The authors thank the Natural Sciences and Engineering Research Council (NSERC) of Canada and the Canada Foundation for Innovation (CFI) for funding and scholarship support.

注：必要な場合重水素化溶媒は、文献の手順に従って乾燥させ、そして他のすべての溶媒をGrubbs&#39;型コラム12の系列上で乾燥し、使用前に脱気しました。カリウム1,2,4-トリス（ジフェニルホスフィノ）シクロペンタ[K] [（PH 2 P）3 C 5 H 2]、N-複素環カルベン-1,3,4,5- tetramethylimidazole -2-イリデン（ME NHC ミー ）は、文献の手順に従って合成し、後者は、使用前に昇華させた。9,13シクロヘキセンは、CaH 2上で乾燥させ、蒸留し、使用前に脱気しました。アセトニトリルD 3（CD 3 CN）およびジクロロメタン-D 2（CD 2 Cl 2）で五酸化リン上で乾燥し、使用前に脱気しました。珪藻土は、使用する前に一晩150ºCのオーブンで乾燥させました。受信されたように、すべての他の試薬を使用しました。 【dppeP] [BR] 1.合成<ol><li> D無水の約40 ml溶液に、1,2-ビス（ジフェニルホスフィノ）エタン（DPPE）のissolve 1.00 gを、ゴム隔膜を装備し、不活性ガス下で250mlのシュレンクフラスコに、ジクロロメタン（DCM）を脱気しました。 </li><li>注射器またはカニューレ転送することで、DPPEの撹拌溶液を含むシュレンクフラスコに乾燥、脱気し、シクロヘキセンの2.53ミリリットルを追加します。 </li><li>この溶液に、注射器、激しく撹拌しながら滴下経由のPBr 3の0.26ミリリットルを追加します。溶液は直ちに20分間溶液を撹拌した後、淡黄色、白色の沈殿物が形成さを有効にしてください。反応は数時間または一晩攪拌します。 </li><li>数時間または一晩撹拌した後、フリット付きフラスコから反応混合物をフィルタリングして沈殿物を除去するために、1インチの厚さの珪藻土のプラグをトッピング。 </li><li>得られた溶液を収集し、シュレンクライン上で真空下でDCMを除去します。 </li><li>得られたオイルに、STながら、テトラヒドロフランの約75ミリリットル（THF）を追加白色の固体として生成物を沈殿させ、激しくirring（または超音波処理）。 </li><li>すぐに白い沈殿物が形成した後、不活性雰囲気下でフリットフラスコに濾過して、それを収集します。すぐに固体を収集し、30分以上攪拌して懸濁液を放置しないでください。 </li><li>一旦集め、純度を確認するために、31 P、1 Hおよび13 C NMRを得るために、CD 2 Cl 2またはCDCl 3中の[dppeP] [BR]を少量溶解させます。 【dppeP] [BR]は不活性雰囲気中で無期限に保存されている、または卓上に数週間のためにすることができます。6 </li></ol> 【dppeP] [BPH 4]の2合成<ol><li>シュレンクフラスコに、DCM 5mlに[dppeP] [BR]塩0.5gを溶解します。窒素ガス下で溶液を撹拌しました。その後、THF 5ml中のテトラフェニルホウ酸ナトリウムの0.35グラムを追加します。 </li><li>解決策は、微細な沈殿が形成されるまで、数時間または一晩攪拌します。 </li><li>遠心分離機の沈殿物（KBr法）を除去し、白色粉末として[dppeP] [BPH 4]を得、減圧下で溶媒を除去しuspension。 </li></ol> 3.合成【 ミー NHC ミー 2 P] [BPH 4] <ol><li>不活性雰囲気下で私 NHC Meおよび撹拌棒の0.200グラムと100ミリリットルシュレンクフラスコをロードします。 </li><li>不活性雰囲気下で[dppeP] [BPH 4]の0.603グラムで100ミリリットル丸底フラスコをロードします。 </li><li> 私の0.200グラムNHC Meおよび磁気撹拌を開始を含むシュレンクフラスコにカニューレ転送20mlのTHFを。 </li><li> 【dppeP] [BPH 4]の0.603グラムと100ミリリットル丸底フラスコにTHFのカニューレ転送20ミリリットル、溶解するまで撹拌します。 </li><li>カニューレは、[dppeP] [BPH 4] THF中のTHF中のミー NHC 私の撹拌溶液への解決策を転送し、黄色の溶液を1時間撹拌することができます。 </li><li>黄色のコンセントレイト減圧下で元の容量（13ミリリットル）の3分のolution。 </li><li>黄色生成物の沈殿を開始し、得られた懸濁液を20分間撹拌することを可能にする攪拌濃縮液にジエチルエーテル（Et 2 O）（40ml）に加えます。 </li><li>シュレンクライン上の100ミリリットルのシュレンクフラスコに取り付け取り付けられた密封されたフリットを置き、フラスコを真空排気を使用し、シュレックラインから窒素でフラスコを補充することにより、不活性雰囲気を作成します。 5分間排気し、不活性雰囲気を保証するために、窒素を3回補充。 </li><li>カニューレは、装置内のEt 2 Oサスペンションを転送し、沈殿物をフィルタリングします。 </li><li> Et 2 Oで3回10mlで沈殿物を洗浄し、沈殿物を減圧下で2時間乾燥させます。 </li><li>オプション）ろ液および洗浄液がDPPEを再結晶化するために、窒素下でゆっくり蒸発させます。ヘキサン、乾燥最小限の量で結晶を洗浄し、収集再利用のための結晶。 </li></ol> （Phは2 P）C 5 H 2（Phで2 P）2の4の合成P <ol><li>不活性雰囲気中で0.484グラム[dppeP] [BR]を含む150ミリリットルシュレンクフラスコに、乾燥の40ミリリットルを追加し、THFを脱気。 </li><li> -78℃にサスペンションを冷却するために、ドライアイス/アセトン浴中でシュレンクを置きます。 </li><li>カニューレは、[dppeP] [BR]を含むシュレンクフラッシュに、丸底フラスコに0.625グラムのTHF溶液[K] [（Phは2 P）3 C 5 H 2]を転送します。 </li><li>添加が完了したら、アセトン浴からシュレンクフラスコを取り外し、室温まで加温することを可能にします。 2時間攪拌した後、溶液を、白色沈殿物が存在で淡黄色です。 </li><li>白色の沈殿物（KBr法）を除去するために、150ミリリットルのシュレンクフラスコを搭載した空気を含まないフリットフィルタにサスペンションを転送します。 </li><li>黄色の溶液を収集し、真空下でTHFを除去。 </li><li> 80:20を追加乾燥および脱気したジエチルエーテルの混合物：得られた油状物をペンタンで20分間撹拌することを可能にします。 </li><li>生成物を回収（PH 2 P）C 5 H 2（Phで2 P）2 P無空気、フリットフラスコを通して懸濁液を濾過することにより、淡黄色の沈殿物として。残りのエーテル/ペンタン溶液をDPPE不純物を含有し、廃棄してもよいし、溶媒を真空、さらなる使用のために収集DPPE下で除去することができます。 </li></ol>

