug delivery mechanisms. The sensitivity of these resonances to their environment leads to simple affinity sensors for the detection of low-level molecular analytes. Coupled with their general lack of toxicity, these applications suggest that noble metal nanoparticles are a highly promising class of nanomaterials for new biomedical applications.
Hongwei Liao, Colleen L Neh & Jason H Hafner
Nanomedicine August 2006, Vol. 1, No. 2, Pages 201-208
In vitro and in vivo two-photon luminescence imaging
Gold nanorods excited at 830 nm on a far-field laser-scanning microscope produced strong two-photon luminescence (TPL) intensities, with a cos4 dependence on the incident polarization. The TPL excitation spectrum can be superimposed onto the longitudinal plasmon band, indicating a plasmon-enhanced two-photon absorption cross section. The TPL signal from a single nanorod is 58 times that of the two-photon fluorescence signal from a single rhodamine molecule. The application of gold nanorods as TPL imaging agents is demonstrated by in vivo imaging of single nanorods flowing in mouse ear blood vessels.
Haifeng Wang, Terry B. Huff, Daniel A. Zweifel, Wei He, Philip S. Low, Alexander Wei, and Ji-Xin Cheng
Plasmon-resonant nanorods as multimodal agents for two-photon luminescent imaging and photothermal therapy
Plasmon-resonant gold nanorods have outstanding potential as multifunctional agents for image-guided therapies. Nanorods have large absorption cross sections at near-infrared (NIR) frequencies, and produce two-photon luminescence (TPL) when excited by fs-pulsed laser irradiation. The TPL signals can be detected with single-particle sensitivity, enabling nanorods to be imaged in vivo while passing through blood vessels at subpicomolar concentrations. Furthermore, cells labeled with nanorods become highly susceptible to photothermal damage when irradiated at plasmon resonance, often resulting in a dramatic blebbing of the cell membrane. However, the straightforward application of gold nanorods for cell-specific labeling is obstructed by the presence of CTAB, a cationic surfactant carried over from nanorod synthesis which also promotes their nonspecific uptake into cells. Careful exchange and replacement of CTAB can be achieved by introducing oligoethyleneglycol (OEG) units capable of chemisorption onto nanorod surfaces by in situ dithiocarbamate formation, a novel method of surface functionalization. Nanorods with a dense coating of methyl-terminated OEG chains are shielded from nonspecific cell uptake, whereas nanorods functionalized with folate-terminated OEG chains accumulate on the surface of tumor cells overexpressing their cognate receptor, with subsequent delivery of photoinduced cell damage at low laser fluence.
Terry B. Huff, Matthew N. Hansen, Ling Tong, Yan Zhao, Haifeng Wang, Daniel A. Zweifel, Ji-Xin Chenga, and Alexander Wei
Plasmon-resonant gold nanorods as low backscattering albedo contrast agents for optical coherence tomography
Plasmon-resonant gold nanorods are demonstrated as low backscattering albedo contrast agents for optical coherence tomography (OCT). We define the backscattering albedo, a , as the ratio of the backscattering to extinction coefficient. Contrast agents which modify a within the host tissue phantoms are detected with greater sensitivity by the differential OCT measurement of both a and extinction. Optimum sensitivity is achieved by maximizing the difference between contrast agents and tissue. Low backscattering albedo gold nanorods (14× 44 nm; λ max = 780 nm) within a high backscattering albedo tissue phantom with an uncertainty in concentration of 20% (randomized 2±0.4% intralipid) were readily detected at 82 ppm (by weight) in a regime where extinction alone could not discriminate nanorods. The estimated threshold of detection was 30 ppm.
