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廉價(jià)的磷能模擬貴金屬催化反應(yīng)
廉價(jià)的磷能模擬貴金屬催化反應(yīng)
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2026年2月24日 |
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化學(xué)家原以為磷元素已盡顯其能——直到它展現(xiàn)出令人驚喜的新本領(lǐng) |
Chemists thought phosphorus had shown all its cards—until it surprised them with a new move |
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作者：霍莉·奧伯（Holly Ober），加州大學(xué)洛杉磯分校 編輯：薩迪·哈雷（Sadie Harley），審校：羅伯特·伊根（Robert Egan） |
by Holly Ober, University of California, Los Angeles edited by Sadie Harley, reviewed by Robert Egan |
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光照射下的光化學(xué)反應(yīng) |
Photochemical reaction under light irradiation |
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加州大學(xué)洛杉磯分校的有機(jī)化學(xué)家取得了一項(xiàng)可能讓催化轉(zhuǎn)化器盜賊失業(yè)的發(fā)現(xiàn)。在新研究中，他們使用儲(chǔ)量豐富、價(jià)格低廉的磷作為催化劑，完成了通常需要鉑等貴金屬才能實(shí)現(xiàn)的化學(xué)反應(yīng)——而鉑正是汽車催化轉(zhuǎn)化器中被盜目標(biāo)金屬之一，這種汽車部件能將尾氣中的化學(xué)物質(zhì)轉(zhuǎn)化為危害較小的形態(tài)。 |
A discovery by UCLA organic chemists may one day put catalytic converter thieves out of business. In new research, they've used abundant, inexpensive phosphorus as a catalyst in chemical reactions that usually require precious metals like platinum, one of the metals targeted in theft of the automotive components that convert chemicals in vehicle exhaust into less harmful forms. |
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然而，這一進(jìn)展可能對(duì)制藥業(yè)更為有用，并有望在未來(lái)降低某些藥品的價(jià)格。 |
This advance, however, will likely be more useful in the pharmaceutical industry and could one day help bring down the price of some drugs. |
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基于磷的催化新方法 |
New phosphorus-based approach to catalysis |
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這項(xiàng)發(fā)表在《自然》雜志上的新研究使用了一種光反應(yīng)分子（即光催化劑），該分子與廉價(jià)的含磷化合物反應(yīng)，將含氮化合物（常見(jiàn)于藥物中）與碳碳雙鍵偶聯(lián)。這種稱為氫胺化的反應(yīng)是構(gòu)建更復(fù)雜結(jié)構(gòu)的有效方法。 |
The new research, published in Nature, uses a light-reactive molecule, known as a photocatalyst, that reacts with an inexpensive phosphorous compound to couple nitrogen-containing compounds (often found in drugs) to a carbon-carbon double bond. This type of reaction, called hydroamination, is an effective way to make more complex structures. |
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"碳氮鍵是藥物發(fā)現(xiàn)和制造中最重要的化學(xué)鍵之一。幾乎所有藥物都含有氮，但將氮固定到分子中很困難，這就是我們使用貴金屬過(guò)渡金屬催化劑的原因，"該論文的通訊作者、加州大學(xué)洛杉磯分校化學(xué)教授阿比蓋爾· Doyle（Abigail Doyle）表示。 |
"Carbon-nitrogen bonds are some of the most important kinds of bonds for drug discovery and manufacturing. Almost all medicines have nitrogen in them, but fixing that nitrogen into molecules is difficult, which is why we use precious transition metal catalysts," said UCLA chemistry professor Abigail Doyle, who is the paper's corresponding author. |
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過(guò)渡金屬是閃亮、導(dǎo)電的金屬，如金、銀、銅、銥、鉑和鈀。在適當(dāng)條件下，它們?nèi)菀着c許多其他元素反應(yīng)，加速化學(xué)反應(yīng)。因此，它們已成為必不可少的工業(yè)催化劑。 |
Transition metals are shiny, electrically conductive metals such as gold, silver, copper, iridium, platinum and palladium. Under the right conditions, they react easily with many other elements, speeding up chemical reactions. They have therefore become essential industrial catalysts. |
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"這些金屬用于汽車發(fā)動(dòng)機(jī)的催化轉(zhuǎn)化器，以及制造各種材料，從牛仔褲的組成部分到藥品，"Doyle說(shuō)。 |
"These metals are used in catalytic converters in car engines, and to make a vast variety of materials, from components of denim jeans to medicines," said Doyle. |
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"然而，使用它們可能非常昂貴，因此人們非常感興趣尋找更便宜的過(guò)渡金屬來(lái)替代，如銅、鎳或鐵，或者尋找周期表中其他既儲(chǔ)量豐富又能像金屬一樣反應(yīng)的催化劑。" |
"However, they can be very expensive to use, so there's a lot of interest in either finding less expensive transition metals to replace these, such as copper, nickel or iron, or to find a catalyst from a different block in the periodic table that is both abundant and can also react the way that metals do." |
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磷和膦為何重要 |
Why phosphorus and phosphines matter |