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著者らは、開示することは何もありません。

結晶構造及び多核NMR（31 P、1 Hおよび13 C）は、接続性を確認するために、報告された全ての製品について得られました。エレクトロスプレーイオン化質量分析は、陽イオンの存在を確認するために使用された、元素分析は、サンプルの分析的純度を確認しました。 すべての反応がまたは分解生成物副産物予期しないが形成されないことを確実にす...

異常に低い酸化または原子価状態での主族元素の化学的性質は、過去20年間の大きな関心のエリアとなっている。1別に独自の結合および構造に起因する根本的な関心から、このような化合物は、しばしば非常に異なる反応性を表示しますそれらのより一般的な酸化状態の対応のもの。この意味で、彼らはより複雑なメイングループ元素含有物質を構築するための試薬としての大きな可能性を提供します。 分子を含む低価のリンのランドマーククラスが最初に1980年代にSchmidpeterによって報告された「triphosphenium」カチオンである。2これらのイオンから構築され、より安定した亜種で、2ホスホニオ置換基により連結したdicoordinateリン（I）イオンを備えています。キレートフレームワーク3,4当社グループはtriphospheniumのハロゲン化物塩の合成を最適化5ている- 7と持っていますこれらの安定な化合物は、リンの制御合成（I）のオリゴマー、8両性イオン、9及びphosphamethineシアニン色素を含有するために有用な多目的のP +移動剤であることを実証した。10,11のこのような化合物の元の合成は、しばしば危険なリンを含むが試薬を含有および/または高還元条件、我々が提示する制御経路は、P-原子効率的、かつ便利、安全です。染料として使用することができる高純度材料のメソッドの結果は、遷移金属錯体と、より複雑なリン含有種の前駆体のためのリガンド。