Amy L. Oldenburg, Matthew N. Hansen, Daniel A. Zweifel, and Alexander Wei, Stephen A. Boppart
Cancer Cells Assemble and Align Gold Nanorods Conjugated to Antibodies to Produce Highly Enhanced, Sharp, and Polarized Surface Raman Spectra: A Potential Cancer Diagnostic Marker
Human oral cancer cells are found to assemble and align gold nanorods conjugated to anti-epidermal growth factor receptor (anti-EGFR) antibodies. Immunoconjugated gold nanorods and nanospheres were shown previously to exhibit strong Rayleigh (Mie) scattering useful for imaging. In the present letter, molecules near the nanorods on the cancer cells are found to give a Raman spectrum that is greatly enhanced (due to the high surface plasmon field of the nanorod assembly in which their extended surface plasmon fields overlap), sharp (due to a homogeneous environment), and polarized (due to anisotropic alignments). These observed properties can be used as diagnostic signatures for cancer cells.
Xiaohua Huang, Ivan H. El-Sayed, Wei Qian, and Mostafa A. El-Sayed
Nano Lett., 2007, 7, (6), pp 1591–1597
Gold Nanorods Coated with Multilayer Polyelectrolyte as Contrast Agents for Multimodal Imaging
Gold nanorods coated with multilayer polyelectrolyte is reported as a biocompatible optical probe with capability for dark-field imaging and for electron microscopy of cancer cells. Transferrin (Tf) was conjugated to the polyelectrolyte-coated nanorods for targeted in vitro delivery to cancer cells. Dark-field imaging was used to confirm the receptor-mediated uptake of nanorods into HeLa cells, which is known to overexpress the transferrin receptor (TfR). Minimal uptake was observed with untargeted nanorods. Electron microscopy was used to confirm that the intracellular uptake of the nanorods predominantly occurred via the Tf-TfR interaction and the nanorods localized in vesicular structures such as endosomes.
Hong Ding, Ken-Tye Yong, Indrajit Roy, Haridas E. Pudavar, Wing Cheung Law, Earl J. Bergey, and Paras N. Prasad
J. Phys. Chem. C,111 (34), 12552 -12557, 2007. 10.1021
Optical coherence tomography with plasmon resonant nanorods of gold
We explored plasmon resonant nanorods of gold as a contrast agent for optical coherence tomography (OCT). Nanorod suspensions were generated through wet chemical synthesis and characterized with spectrophotometry, transmission electron microscopy, and OCT. Polyacrylamide-based phantoms were generated with appropriate scattering and anisotropy coefficients (30 cm−1 and 0.89, respectively) to image distribution of the contrast agent in an environment similar to that of tissue. The observed signal was dependent on whether the plasmon resonance peak overlapped the source bandwidth of the OCT, confirming the resonant character of enhancement. Gold nanorods with plasmon resonance wavelengths overlapping the OCT source yielded a signal-to-background ratio of 4.5 dB, relative to the tissue phantom. Strategies for OCT imaging with nanorods are discussed.
Timothy S. Troutman, Jennifer K. Barton, and Marek Romanowski
Optics Letters, Vol. 32, Issue 11, pp. 1438-1440
IN-VIVO Developments
Controlling the Cellular Uptake of Gold Nanorods
Gold nanorods coated with cetyltrimethylammonium bromide (CTAB, a cationic micellar surfactant used in nanorod synthesis, were rapidly and irreversibly internalized by KB cells via a nonspecific uptake mechanism. Internalized nanorods near the cell surface were monitored by two-photon luminescence (TPL) microscopy and observed to migrate toward the nucleus with a quadratic rate of diffusion. The internalized nanorods were not excreted but formed permanent aggregates within the cells, which remained healthy and grew to confluence over a 5-day period. Nonspecific nanorod uptake could be greatly reduced by displacing the CTAB surfactant layer with chemisorptive surfactants, particularly by the conjugation of poly(ethylene glycol) chains onto nanorods using in situ dithiocarbamate formation.
Terry B. Huff, Matthew N. Hansen, Yan Zhao, Ji-Xin Cheng, and Alexander Wei
PEG-modified gold nanorods with a stealth character for in vivo applications
Gold nanorods prepared in hexadecyltrimethylammonium bromide (CTAB) solution are expected to provide novel materials for photothermal therapy and photo-controlled drug delivery systems. Since gold nanorods stabilized with CTAB show strong cytotoxicity, we developed a technique to modify these with polyethyleneglycol (PEG) for medical applications. PEG-modification was achieved by adding mPEG-SH in the CTAB solution, then, excess CTAB was removed by dialysis. PEG-modified gold nanoparticles showed a nearly neutral surface, and had little cytotoxicity in vitro. Following intravenous injection into mice, 54% of injected PEG-modified gold nanoparticles were found in blood at 0.5 h after intravenous injection, whereas most of gold was detected in the liver in the case of original gold nanorods stabilized with CTAB.
