Sites Of Core Research Articles

Synthesis of heavy-atom-free thienoisoindigo dye as near-infrared photosensitizer for type I photodynamic therapy and photoacoustic imaging

Thienoisoindigo (TIIG) has been extensively employed as promising building block of near-infrared (NIR) dyes and organic semiconductor materials. Herein, heavy-atom-free TIIG-based NIR dye TIIGTPA is reported as photosensitizer for combinational photodynamic and photothermal therapy and photoacoustic imaging (PAI). By introducing two methoxy-substituted triphenylamines as the rotors and electron donors at the periphery sites of the electron-deficient TIIG core, dye TIIGTPA featuring Donor-Acceptor-Donor (D-AD) structure is constructed with intensive NIR absorption. Through co-assembly with amphipathic F-127, water-soluble TIIGTPA NPs were prepared with good superoxide anion radical (O2-•) production and high photothermal conversion efficiency (PCE) of 59.0 % under 730 nm photoirradiation. Additionally, the excellent photothermal effect enabled a superior photoacoustic response for tumor blood vessel visualization through PAI. All results indicated the favorable potential of TIIGTPA NPs for PAI-mediated combinational phototherapy.

Dendritic polymer prodrug-based unimolecular micelles for pH-responsive co-delivery of doxorubicin and camptothecin with synergistic controlled drug release effect

Combination chemotherapy has been recognized as a more powerful strategy for tumor treatment rather than the single chemotherapy. However, the interactive mechanism of the two hydrophobic chemotherapeutic drugs has not been explored by now. Aiming for a better synergistic effect, such interactive mechanism was investigated in the present work, by designing CPT@DOX-DPUTEA-PEG nanomedicine with encapsulated camptothecin (CPT) and conjugated doxorubicin (DOX). The synergistic controlled drug release effect was found for the two drugs loaded on the different sites of the dendritic polyurethane core. Synergism was achieved on the HepG2 cells with a combination index (CI) of 0.58 in the in vitro cellular experiments. The results demonstrated the promising application of the unimolecular micelles-based nanomedicine with independently loading of two hydrophobic chemotherapeutic drugs.

Polymeric carbon quantum dots as efficient chlorophyll sensor-analysis based on experimental and computational investigation

This report introduces a microfiber chlorophyll sensor based on polymeric amine functionalized carbon quantum dots (NCQD) using the surface plasmon resonance technique. The silver (Ag) thin film, followed by NCQD-polyvinyl alcohol composite film, was deposited on the tapered optical fiber. The characterization of surface morphologies of NCQD-PVA film using a field emission scanning electron microscope shows that the contact area with the analyte was well covered with Ag and NCQD-PVA. The experimental results show that the fiber optic SPR sensor can detect chlorophyll in the 0.01–2.0 ppm range with a high sensitivity response and a detection limit of 1.90 nm ppm−1 and 0.78 ppm, respectively. This study observed no significant interference among the other ionic species (Fe3+, NH4+, NO3–, NO2–, and PO4-) due to the electrostatic and π-π interactions between NCQD and chlorophyll. Results from density functional theory calculation also confirm that the interaction of the NCQD with chlorophyll existed, and the strongest interaction occurs between nitrogen at pyridine sites of the carbon core and the oxygen group of chlorophyll. The proposed NCQD/PVA optical fiber sensor exhibits good sensing performance and correlates well with the standard method (R2 = 0.9501), suggesting a suitable technology candidate for real-time environmental monitoring applications.