<table border="0" cellpadding="0" cellspacing="0" width="968">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">bis(diphenyl)phosphino ethane (dppe)</td>
			<td style="width:99px;">Strem</td>
			<td style="width:119px;">1663-45-2</td>
			<td style="width:468px;">98% Stored in gloved box, used as is.&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Anhydrous Dichloromethane (DCM)</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">270997</td>
			<td>Purified through solvent purification system, or standard methods</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Anhydrous Cyclohexene&#160;</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">29240</td>
			<td>Dried over calcium hydride and distilled.&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Phosphorus Tribromide (PBr3)</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">157783</td>
			<td>99% Stored in glove box, used as is. Air sensitive</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Anyhydrous Tetrahydrofuran (THF)</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">401757</td>
			<td>Purified through solvent purification system, or standard methods</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Methylene Chloride-D2 (CD2Cl2)</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td style="width:119px;">DLM-23-25</td>
			<td>Dried over phosphorus pentoxide, vacuum transferred or distilled</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Acetonitrile</td>
			<td style="width:99px;">Alfa Aesar</td>
			<td align="right" style="width:119px;">5/8/1975</td>
			<td>Stored in glove box, used as is</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Sodium Tetraphenylborate</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td style="width:119px;">T25402</td>
			<td>Stored in glove box, used as is</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Anyhydrous Diethyl Ether&#160;</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">673811</td>
			<td>Purified through solvent purification system, or standard methods</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Anhydrous Pentane</td>
			<td style="width:99px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">236705</td>
			<td>Purified through solvent purification system, or standard methods</td>
		</tr>
	</tbody>
</table>

preparation and reactivity of a triphosphenium bromide salt: a convenient and stable source of phosphorus(i)

私たちは、ここでtriphospheniumの臭化物塩の最適化された合成を提示します。別に多目的なメタセシス試薬であることから、この異常に安定した低価のリン含有化合物は、有用なP +移動剤として作用します。通常発火リン含有前駆体（白リン、トリス（トリメチルシリル）ホスフィンなど ）、または過酷な還元剤（ 等のアルカリ金属、カリウムグラファイト）、電流を必要とする低座標リン種をアクセスするために用いられる従来の方法とは異なりアプローチは、自然発火や爆発の試薬を伴わないと、基本的な空気のない合成訓練を受けた大学生により優れた収率で大きなスケール（&gt; 20グラム）で行うことができます。臭化物対イオンは、容易に所望の特性および反応性を有する材料を得るために、典型的な塩メタセシス試薬を使用して、そのような（本明細書中に記載）テトラフェニルボレートなどの他の陰イオンと交換されます。このPの+転送 aの汎用性pproach容易それぞれ、双性イオンを含むNHC安定化リン（I）のカチオンと、リン（I）を与えるために、中性ビスホスフィンを変位各々がN-複素環カルベンおよびアニオンビスホスフィン、これらtriphosphenium前駆体の反応によって例示されます。

低原子価リン（I）源を含む安定な塩（[dppeP] [BR]）は（ 図1）6過剰シクロヘキセンの存在下でdiphenylphosphinoethaneへのPBr 3を加え（DPPE）によって容易に合成することができます。 反応のワークアップ時に、31 P NMRスペクトルは大幅-220 ppmに遮蔽されているトリプレット信号の存在、および50 ppmの二重のシグナルを?...

Watch this Scientific Journal Video about Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI at JoVE.com

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.

Triphosphenium臭化物塩の調製と反応性：リンの便利で安定したソース（I）

We present herein the optimized synthesis of a triphosphenium bromide salt. Apart from being a versatile metathesis reagent, this unusually stable ...