Journal of Controlled Release Volume 114, Issue 3, 12 September 2006, Pages 343-347
OPTICAL FILTERS, POLARIZERS, AND NON-LINEAR OPTICS
Optical properties of nanometer-sized gold spheres and rods embedded in anodic alumina matrices
This letter discusses theoretical studies of optical properties of gold nanospheres and nanorods with various aspect ratios; these are embedded in a porous anodic alumina matrix. The nanoparticles have potential applications in optical filters and sensors. In recent years, the interaction of light at metal/dielectric interfaces that leads to the formation of surface plasmon waves at specific frequencies has been the focus of intense research. The structures of interest for plasmonics are small metallic particles, wires, rods, and thin films that act as dipole oscillators and whose plasmon frequencies are in or near the visible spectral range. The interesting cases are usually those in which the plasmon lines incur minimal interference from interband optical transitions. In these cases, the surface plasmon resonances are usually dependent on the size, shape, and degree of particle-to-particle coupling; furthermore, they are also dependent on the dielectric properties of the metal from which the nanoparticles are made, and the dielectric properties of the matrix into which the nanoparticles are embedded.
V. G. Stolerua and E. Toweb
APPLIED PHYSICS LETTERS VOLUME 85, NUMBER 22 29 NOVEMBER 2004
Optical Control and Patterning of Gold-Nanorod-Poly(vinyl alcohol) Nanocomposite Films
Gold nanorods with well-defined aspect ratios are homogeneously incorporated within poly(vinyl alcohol) thin films and subsequently aligned by heating and stretching the nanocomposite films. The spatial alignment of the nanorods is directly proved using transmission electron microscopy. The polarization-dependent optical response of the rods is measured and compared with a dipole model. Excellent agreement is found. Additionally, irradiation of the film with nanosecond laser pulses (1064 nm) leads to selective reshaping of the nanorods into nanospheres, and we demonstrate that this effect can be used to micropattern optical structures into the films.
Jorge Perez-Juste, Benito Rodriguez-Gonzalez, Paul Mulvaney, and Luis M. Liz-Marzan
Spectrally-selective Gold Nanorod Coatings for Window Glass
The unique optical properties of gold nanorods, which exhibit tuneable absorption as a function of their aspect ratio, suggest that they might have potential applications in coatings for solar control on windows. Here we explore the properties of coatings produced by attaching gold nanorods to the surface of glass. Such coatings can attenuate solar radiation effectively, even at very low gold contents, but the figure-of-merit, Tvis/Tsol, of our experimental coatings was close to unity, indicating that they are not spectrally selective, However, calculations are presented to show how coatings comprised of a blend of rods with aspect ratios of greater than 3 can produce coatings with Tvis/Tsol of up to at least 1.4. The maximum value possible for perfectly spectrally-selective coating in sunlight is 2.08. Unfortunately, the practical realization of such coatings requires the further development of reliable methods to scale up the production of gold nanorods of longer aspect ratios.
Xu, X.; Gibbons, T.H.; Cortie, M.B.
Gold Bulletin, Volume 39, Number 4, December 2006 , pp. 156-165(10)
Second harmonic generation from resonantly excited arrays of gold nanoparticles
We show that second harmonic generation from lithographically prepared arrays of symmetric gold nanorods can be increased by two orders of magnitude by choosing the nanoparticle size to be resonant with the 800-nm wavelength of the 50-fs pump laser. The angular variation of the second-harmonic yield, which is defined by the pitch of the nanorod array, can be predicted using standard diffraction theory. This in turn makes it possible to bound approximately the relative contributions of dipole and quadrupole oscillations to the total second-harmonic yield; the two contributions appear to be of similar magnitude. Resonant ultrafast irradiation also changes the nanorod morphology, apparently due to surface melting and refreezing. At higher fluence, the intensity dependence of the second-harmonic yield changes from quadratic to cubic, an indication that the reshaping influences the mechanism of second-harmonic generation.