Self-sacrifice-template epitaxial growth of hierarchical MnO2@NiCo2O4 heterojunction electrode for high-performance asymmetric supercapacitor

Constructing three-dimensional (3D) hierarchical bimetallic pseudocapacitive materials with abundant opening channel and heterojunction structures is rather promising but still challenging for high-performance supercapacitors. Herein, a self-sacrifice-template epitaxial growth strategy was proposed for the first time to construct 3D hierarchical bimetallic pseudocapacitive material. By using this strategy, NiCo2O4 nanowires (NiCo2O4NW) arrayed randomly to form a porous shell via in-situ epitaxial growth fully enclosing a MnO2 tube core, forming multiple transport channels and nano-heterojunctions between MnO2 and NiCo2O4NW, which facilitates electron transfer, i.e. exhibiting high electronic conductivity than any single component. As a result of the self-sacrifice-template epitaxial growth method, special hollow tectorum-like 3D hierarchical structure with considerable inter-nanowire space and hollow interior space enables easy access of electrolyte to NiCo2O4NW surface and MnO2 core, thereby resulting in highly exposed redox active sites of MnO2 core and NiCo2O4NW shell for energy storage. Comprehensive evaluations confirmed MnO2@NiCo2O4NW was a supercapacitor electrode candidate, delivering a superior energy density of 106.37 Wh kg−1. Such performance can be ascribed to the synergistic coupling effect of 3D hierarchical tube and nano-heterojunction structures. The proposed self-sacrifice-template epitaxial growth strategy provides important guidance for designing high-performance energy storage materials.

Construction of hierarchical core-shell Pt/USY@MSA bifunctional catalysts for hydroisomerization of n-hexadecane

Hydroisomerization of long-chain n-alkanes is an indispensable process in the upgrading of fuel oil and lubricants to meet the state of art regulations. In this work, a novel core-shell structural material comprising USY zeolite core and mesoporous aluminosilicate (MSA) shell, denoted as USY@MSA, was fabricated by virtue of a desilication and recrystallization approach. Comprehensive characterizations demonstrate that the USY@MSA composite exhibits a hierarchical pore architecture and a gradient acidity. Due to the confinement effect of the mesoporous aluminosilicate shell, highly dispersed platinum particles were selectively deposited on the shell, generating a nanoscale distance with acidic sites of USY zeolite core. In the hydroisomerization of n-hexadecane, the Pt/USY@MSA composite catalyst outperforms the conventional Pt/USY and desilicated Pt/USY-ds catalysts, effectively suppressing the cracking side reactions and producing higher selectivity to branched isomers.

Construction of C-N Atropisomers by Aminocatalytic Enantioselective Addition of Indole-2-carboxaldehydes to o-Quinone Derivatives.

The first atroposelective aminocatalytic methodology for the construction of C-N atropisomers is presented. The synthesis of this class of axially chiral molecules typically encompasses substrates in which the C-N bond is pre-formed. In contrast, this work presents the direct coupling of indole-2-carboxaldehydes to ortho-quinones, to form the stereogenic C-N axis in an atroposelective way. Application of typical secondary amine catalysts furnished the desired product, however, in low yields and as a complex mixture arising from poor regiocontrol among the C3 - and N1 -sites of the indole core. A new aminocatalyst was designed and synthesized with increased outer-sphere steric bulk to address these challenges thereby providing good levels of regio- and enantioselectivity. A novel library of functionalized and enantioenriched C-N atropisomers was obtained and their synthetic utility was demonstrated by various transformations.

Core-Shell Carbon-Based Bifunctional Electrocatalysts Derived from COF@MOF Hybrid for Advanced Rechargeable Zn-Air Batteries.

The development of highly active carbon-based bifunctional electrocatalysts for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is highly desired, but still full of challenges in rechargeable Zn-air batteries. Metal organic frameworks (MOFs) and covalent organic frameworks (COFs) have gained great attention for various applications due to their attractive features of structural tunability, high surface area and high porosity. Herein, a core-shell structured carbon-based hybrid electrocatalyst (H-NSC@Co/NSC), which contains high density active sites of MOF-derived shell (Co/NSC) and COF-derived hollow core (H-NSC), is successfully fabricated by direct pyrolysis of covalently-connected COF@ZIF-67 hybrid. The core-shell H-NSC@Co/NSC hybrid manifests excellent catalytic properties toward both OER and ORR with a small potential gap (∆E= 0.75 V). The H-NSC@Co/NSC assembled Zn-air battery exhibits a high power-density of 204.3 mW cm-2 and stable rechargeability, outperforming that of Pt/C+RuO2 assembled Zn-air battery. Density functional theory calculations reveal that the electronic structure of the carbon frameworks on the Co/NSC shell can be effectively modulated by the embedded Co nanoparticles (NPs), facilitating the adsorption of oxygen intermediates and leading to enhanced catalytic activity. This work will provide a strategy to design highly-efficient electrocatalysts for application in energy conversion and storage.