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磷是生命必需的元素。因此，含磷化合物在自然界中非常常見(jiàn)，并在有機(jī)化學(xué)中被廣泛使用。 |
Phosphorus is an element essential to life. Phosphorous compounds are therefore very common in nature and widely used in organic chemistry. |
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"化學(xué)家已經(jīng)開(kāi)發(fā)了各種使用磷化合物的命名反應(yīng)，包括膦作為催化劑的例子，"Doyle說(shuō)。 |
"Chemists have developed all sorts of named reactions using phosphorus compounds, including examples where phosphines serve as catalysts," said Doyle. |
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膦是磷原子與三個(gè)碳原子鍵合的分子。"但我們發(fā)現(xiàn)了一種新的磷反應(yīng)模式，模仿鈀和銥等過(guò)渡金屬在催化中常見(jiàn)的模式，"Doyle說(shuō)。 |
Phosphines are molecules containing a phosphorus atom bonded with three carbon atoms. "But we've discovered a new reactivity mode for phosphorus that mimics a mode that transition metals like palladium and iridium commonly perform in catalysis," Doyle said. |
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實(shí)驗(yàn)室中的意外發(fā)現(xiàn) |
A surprise discovery in the lab |
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Doyle實(shí)驗(yàn)室發(fā)現(xiàn)光可用于將膦轉(zhuǎn)化為能夠替代稀有昂貴催化劑的物質(zhì)，這是在嘗試形成碳氮鍵的方法時(shí)偶然獲得的意外結(jié)果。 |
The Doyle lab's discovery that light could be used to transform phosphines into something that could do the work of rarer and expensive catalysts was the serendipitous result of experimenting with ways to form carbon-nitrogen bonds. |
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"我們驚訝地發(fā)現(xiàn)，對(duì)于與我們預(yù)期完全不同的產(chǎn)物卻表現(xiàn)出高反應(yīng)活性。弄清楚發(fā)生了什么是個(gè)謎，"first作者、博士生范弗洛拉（Flora Fan）說(shuō)。雖然最初并非為此設(shè)計(jì)，但團(tuán)隊(duì)最終確定磷在反應(yīng)中必須像金屬一樣起作用。 |
"We were surprised to see high reactivity for a completely different product than what we expected. It was definitely a puzzle to try to figure out what was going on," said first author and doctoral student Flora Fan. Though initially not designed to perform this way, the team eventually determined that phosphorus had to be working like a metal in the reaction. |
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該反應(yīng)通過(guò)一種壽命短、高反應(yīng)活性的磷形式進(jìn)行。這種形式可以通過(guò)與金屬催化劑活化這些雙鍵的方式非常相似的途徑與碳碳雙鍵反應(yīng)。雖然膦模仿了金屬催化劑的行為，但它也遵循根本不同的規(guī)則。 |
The reaction proceeds through a short-lived, highly reactive form of phosphorus. This form can react with carbon-carbon double bonds through pathways that closely resemble the ways metal catalysts activate these double bonds. While the phosphine mimics the behavior of metal catalysts, it also operates by fundamentally different rules. |
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關(guān)鍵區(qū)別在于，膦起始狀態(tài)可以進(jìn)行涉及轉(zhuǎn)移一個(gè)和兩個(gè)電子的反應(yīng)，而過(guò)渡金屬催化劑通常涉及轉(zhuǎn)移兩個(gè)電子。因此，氫胺化反應(yīng)遵循獨(dú)特的路線，能夠使用更多樣化的含氮化合物。 |
The key difference is that the phosphine starts in a state that can undergo reactions that involve the transfer of both one and two electrons, whereas transition metal catalysts most commonly involve the transfer of two electrons. Because of this, the hydroamination reaction follows a unique route that enables more diverse nitrogen-containing compounds to be used. |
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這對(duì)未來(lái)藥物意味著什么 |
What this could mean for future drugs |
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Doyle團(tuán)隊(duì)希望這些反應(yīng)活性的相似性和差異性能激發(fā)基于磷催化劑設(shè)計(jì)化學(xué)反應(yīng)的新策略。 |
Doyle's team hopes that these similarities and differences in reactivity inspire new strategies with phosphorus-based catalysts for designing chemical reactions. |
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"我們很興奮能嘗試了解能將這種化學(xué)推進(jìn)多遠(yuǎn)，"范弗洛拉說(shuō)。"希望它能為制造藥物化合物和其他高附加值化學(xué)品打開(kāi)更多通用方法的大門(mén)。" |
"We're excited about trying to understand how far we can take this chemistry," said Fan. "Hopefully, it will open doors to more versatile methods for making drug compounds and other value-added chemicals." |
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與此同時(shí)，汽車車主可以期待這一發(fā)現(xiàn)最終應(yīng)用于不再吸引盜賊的催化轉(zhuǎn)化器。 |
Meanwhile, automobile owners can hope that the discovery eventually finds its way into catalytic converters that no longer appeal to thieves. |