Applied Physics B, Volume 87, Number 2, April 2007 , pp. 259-265(7)
Light propagation in nanorod arrays
We study the propagation of TM- and TE-polarized light in two-dimensional arrays of silver nanorods of various diameters in a gelatin background. We calculate the transmittance, reflectance and absorption of arranged and disordered nanorod arrays and compare the exact numerical results with the predictions of the Maxwell–Garnett effective-medium theory. We show that interactions between nanorods, multipole contributions and formations of photonic gaps affect strongly the transmittance spectra that cannot be accounted for in terms of the conventional effective-medium theory. We also demonstrate and explain the degradation of the transmittance in arrays with randomly located rods as well as the weak influence of their fluctuating diameter. For TM modes we outline the importance of the skin effect, which causes the full reflection of the incoming light. We then illustrate the possibility of using periodic arrays of nanorods as high-quality polarizers.
A I Rahachou and I V Zozoulenko
A I Rahachou et al 2007 J. Opt. A: Pure Appl. Opt. 9 265-270
DIAGNOSTICS
Nanoparticles in biomolecular detection
The use of nanoparticles as labels in biomolecular detection in place of conventional molecular fluorophores has led to improvements in sensitivity, selectivity, and multiplexing capacity. Nevertheless, further simplification is needed to take these technologies from the laboratory to point of care. Here, we summarize the latest developments in the use of nanoparticles as labels, especially in bioaffinity sensors for the detection of nucleic acids and proteins.
Comparing the influence of gold nanorods and -discs on the spontaneous decay rate of Eu-chelate dye
Nanometre-sized metal structures support localized surface plasmons associated with the collective oscillations of conduction band electrons. These modes can give rise to a drastic enhancement of local electromagnetic fields close to the surface of the structures. As a consequence, the fluorescence properties of molecules in that near field zone become strongly modified. In this paper, we investigate the modifications of the de-excitation processes in Eu-chelate dye for various nanoparticle sizes and shapes. By this coupling, in the electronic de-excitation process the corresponding radiative and non-radiative rates can be enhanced by orders of magnitude with respect to the free-space case. When the plasmon resonance overlaps well with the molecule's fluorescence emission frequency the interacting molecules show a dramatically shortened fluorescence lifetime but an enhanced signal amplitude. This is a valuable mechanism for new labelling techniques in biosciences and for modifications of OLED emission properties.
Reil, Frank; Gerber, Sebastian; Krenn, Joachim R.; Leitner, Alfred
Journal of Optics A: Pure and Applied Optics, Volume 9, Number 9, September 2007 , pp. S437-S442(1)
MATERIALS
Light scattering from gold nanorods: tracking material deformation
We demonstrate the use of optical patterns, produced by resonant Rayleigh scattering from gold nanorods, as markers by which local deformations can be measured using image correlation techniques. While the use of optical data, in this case from dark-field microscopy, to generate deformational field information (displacements and strains) is not new, the use of the light scattered from gold nanorods as the correlated pattern is new, and has the potential to enable smaller scale measurements even over large deformations. We find excellent agreement between the measured and theoretical deformation and strain fields for two sample polymers with gold nanorod markers. The gold nanorod surface can be modified to make biocompatible nanomaterials, which will be useful for examining mechanical effects in biological tissue.
Hybrid Microgels Photoresponsive in the Near-Infrared Spectral Range
We report for the first time a photothermally responsive composite material based on polymer microgel particles doped with gold nanorods. We used the dependence of the longitudinal surface plasmon of the gold nanorods on their aspect ratio to synthesize nanoparticles with strong absorption in the near-IR spectral range (in the "water window"). The nanoparticles were incorporated in the interior of temperature-responsive poly(N-isopropylacrylamide-acrylic acid) microgels. Upon irradiation at = 810 nm, hybrid microgel particles doped with Au nanorods underwent a strong deswelling phase transition. These photothermally responsive microgels can be used to carry and release small molecules (e.g., small protein molecules and drugs).