Leveraging structural and 2D-QSAR to investigate the role of functional group substitutions, conserved surface residues and desolvation in triggering the small molecule-induced dimerization of hPD-L1

Small molecules are rising as a new generation of immune checkpoints’ inhibitors, with compounds targeting the human Programmed death-ligand 1 (hPD-L1) protein are pioneering this area of research. Promising examples include the recently disclosed compounds from Bristol-Myers-Squibb (BMS). These molecules bind specifically to hPD-L1 through a unique mode of action. They induce dimerization between two hPD-L1 monomers through the hPD-1 binding interface in each monomer, thereby inhibiting the PD-1/PD-L1 axis. While the recently reported crystal structures of such small molecules bound to hPD-L1 reveal valuable insights regarding their molecular interactions, there is still limited information about the dynamics driving this unusual complex formation. The current study provides an in-depth computational structural analysis to study the interactions of five small molecule compounds in complex with hPD-L1. By employing a combination of molecular dynamic simulations, binding energy calculations and computational solvent mapping techniques, our analyses quantified the dynamic roles of different hydrophilic and lipophilic residues at the surface of hPD-L1 in mediating these interactions. Furthermore, ligand-based analyses, including Free-Wilson 2D-QSAR was conducted to quantify the impact of R-group substitutions at different sites of the phenoxy-methyl biphenyl core. Our results emphasize the importance of a terminal phenyl ring that must be present in any hPD-L1 small molecule inhibitor. This phenyl moiety overlaps with a very unfavorable hydration site, which can explain the ability of such small molecules to trigger hPD-L1 dimerization.

Oxidation of ferumoxytol by ionizing radiation releases iron. An electron paramagnetic resonance study.

Ferumoxytol (FMX) is an iron oxide nanoparticle that is FDA approved for the treatment of iron deficiency anemia. FMX contains an Fe3O4 core. Currently, the redox chemistry of Fe3O4 nanoparticles remains relatively unexplored. FMX has recently gained interest as an anti-cancer agent. Ionizing radiation (IR) is a treatment modality employed to treat several types of cancer. Utilizing electron paramagnetic resonance (EPR) spectroscopy, we found that the products produced from the radiolysis of water can oxidize the Fe3O4 core of FMX. Because of the limited diffusion of the HO2• and HO• produced, these highly oxidizing species have little direct effect on FMX oxidation. We have determined that H2O2 is the primary oxidant of FMX. In the presence of labile Fe2+, we found that reducing species generated from the radiolysis of H2O are able to reduce the Fe3+ sites of the Fe3O4 core. Importantly, we also have shown that IR stimulates the release of ferric iron from FMX. Because of its release of iron, FMX may serve as an adjuvant to enhance radiotherapy.

Analysis of site and structure specific core fucosylation in liver cirrhosis using exoglycosidase-assisted data-independent LC-MS/MS

Carbohydrates form one of the major groups of biological macromolecules in living organisms. Many biological processes including protein folding, stability, immune response, and receptor activation are regulated by glycosylation. Fucosylation of proteins regulates such processes and is associated with various diseases including autoimmunity and cancer. Mass spectrometry efficiently identifies structures of fucosylated glycans or sites of core fucosylated N-glycopeptides but quantification of the glycopeptides remains less explored. We performed experiments that facilitate quantitative analysis of the core fucosylation of proteins with partial structural resolution of the glycans and we present results of the mass spectrometric SWATH-type DIA analysis of relative abundances of the core fucosylated glycoforms of 45 glycopeptides to their nonfucosylated glycoforms derived from 18 serum proteins in liver disease of different etiologies. Our results show that a combination of soft fragmentation with exoglycosidases is efficient at the assignment and quantification of the core fucosylated N-glycoforms at specific sites of protein attachment. In addition, our results show that disease-associated changes in core fucosylation are peptide-dependent and further differ by branching of the core fucosylated glycans. Further studies are needed to verify whether tri- and tetra-antennary core fucosylated glycopeptides could be used as markers of liver disease progression.

