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1.
J Am Chem Soc ; 146(9): 5759-5780, 2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38373254

RESUMO

This perspective highlights advances in the preparation and understanding of metal nanoclusters stabilized by organic ligands with a focus on N-heterocyclic carbenes (NHCs). We demonstrate the need for a clear understanding of the relationship between NHC properties and their resulting metal nanocluster structure and properties. We emphasize the importance of balancing nanocluster stability with the introduction of reactive sites for catalytic applications and the importance of a better understanding of how these clusters interact with their environments for effective use in biological applications. The impact of atom-scale simulations, development of atomic interaction potentials suitable for large-scale molecular dynamics simulations, and a deeper understanding of the mechanisms behind synthetic methods and physical properties (e.g., the bright fluorescence displayed by many clusters) are emphasized.

2.
Chem Sci ; 14(38): 10500-10507, 2023 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-37800004

RESUMO

Atomically precise gold nanoclusters (AuNCs) are interesting nanomaterials with potential applications in catalysis, bioimaging and optoelectronics. Their compositions and properties are commonly evaluated by various analytical techniques, including UV-vis spectroscopy, NMR spectroscopy, ESI mass spectrometry, and single-crystal X-ray diffraction. While these techniques have provided detailed insights into the structure and properties of nanoclusters, synthetic methods still suffer from a lack of in situ and real-time reaction monitoring methodologies. This limits insight into the mechanism of formation of AuNCs and hinders attempts at optimization. We have demonstrated the utility of HPLC-MS as a monitoring methodology in the synthesis of two NHC-protected gold nanoclusters: [Au13(NHC)9Cl3]2+ and [Au24(NHC)14Cl2H3]3+. Herein we show that HPLC coupled with mass spectrometry and 13C NMR spectroscopy of labelled derivatives enables new insight into critical reaction dynamics of AuNCs synthesis and rapid reaction optimization.

3.
J Sleep Res ; 32(4): e13872, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-36889676

RESUMO

The norepinephrine locus coeruleus system (LC NE) represents a promising treatment target in patients with insomnia disorder (ID) due to its well understood links to arousal and sleep regulation. However, consistent markers of LC NE activity are lacking. This study measured three potential indirect markers of LC NE activity - REM sleep, P3 amplitude during an auditory oddball paradigm (as a marker of phasic LC activation), and baseline pupil diameter (as a marker of tonic LC activation). The parameters were then combined in a statistical model and tested to compare LC NE activity between 20 subjects with insomnia disorder (13 female; age 44.2 ± 15.1 year) and 20 healthy, good sleeping controls (GSC; 11 female; age 45.4 ± 11.6 year). No group differences regarding the primary outcome parameters were detected. Specifically, insomnia disorder did not display the hypothesised changes in markers of LC NE function. While increased LC NE function remains an interesting speculative pathway for hyperarousal in insomnia disorder, the investigated markers do not appear closely related to each other and fail to discriminate between insomnia disorder and good sleeping controls in these samples.


Assuntos
Distúrbios do Início e da Manutenção do Sono , Humanos , Feminino , Adulto , Pessoa de Meia-Idade , Distúrbios do Início e da Manutenção do Sono/metabolismo , Locus Cerúleo/metabolismo , Norepinefrina , Nível de Alerta/fisiologia , Sono
4.
J Am Chem Soc ; 144(20): 9000-9006, 2022 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-35549258

RESUMO

Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au24(NHC)14Cl2H3]3+. This cluster comprises a dimer of two Au12 kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this Au24H3 cluster in the electrocatalytic reduction of CO2 is demonstrated and benchmarked against related catalysts.

5.
J Photochem Photobiol B ; 182: 52-61, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29604554

RESUMO

The blood compatibility of AgNPs is of great relevance as it has good antifungal, antibacterial and anti-inflammatory properties and the toxicological information of their effects on cells need to be analyzed before using it as drug carriers in the biomedical field. The present study deals with the synthesis of AgNPs from an aqueous solution of silver nitrate using Acalypha hispida leaf extract as the reducing and capping agent. The presence of AgNPs in the reaction mixture was confirmed by visual observation of color change and subsequently identified using UV-Visible Spectroscopy. XRD results revealed the crystalline nature of synthesized AgNPs. The shape and size of particles were characterized by TEM. These results revealed the elemental status of nanopowder. The components present in leaf extract were identified by GC-MS and functional groups present in the sample when treated with silver nitrate were obtained from FT-IR results. The surface of synthesized AgNPs was modified using four different compounds such as CTAB, PEG, PEI, and APTMS to evaluate the blood compatibility. The results showed that 50 µg/mL CTAB coated AgNPs and 50 and 100 µg/mL PEG coated AgNPs had non-hemolytic property and considered as more blood compatible surface modified AgNPs. This investigation gives an idea of using surface modified AgNPs in the field of biomedicine and therapeutic applications.


Assuntos
Acalypha/química , Tecnologia Biomédica/métodos , Química Verde , Nanopartículas Metálicas/química , Extratos Vegetais/química , Folhas de Planta/química , Prata/química , Estabilidade de Medicamentos , Hemólise/efeitos dos fármacos , Humanos , Extratos Vegetais/farmacologia , Substâncias Redutoras/química , Prata/farmacologia , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície
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