Ivan Gorelikov, Lora M. Field, and Eugenia Kumacheva
J. Am. Chem. Soc., 126 (49), 15938 -15939, 2004
SENSORS
Pushing the Limits of Mercury Sensors with Gold Nanorods
The method presented here provides a direct way to determine mercury in tap water samples at the parts-per-trillion level. Its outstanding selectivity and sensitivity results from the well-known amalgamation process that occurs between mercury and gold. The entire procedure takes less than 10 minutes. No sample separation and/or sample pre-concentration is required. The only step prior to mercury determination consists of mixing the water sample with a gold nanorod solution in sodium borohydride. The analytical figures of merit demonstrate precise and accurate analysis at the parts-per-trillion level. The limit of detection (6.6x10-13 g.L-1) shows excellent potential for monitoring ultra-low levels of mercury in water samples.
F.E. Hernandez, M. Rexand and A.D. Campiglia
Anal. Chem., 78 (2), 445 -451, 2006
NANO-BUILDING BLOCKS
Imaging and Manipulation of Gold Nanorods with an Atomic Force Microscope
Designed fabrication of nanostructures requires progress on a number of fronts in research and development. The ability to synthesize, deposit, and position nanometer scale materials is important for the development of this technology. We report here on studies of deposition and manipulation of electrochemically prepared, micelle-capped Au nanorods deposited on silicon dioxide (SiO2) surfaces. A thiol-terminated silane (3-mercaptopropylmethyldimethoxysilane, MPMDMS) was used as an active interface for gold nanorod assembly. A scanning force microscope (SFM) was used to image and manipulate individual Au nanorods. It was found that mechanical movement of the rods depends on the location of the pushing point along the rod.
Shuchen Hsieh, Sheffer Meltzer, C. R. Chris Wang, Aristides A. G. Requicha, Mark E. Thompson, and Bruce E. Koel
For the first time, researchers have created solar cells made of different-sized quantum dots, each tuned to a specific wavelength of light. By arranging these quantum dots in an ordered pattern, the scientists hope that they can one day fabricate “rainbow” solar cells, which can efficiently harvest a large part of the useful spectrum of sunlight.
The group of researchers from the University of Notre Dame, Anusorn Kongkanand, Kevin Tvrdy, Kensuke Takechi, Masaru Kuno, and Prashant Kamat, have published their study in a recent issue of the Journal of the American Chemical Society. Their research was funded by the Office of Basic Energy Sciences of the Department of Energy.
Using quantum dots to absorb light has a unique advantage over other light-absorbing materials: the “size quantization effect.” By varying the size of the tiny semiconductor quantum dots, the researchers can tune the solar cells to absorb light of certain wavelengths. Smaller quantum dots absorb shorter wavelengths of light, while larger quantum dots absorb longer wavelengths.
By combining different-sized quantum dots on one solar cell, the researchers can create solar cells that absorb more light and thereby deliver power at greater efficiencies compared with solar cells made of bulk semiconductors.
In the Notre Dame study, the scientists assembled cadmium selenide (CdSe) quantum dots in a single layer on the surface of nano films and tubes made of titanium dioxide (TiO2). After absorbing light, the quantum dots inject electrons into the TiO2 structures, which are then collected at a conducting electrode that generates photocurrent.
“Anchoring CdSe quantum dots on TiO2 nanotubes allowed us to create an ordered assembly of nanostructures,” Kamat told PhysOrg.com. “This architecture facilitated efficient transport of electrons to the collecting electrode surface and allowed us to achieve efficiency improvement.”