Molecular bixbyite-like In12-oxo clusters with tunable functionalization sites for lithography patterning applications.

Indium oxides have been widely applied in many technological areas, but their utilization in lithography has not been developed. Herein, we illustrated a family of unprecedented In12-oxo clusters with a general formula [In12(μ4-O)4(μ2-OH)2(OCH2CH2NHCH2CH2O)8(OR)4X4]X2 (where X = Cl or Br; R = CH3, C6H4NO2 or C6H4F), which not only present the largest size record in the family of indium-oxo clusters (InOCs), but also feature the first molecular model of bixbyite-type In2O3. Moreover, through the labile coordination sites of the robust diethanolamine-stabilized In12-oxo core, these InOCs can be accurately functionalized with different halides and alcohol or phenol derivatives, producing tunable solubility. Based on the high solution stability as confirmed by ESI-MS analysis, homogeneous films can be fabricated using these In12-oxo clusters by the spin-coating method, which can be further used for electron beam lithography (EBL) patterning studies. Accordingly, the above structural regulations have significantly influenced their corresponding film quality and patterning performance, with bromide or p-nitrophenol functionalized In12-oxo clusters displaying better performance of sub-50 nm lines. Thus, the here developed bixbyite-type In12-oxo cluster starts the research on indium-based patterning materials and provides a new platform for future lithography radiation mechanism studies.

Epigallocatechin gallate and theaflavin gallate interaction in SARS-CoV-2 spike-protein central channel with reference to the hydroxychloroquine interaction: Bioinformatics and molecular docking study.

SARS‐CoV‐2 or COVID‐19 pandemic global outbreak created the most unstable situation of human health–economy. In the past two decades different parts of the word experienced smaller or bigger outbreak related to human coronaviruses. The spike glycoproteins of the COVID‐19 (similar to SARS‐CoV) attach to the angiotensin‐converting enzyme (ACE2) and transit over a stabilized open state for the viral internalization to the host cells and propagate with great efficacy. Higher rate of mutability makes this virus unpredictable/less sensitive to the protein/nucleic acid based drugs. In this emergent situation, drug‐induced destabilization of spike binding to RBD could be a good strategy. In the current study we demonstrated by bioinformatics (CASTp: computed atlas of surface topography of protein, PyMol: molecular visualization) and molecular docking (PatchDock and Autodock) experiments that tea flavonoids catechin products mainly epigallocatechin gallate or other like theaflavin gallate demonstrated higher atomic contact energy (ACE) value, binding energy, Ki value, ligand efficiency, surface area and more amino acid interactions than hydroxychloroquine (HCQ) during binding in the central channel of the spike protein. Moreover, out of three distinct binding sites (I, II and III) of spike core when HCQ binds only with site III (farthest from the nCoV‐RBD of ACE2 contact), epigallocatechin gallate and theaflavin gallate bind all three sites. As sites I and II are in closer contact with open state location and viral–host contact area, these drugs might have significant effects. Taking into account the toxicity/side effects by chloroquine/HCQ, present drugs may be important. Our laboratory is working on tea flavonoids and other phytochemicals in the protection from toxicity, DNA/mitochondrial damage, inflammation and so on. The present data might be helpful for further analysis of flavonoids in this emergent pandemic situation.

Imidazo[1,2-b]pyridazine as Building Blocks for Host Materials for High-Performance Red-Phosphorescent Organic Light-Emitting Devices.