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Chemistry

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

7.7K ビュー.  University of Windsor. The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.

ビデオ: Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

二ヨウ化サマリウム（SMIの調製および使用<sub&gt; 2</sub&gt;）有機合成における：サマリウムバルビエ反応におけるHMPAとNi（II）塩の力学的役割

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

化学

Preparing Adherent Cells for X-ray Fluorescence Imaging by Chemical Fixation

X-ray fluorescence imaging allows us to non-destructively measure the spatial distribution and concentration of multiple elements simultaneously over large or small sample areas. It has been applied in many areas of science, including materials science, geoscience, studying works of cultural heritage, and in chemical biology. In the case of chemical biology, for example, visualizing the metal distributions within cells allows us to study both naturally-occurring metal ions in the cells, as well as exogenously-introduced metals such as drugs and nanoparticles. Due to the fully hydrated nature of nearly all biological samples, cryo-fixation followed by imaging under cryogenic temperature represents the ideal imaging modality currently available. However, under the circumstances that such a combination is not easily accessible or practical, aldehyde based chemical fixation remains useful and sometimes inevitable. This article describes in as much detail as possible in the preparation of adherent mammalian cells by chemical fixation for X-ray fluorescent imaging.

Here, we present a protocol on how to determine the quantity and distribution of metals in a sample using synchrotron X-ray fluorescence. We focus on adherent cells, and describe the chemical fixation method to prepare this sample. We then describe how to mount and image the sample using synchrotron X-rays.

化学固定することによりX線蛍光イメージングのための接着細胞の準備

X-ray fluorescence imaging allows us to non-destructively measure the spatial distribution and concentration of multiple elements simultaneously over ...

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性<em&gt; N</em&gt; -triphos<sup&gt; Phで</sup&gt;錯体

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

Preparation of Mica and Silicon Substrates for DNA Origami Analysis and Experimentation

The designed nature and controlled, one-pot synthesis of DNA origami provides exciting opportunities in many fields, particularly nanoelectronics. Many of these applications require interaction with and adhesion of DNA nanostructures to a substrate. Due to its atomically flat and easily cleaned nature, mica has been the substrate of choice for DNA origami experiments. However, the practical applications of mica are relatively limited compared to those of semiconductor substrates. For this reason, a straightforward, stable, and repeatable process for DNA origami adhesion on derivatized silicon oxide is presented here. To promote the adhesion of DNA nanostructures to silicon oxide surface, a self-assembled monolayer of 3-aminopropyltriethoxysilane (APTES) is deposited from an aqueous solution that is compatible with many photoresists. The substrate must be cleaned of all organic and metal contaminants using Radio Corporation of America (RCA) cleaning processes and the native oxide layer must be etched to ensure a flat, functionalizable surface. Cleanrooms are equipped with facilities for silicon cleaning, however many components of DNA origami buffers and solutions are often not allowed in them due to contamination concerns. This manuscript describes the set-up and protocol for in-lab, small-scale silicon cleaning for researchers who do not have access to a cleanroom or would like to incorporate processes that could cause contamination of a cleanroom CMOS clean bench. Additionally, variables for regulating coverage are discussed and how to recognize and avoid common sample preparation problems is described.

Reproducible cleaning processes for substrates used in DNA origami research are described, including bench-top RCA cleaning and derivatization of silicon oxide. Protocols for surface preparation, DNA origami deposition, drying parameters, and simple experimental set-ups are illustrated.

DNA折り紙解析と実験のためのマイカとシリコン基板の作製

The designed nature and controlled, one-pot synthesis of DNA origami provides exciting opportunities in many fields, particularly nanoelectronics. Many of ...