The researchers used four different sizes of quantum dots (between 2.3 and 3.7 nm in diameter) which exhibited absorbent peaks at different wavelengths (between 505 and 580 nm). The group observed a trade-off in performance corresponding with quantum dot size: smaller quantum dots could convert photons to electrons at a faster rate than larger quantum dots, but larger quantum dots absorbed a greater percentage of incoming photons than smaller dots. The 3-nm quantum dots offered the best compromise, but the researchers plan to improve both the conversion and absorption performances in future prototypes. Besides investigating the quantum dots’ size quantization effect, the researchers also experimented with two different nano architectures – particle films and nanotubes – that act as scaffolds for transporting electrons from the quantum dots to the electrodes. The group found that the hollow 8000-nm-long nanotubes, where both the inner and outer surfaces were accessible to quantum dots, could transport electrons more efficiently than films.
With the development of the first solar cell with multi-sized quantum dots, the researchers plan to take the next steps and design rainbow solar cells, which would contain different-sized quantum dots assembled in an orderly fashion. With small quantum dots on the outer edge of the cell absorbing blue light, the red light (with longer wavelengths) would pass through the outer layer but still be absorbed by larger quantum dots located in the inner layer. This “rainbow” gradient would combine the faster electron injection rate of small quantum dots and greater absorption range of larger quantum dots, and ultimately lead to a highly efficient solar cell.
“Usually, silicon-based photovoltaic panels operate with an efficiency of 15-20%,” Kamat said. “Silicon solar cells generate only one electron-hole pair per incident photons, irrespective of their energy. Thus, the higher energy of blue light is simply wasted in terms of heat. The obvious question is, can nanotechnology provide new ways to harvest these higher energy photons more efficiently?
“Semiconductor quantum dots seem to be the answer. They are capable of producing multiple charge carriers when excited with high energy light. If we succeed in capturing these charge carriers, we can expect significantly higher efficiencies. The target is to reach efficiency values greater than 30% using quantum dot rainbow solar cells.”
To achieve this efficiency, Kamat explained that there are two main challenges. The first is organizing the light harvesting nanostructures so that they efficiently absorb light in the visible and near infrared region, and transport electrons within the films. Secondly, the quantum dots should generate multiple charge carriers to be captured to generate photocurrent.
“New advances in nanotechnology are key to the success of developing highly efficient and cost-effective solar cells,” he said.
Home owners can attach solar cells to roofs, of course. But, as the Notre Dame researchers suggest, rainbow solar cells might also be used to develop colored windows, where the color can be tuned by changing the size of the quantum dots. Just as in rooftop cells, the quantum dots in the glass could absorb light that could then be converted into electricity.
More information: Kongkanand, Anusorn; Tvrdy, Kevin; Takechi, Kensuke; Kuno, Masaru; and Kamat, Prashant V. “Quantum Dot Solar Cells. Tuning Photoresponse through Size and Shape Control of CdSe-TiO2 Architecture.” J. Am. Chem. Soc. March 1, 2008. DOI: 10.1021/ja0782706.
Copyright 2008 PhysOrg.com. All rights reserved. This material may not be published, broadcast, rewritten or redistributed in whole or part without the express written permission of PhysOrg.com.
IBM researchers quell nanoscale interference
The image shows a single layer, or sheet of carbon molecules known as Graphene. The noise that occurs from electrical signals bouncing around in the material as a current is passed through it is greater as the device is made smaller and smaller, impeding the performance for nanoscale electronics. In the image on the right, the IBM scientists demonstrated for the first time that adding a second sheet of Graphene reduces the noise significantly, giving promise to this material for potential use in future nanoelectronics. Credit: IBM
IBM researchers have discovered a way to use graphite effectively in building nanoelectonic circuits vastly smaller than those in silicon-based computer chips.
IBM researchers today announced a discovery that combats one of the industry's most perplexing problems in using graphite -- the same material found inside pencils -- as a material for building nanoelectonic circuits vastly smaller than those found in today's silicon based computer chips.
For the first time anywhere, IBM scientists have found a way to suppress unwanted interference of electrical signals created when shrinking graphene, a two-dimensional, single-atomic layer thick form of graphite, to dimensions just a few atoms long.