A novel electron-transporting unit, imidazo [1,2-b]pyridazine (IP), was first reported for developing host materials. The IP moiety possesses excellent electron-transporting ability and great thermal stability. Using carbazole as p-type units and IP as n-type units, several bipolar host materials, namely, IP6Cz, IP68Cz, IP36Cz, and IP368Cz, were developed through altering the substitution site of the IP core. Among these four materials, 6-site-substituted IP6Cz and 6,8-site-substituted IP68Cz exhibit the best electroluminescence (EL) performance. IP6Cz- and IP68Cz-based red phosphorescent organic light-emitting diodes using Ir(pq)2acac as the emitter exhibit extremely high EL efficiency with the maximum external quantum efficiency (ηext,max) of 26.9 and 25.2% and an insignificant efficiency roll-off. Moreover, IP6Cz- and IP68Cz-based deep-red devices doped by Ir(piq)2acac also show satisfactory EL performance with a ηext,max of 20.5 and 19.9%, respectively. The influence of different substitution sites of the IP core on the photophysical and electrochemical properties was systematically investigated. This study demonstrates that IP could be a first-rate electron-transporting unit for bipolar materials for red-emitting devices.

Enhanced and Heteromolecular Guest Encapsulation in Nonporous Crystals of a Perfluorinated Triketonato Dinuclear Copper Complex

The flexible host framework of a perfluorinated mononuclear copper complex, [Cu(L1 )2 ] (1, HL1 =3-hydroxy-1,3-bis(pentafluorophenyl)-2-propen-1-one), with a CuO4 core reversibly encapsulated several organic guest molecules through electrostatic interactions in its crystals. Hence, the corresponding dinuclear complex, [Cu2 (L2 )2 ] (2, H2 L2 =1,5-dihydroxy-1,5-bis(pentafluorophenyl)-1,4-pentadien-3-one), was prepared to enhance guest recognition and the ability to separate molecular mixtures. Complex 2 comprises a Cu2 O6 core and four pentafluorophenyl groups. In crystal 2, cavities are formed on the axial sites of the metal core that are surrounded by pentafluorophenyl groups. The crystal of 2 encapsulates various guest molecules, that is, benzene (3), toluene (4), xylene (5), mesitylene (6), durene (7), and anisole (8). X-ray crystallographic and thermogravimetric (TG) studies show that three guest molecules are present in the crystal cavities. The number of guest molecules found in complex 2 was higher than that in complex 1, for example, (2)3 ⋅(6)10 >1⋅(6)2 , (2)2 ⋅(7)7 >1⋅7, or 2⋅(8)3 >1⋅(8)2 . Naphthalene (9), was encapsulated in 2 to give 2⋅(9)3 , but not in 1. In the crystal of complex 2, heteromolecular guest encapsulation was confirmed, designated as 2⋅(3)2 ⋅9. TG analysis indicates that the thermal stability of the guest-included crystals of 2 is higher than that of 1.

To direct the self-assembly of AIEgens by three-gear switch: Morphology study, amine sensing and assessment of meat spoilage

Abstract In this study, we synthesized a class of positional isomers by attaching a carboxylic group in different sites (para-, meta- and ortho-position) of an aromatic core. The isomers undergo both aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) mechanisms, as proved by their photoluminescence (PL) behaviour. Changing the position of the carboxylic group will adjust the dipole–dipole direction, which further controls the self-assembled architecture: The morphology undergoes a transition from 1D nanowire to 2D microsheet, and even to 3D microcube. The benzoic acid moiety of the AIE isomers has strong affinity to amines, and adsorbing amines leads to spectral changes including hypochromatic shift and emission quenching. The sensing mechanism was studied by density functional theory (DFT), which reveals that the amine-responsive fluorescence can be ascribed to the weakened ICT effect. A prototype of amine sensor based on m-DB self-assemblies was developed accordingly, showing a remarkable quenching efficiency as high as 85.4%. A linear relation was obtained from the quantitative determination of amine, offering a low detection limit of 2.02 Pa. It can also respond to other organic amines such as diisopropylamine (DIPA), triethylamine (TEA), isopropylamine (IPA) and cyclohexylamine (CHA). Finally, the practicality of the sensor was also demonstrated: When placing the sensing film beside the spoiled meat, the spectrum shows a remarkable fluorescence quenching; in contrast, fresh meat samples have induced a much lower quenching efficiency. This demonstrates that the AIE isomers have a great potential to serve as indicators for meat spoilage.