Preparation and Characterization of Individual and Multi-drug Loaded Physically Entrapped Polymeric Micelles

Amphiphilic block copolymers like polyethyleneglycol-block-polylactic acid (PEG-b-PLA) can self-assemble into micelles above their critical micellar concentration forming hydrophobic cores surrounded by hydrophilic shells in aqueous environments. The core of these micelles can be utilized to load hydrophobic, poorly water soluble drugs like docetaxel (DTX) and everolimus (EVR). Systematic characterization of the micelle structure and drug loading capabilities are important before in vitro and in vivo studies can be conducted. The goal of the protocol described herein is to provide the necessary characterization steps to achieve standardized micellar products. DTX and EVR have intrinsic solubilities of 1.9 and 9.6 &#181;g/ml respectively Preparation of these micelles can be achieved through solvent casting which increases the aqueous solubility of DTX and EVR to 1.86 and 1.85 mg/ml, respectively. Drug stability in micelles evaluated at room temperature over 48 hr indicates that 97% or more of the drugs are retained in solution. Micelle size was assessed using dynamic light scattering and indicated that the size of these micelles was below 50 nm and depended on the molecular weight of the polymer. Drug release from the micelles was assessed using dialysis under sink conditions at pH 7.4 at 37 oC over 48 hr. Curve fitting results indicate that drug release is driven by a first order process indicating that it is diffusion driven.

The goal of this protocol is to describe the preparation and characterization of physically entrapped, poorly water soluble drugs in micellar drug delivery systems composed of amphiphilic block copolymers.

調製とキャラクタリゼーション個々のとマルチ薬ロード物理的に捕捉さ高分子ミセル

Amphiphilic block copolymers like polyethyleneglycol-block-polylactic acid (PEG-b-PLA) can self-assemble into micelles above their critical micellar ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

周囲条件下での金ナノ粒子の安定オリゴマークラスターのサイズ制御された合成のための簡単​​な方法

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたはIV）

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the inverse electron demand Diels-Alder (IEDDA) cycloaddition between a radiolabeled tetrazines and trans-cyclooctene (TCO) linked to a biomolecule has proven to be a highly effective bioorthogonal approach to imaging specific biological targets. Despite the fact that technetium-99m remains the most widely used isotope in diagnostic nuclear medicine, there is a scarcity of methods for preparing 99mTc-labeled tetrazines. Herein we report the preparation of a family of tridentate-chelate-tetrazine derivatives and their Tc(I) complexes. These hitherto unknown compounds were radiolabeled with 99mTc using a microwave-assisted method in 31% to 83% radiochemical yield. The products are stable in saline and PBS and react rapidly with TCO derivatives in vitro. Their in vivo pre-targeting abilities were demonstrated using a TCO-bisphosphonate (TCO-BP) derivative that localizes to regions of active bone metabolism or injury. In murine studies, the 99mTc-tetrazines showed high activity concentrations in knees and shoulder joints, which was not observed when experiments were performed in the absence of TCO-BP. The overall uptake in non-target organs and pharmacokinetics varied greatly depending on the nature of the linker and polarity of the chelate.

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Here, we describe a protocol for radiolabeling and in vivo testing of tridentate 99mTc(I) chelate-tetrazine derivatives for pre-targeting and bioorthogonal chemistry.

の調製と評価<sup&gt; 99メートル</sup&gt; Tc標識三座キレートバイオ直交化学反応を用いて事前ターゲティングするため

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the ...

A Convenient Method for Extraction and Analysis with High-Pressure Liquid Chromatography of Catecholamine Neurotransmitters and Their Metabolites

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and related diseases, but their precise measurement is still a challenge. Many protocols have been described for neurotransmitter measurement by a variety of instruments, including high-pressure liquid chromatography (HPLC). However, there are shortcomings, such as complicated operation or hard-to-detect multiple targets, which cannot be avoided, and presently, the dominant analysis technique is still HPLC coupled with sensitive electrochemical or fluorimetric detection, due to its high sensitivity and good selectivity. Here, a detailed protocol is described for the pretreatment and detection of catecholamines with high pressure liquid chromatography with electrochemical detection (HPLC-ECD) in real urine samples of infants, using electrospun composite nanofibers composed of polymeric crown ether with polystyrene as adsorbent, also known as the packed-fiber solid phase extraction (PFSPE) method. We show how urine samples can be easily precleaned by a nanofiber-packed solid phase column, and how the analytes in the sample can be rapidly enriched, desorbed, and detected on an ECD system. PFSPE greatly simplifies the pretreatment procedures for biological samples, allowing for decreased time, expense, and reduction of the loss of targets. 
Overall, this work illustrates a simple and convenient protocol for solid-phase extraction coupled to an HPLC-ECD system for simultaneous determination of three monoamine neurotransmitters (norepinephrine (NE), epinephrine (E), dopamine (DA)) and two of their metabolites (3-methoxy-4-hydroxyphenylglycol (MHPG) and 3,4-dihydroxy-phenylacetic acid (DOPAC)) in infants' urine. The established protocol was applied to assess the differences of urinary catecholamines and their metabolites between high-risk infants with perinatal brain damage and healthy controls. Comparative analysis revealed a significant difference in urinary MHPG between the two groups, indicating that the catecholamine metabolites may be an important candidate marker for early diagnosis of cases at risk for brain damage in infants.

