Cientistas desvendam o mecanismo químico por trás dos nanodiamantes revestidos de sílica
Revestir algo raro – pequenos fragmentos de diamante – com o ingrediente principal na areia pode parecer incomum, mas o resultado final acaba tendo uma série de aplicações valiosas. O truque é que ninguém sabe ao certo como os dois materiais se ligam
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As instalações de raios X e o sensor de borda de transição do SSRL revelam informações sobre o nanodiamante escondido abaixo de um revestimento de sílica. Os elétrons irradiados escapam da superfície do nanodiamante, viajam através da sílica e são coletados como sinais. Quanto mais espesso o revestimento, menos elétrons chegam à superfície. Compreender a química dos revestimentos de sílica ajudará os pesquisadores a otimizar as cascas de sílica e a testar outros materiais como revestimentos, expandindo as aplicações dos nanodiamantes na computação quântica e na rotulagem biológica. Crédito: Greg Stewart/Laboratório Nacional de Aceleradores SLAC
Revestir algo raro – pequenos fragmentos de diamante – com o ingrediente principal na areia pode parecer incomum, mas o resultado final acaba tendo uma série de aplicações valiosas. O truque é que ninguém sabe ao certo como os dois materiais se ligam.
Agora, pesquisadores da Universidade Estadual de San Jose (SJSU) relatam na revista ACS Nanoscience Au que grupos químicos de álcool na superfície de um diamante são responsáveis por cascas de sílica utilmente uniformes , um resultado que poderia ajudá-los a criar melhores nanodiamantes revestidos de sílica – pequenas ferramentas com aplicações desde biomarcação de células cancerígenas até detecção quântica.
A equipe desvendou o mecanismo de ligação graças aos poderosos raios X gerados pela fonte de luz de radiação síncrotron de Stanford (SSRL) no Laboratório Nacional de Aceleradores SLAC do DOE.
"Agora que conhecemos esses detalhes mais sutis - como funciona o vínculo, em vez de apenas adivinhar - podemos explorar melhor novos sistemas híbridos de diamantes", disse Abraham Wolcott, investigador principal do estudo e professor da SJSU.
Grande parte do trabalho de Wolcott diz respeito aos nanodiamantes, diamantes sintéticos quebrados em pedaços tão pequenos que seriam necessários 40 mil deles para abranger a largura de um único fio de cabelo humano. Teoricamente, os nanodiamantes têm redes de carbono perfeitas, mas ocasionalmente um átomo de nitrogênio entra furtivamente e substitui um átomo de carbono próximo a um átomo de carbono ausente. É tecnicamente um defeito, mas é útil – o defeito responde a campos magnéticos, campos elétricos e luz, todos à temperatura ambiente , o que significa que os nanodiamantes têm muitas aplicações.
Eles podem ser usados como qubits, a unidade básica de um computador quântico. Acerte-os com luz verde e eles brilharão em vermelho, para que os biólogos possam colocá-los em células vivas e rastreá-los enquanto se movem. Mas os cientistas não conseguem programar facilmente os nanodiamantes para irem onde querem, e as bordas dos diamantes são pontiagudas e podem romper as membranas celulares.
Revesti-los com sílica resolve ambos os problemas. A sílica forma uma casca lisa e uniforme que cobre as arestas vivas. Também cria uma superfície modificável, que os cientistas podem decorar com etiquetas para direcionar as partículas para células específicas, como células cancerígenas ou neurônios. “O diamante com casca de sílica torna-se um sistema controlável”, disse Wolcott.
Mas há algum tempo, disse Wolcott, os cientistas discordam sobre como essa concha se forma. Sua equipe mostrou que o hidróxido de amônio com etanol, produtos químicos normalmente incluídos no processo de revestimento, produz muitos grupos alcoólicos na superfície do nanodiamante , e esses álcoois facilitam o crescimento da casca.
“Ninguém foi capaz de explicar isso por mais de 10 anos”, disse Wolcott, “mas conseguimos extrair essa informação”.
Depois de estudar as partículas com microscópios eletrônicos de transmissão no Laboratório Nacional de Fundição Molecular Lawrence Berkeley do DOE, os pesquisadores dispararam raios X SSRL em nanodiamantes para explorar as superfícies escondidas abaixo do revestimento de sílica.
O sensor de borda de transição do SSRL – um termômetro supersensível que coleta mudanças de temperatura e as converte em energias de raios X – revelou quais grupos químicos estavam presentes nas superfícies dos nanodiamantes.
Usando uma segunda técnica – espectroscopia de absorção de raios X (XAS) – a equipe gerou elétrons móveis na superfície do nanodiamante e, em seguida, capturou-os enquanto viajavam através da camada de sílica e escapavam. Quanto mais espesso o revestimento, menos elétrons chegaram à superfície. Os sinais funcionavam como uma pequena fita métrica, mostrando a espessura do revestimento de sílica em escala nanométrica.
“O XAS é poderoso porque você pode detectar algo que está submerso, que está escondido – como um diamante debaixo de uma casca de sílica”, disse Wolcott. "As pessoas nunca fizeram isso com nanodiamantes antes, então, além de descobrir o mecanismo de ligação, também mostramos que o XAS é útil para cientistas de materiais e químicos."
No futuro, Wolcott, que é conhecido por oferecer oportunidades de pesquisa prática, quer colocar os alunos para trabalhar no revestimento de nanodiamantes com outros materiais. Titânio, zinco e outros óxidos metálicos, por exemplo, poderiam abrir novos caminhos em aplicações de detecção quântica e rotulagem biológica.
“Os nanodiamantes são microferramentas incríveis com aplicações imediatas”, disse Karen Lopez, Ph.D. em engenharia biomédica. estudante da Universidade da Califórnia, Irvine que, como os outros autores da SJSU, trabalhou no estudo ainda na graduação. "Agora que entendemos como a camada de sílica se forma, podemos começar a otimizá-la e expandi-la para outros tipos de materiais."
Mais informações: Perla J. Sandoval et al, Quantum Diamonds at the Beach: Chemical Insights into Silica Growth on Nanoscale Diamond using Multimodal Characterization and Simulation, ACS Nanoscience Au (2023). DOI: 10.1021/acsnanoscienceau.3c00033