Scientists around the world are exploring the use of graphene as a much smaller replacement for today's silicon transistors. Graphene is a two-dimensional honeycomb lattice of carbon atoms, similar to atomic-scale chicken-wire, which has attracted strong scientific and technological interest because it exhibits promising electrical properties and could be used in transistors and circuits at scales vastly smaller than components inside of today's tiniest computer chips.
One problem in using these nano-devices is the inverse relationship between the size of the device and the amount of uncontrolled electrical noise that is generated: as they are made smaller and smaller, the noise -- electrical charges that bounce around the material causing all sorts of interference that impede their usefulness -- grows larger and larger. This trend is known as Hooge's rule, and occurs in traditional silicon based devices as well as in graphene nano-ribbons and carbon nanotube based devices
"The effect of noise from Hooge's rule is exaggerated at the nanoscale because the dimensions are approaching the nearly smallest limits, down to only a handful of atoms, and the noise that is created can overwhelm the electrical signal that needs to be achieved to be useful," said IBM Researcher Dr. Phaedon Avouris, who leads IBM's exploration into carbon nanotubes and graphene. "To quote the famous physicist Rolf Landauer, at the nanoscale 'the noise is your signal'; in other words, you cannot produce any useful electronic device at the nanoscale if the noise is comparable to the signal you are trying to switch on and off."
Now, IBM scientists have found that the noise in graphene-based semiconductor devices can, in fact, be suppressed and report the results today in the journal Nano Letters.
In their experiments, the IBM Researchers first used a single layer, or sheet, of graphene to build a transistor and noted that the device does in fact follow Hooge's Rule: as they are made smaller and smaller, there is an increase in the noise that is created.
Two Layers Are Better Than One
However, when the IBM Researchers built the same device with two sheets of graphene instead of one -- one stacked on top of the other -- they noted that the noise is suppressed, and is weak enough that these so-called bilayer graphene ribbons could prove useful for building future semiconductor devices for use in sensors, communications devices, computing systems and more. The noise is inhibited because of the strong electronic coupling between the two graphene layers that counteracts the influence of the noise sources: the system acts as a noise insulator.
While further detailed analysis and studies are required to better understand these phenomena, the findings provide exciting opportunities for graphene bilayers in a variety of applications.
The report on this work, entitled "Strong Suppression of Electrical Noise in Bilayer Graphene Nanoribbons" by Yu-Ming Lin and Phaedon Avouris of IBM's T.J.Watson Research Center in Yorktown Heights, N.Y. is available online at the journal Nano Letters: http://pubs.acs.org/cgi-bin/abstract.cgi/nalefd/asap/abs/nl080241l.html
“Elmet Technologies seeks out those opportunities that challenge our engineering and design teams to develop the difficult value-added solutions to customer’s problems. If it’s a difficult product to make, that’s the one we want.”
- Jack Jensen, CEO Elmet Technologies
About Elmet Technologies
Elmet Technologies engineering and design teams thrive on new opportunities and solving challenges. By capitalizing on Elmet’s highly specialized machining and fabrication capabilities in metal production in our ISO 9000 and ISO 14000 certified factory, we offer “total cost of ownership” solutions to our customers.
Elmet’s product lines include high performance materials such as wire, rod, sheet, plate and pressed and sintered parts coupled with world-class custom precision-machined and fabricated parts produced to customer drawings and specifications.
Since 1929 Elmet Technologies has been a manufacturer specializing in molybdenum and tungsten metal, in addition to wire products and other refractory metal products, from our factory in Lewiston, Maine, USA. With it's Maine work ethic and high quality products, Elmet has grown in plant size and production volume as well as in product and service diversity.
Originating with fifty employees and 13,400 square feet in 1929, Elmet now employs more than 230 people with over 220,000 square feet of manufacturing space. With its comprehensive customer service and field sales infrastructure, Elmet is an industry leader offering unique personalized customer purchasing experience as well as customized logistic arrangements.
With a combined market basket of refractory metals and lighting component products and services, Elmet serves a wide range of industries, including electronics, lighting, semiconductor, automotive, fiberglass, aircraft, medical and many others with quality products.
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