We present a convenient solid-phase extraction coupled to high-pressure liquid chromatography (HPLC) with electrochemical detection (ECD) for simultaneous determination of three monoamine neurotransmitters and two of their metabolites in infants' urine. We also identify the metabolite MHPG as a potential biomarker for the early diagnosis of brain damage for infants.

抽出と神経伝達物質カテコールアミン及びその代謝物の高速液体クロマトグラフィーによる分析のための便利な方法

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and ...

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the aziridine ring. The utility of bicyclic aziridinium ions, specifically 1-azoniabicyclo[3.1.0]hexane and 1-azoniabicyclo[4.1.0]heptane tosylate highlighted in the aziridine ring openings by the nucleophile with the release of the ring strain to yield the corresponding ring-expanded azaheterocycles such as pyrrolidine, piperidine and azepane with diverse substituents on the ring in regio- and stereospecific manner. Herein, we report a simple and convenient method for the preparation of the stable 1-azabicyclo[4.1.0]heptane tosylate followed by selective ring opening via a nucleophilic attack either at the bridge or at the bridgehead carbon to yield piperidine and azepane rings, respectively. This synthetic strategy allowed us to prepare biologically active natural products containing piperidine and azepane motif including sedamine, allosedamine, fagomine and balanol in highly efficient manner.

Bicyclic aziridinium ions such as 1-azoniabicyclo[4.1.0]heptane tosylate were generated from 2-[4-tolenesulfonyloxybutyl]aziridine, which was utilized for the preparation of substituted piperidines and azepanes via regio- and stereospecific ring-expansion with various nucleophiles. This highly efficient protocol allowed us to prepare diverse azaheterocycles including natural products such as fagomine, febrifugine analogue and balanol.

安定した二環性 Aziridinium イオンと開環の Azaheterocycles の合成のための準備

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the ...

Triphosphenium臭化物塩の調製と反応性：リンの便利で安定したソース（I）

要約

さらに動画を探す

この動画の章

二ヨウ化サマリウム（SMIの調製および使用

化学固定することによりX線蛍光イメージングのための接着細胞の準備

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性

DNA折り紙解析と実験のためのマイカとシリコン基板の作製

調製とキャラクタリゼーション個々のとマルチ薬ロード物理的に捕捉さ高分子ミセル

周囲条件下での金ナノ粒子の安定オリゴマークラスターのサイズ制御された合成のための簡単な方法

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたはIV）

の調製と評価

抽出と神経伝達物質カテコールアミン及びその代謝物の高速液体クロマトグラフィーによる分析のための便利な方法

安定した二環性 Aziridinium イオンと開環の Azaheterocycles の合成のための準備

Triphosphenium臭化物塩の調製と反応性：リンの便利で安定したソース（I）

要約

さらに動画を探す

この動画の章

二ヨウ化サマリウム（SMIの調製および使用

化学固定することによりX線蛍光イメージングのための接着細胞の準備

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性

DNA折り紙解析と実験のためのマイカとシリコン基板の作製

調製とキャラクタリゼーション個々のとマルチ薬ロード物理的に捕捉さ高分子ミセル

周囲条件下での金ナノ粒子の安定オリゴマークラスターのサイズ制御された合成のための簡単​​な方法

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたはIV）

の調製と評価

抽出と神経伝達物質カテコールアミン及びその代謝物の高速液体クロマトグラフィーによる分析のための便利な方法

安定した二環性 Aziridinium イオンと開環の Azaheterocycles の合成のための準備

周囲条件下での金ナノ粒子の安定オリゴマークラスターのサイズ制御された合成のための簡単な方法