The Hyperarid Core of the Atacama Desert, an Extremely Dry and Carbon Deprived Habitat of Potential Interest for the Field of Carbon Science.

The Atacama Desert in Chile is the driest and oldest desert on Earth, also considered one of the best Mars analog models. Here, several heterotrophic microbial communities have been discovered in its driest regions, with the ones present in the soil subsurface being one of the most interesting due to its existence in a habitat with almost no water available and almost undetectable organic carbon sources. Our recent discovery of the driest site of the Atacama known to date (and the heterotrophic microbial species that are able to survive in this site) reaffirms the opportunity to better characterize the physiological and molecular mechanisms that these species use to detect, mobilize, incorporate and use carbon under these extremely harsh conditions. Here we summarize what has been reported up to date on the organic carbon concentrations in different sites of the hyperarid core of the Atacama Desert, proposing that due to the meager amounts of carbon and extremely dry conditions, the microbial communities of the hyperarid core of the Atacama Desert may be of interest for the field of carbon science.

Single step mechanism for nucleophilic substitution of 2,3-dichloro naphthoquinone using nitrogen, oxygen and sulfur nucleophiles: A DFT approach

The reactivity of 2,3-dichoro-1,4-naphthoquinone with difunctional nucleophiles (2-mercaptoethanol, 1,2-ethanedithiol, 2-aminoethanol and ethylene glycol) was investigated in mild conditions. Using DFT calculations (B3LYP/6–31++G(d,p) and M11/6–31++G(d,p)), we identified intramolecular interactions in the 2-(substituted)-3-chloro-1,4-naphthoquinone derivatives, which modify the electrophilicity and reactivity of the monosubstituted species, allowing the occurrence of a second nucleophilic attack. Formation of intramolecular hydrogen bonds between the terminal group of the substituent chain and the carbonyl group in the naphthoquinone increases the electrophilicity of the substitution sites of the quinone core, resulting in lower energy barriers for this process. Furthermore, transition state structures and Intrinsic Reaction Coordinate (IRC) calculations showed that the substitution reactions may occur in a single step process, without a tetrahedral intermediate.

Composition-dependent electronic energy relaxation dynamics of metal domains as revealed by bimetallic Au144-xAgx(SC8H9)60 monolayer-protected clusters.

We examined the electronic relaxation dynamics for mono and bimetallic Au144-xAgx(SC8H9)60 monolayer-protected clusters (MPCs) using femtosecond time-resolved transient extinction spectroscopy. MPCs provide compositionally well-defined model systems for structure-specific determination of nanoscale electronic properties. Based on pulse-energy-dependent transient extinction data, we quantified electron-phonon coupling constants for three distinct Au144-xAgx(SC8H9)60 MPC samples, where x = 0, 0 < x < 30, and x ∼ 30, as Gx=0 = (1.61 ± 0.1) × 1016 W m-3 K-1, Gx<30 = (1.74 ± 0.1) × 1016 W m-3 K-1 and Gx∼30 = (2.07 ± 0.15) × 1016 W m-3 K-1, respectively. These results reflect a trend of greater electron-phonon coupling efficiency with increasing silver content. Based on these data, we conclude that gold-atom replacement by silver occurs at surface sites of the 114-atom metal core of the MPC. Definitive determinations of functional response to nanoscale "alloy" formation and dopant inclusion are critical to establishing predictive models for the development of materials that feature nanoparticles as active components.

Displacement field induced by a vacancy in nickel and some implications for the solubility of hydrogen

The displacement field induced by a vacancy in nickel and its possible implications for the hydrogen solubility in the interstitial sites is investigated up to 1100 K. The displacement field is extracted from our previous atomistic-scale density functional theory calculations and is compared with continuous isotropic models with and without image forces due to the distribution of the defects. This procedure put in forward the contribution of the elastic anisotropy and the vacancy concentration on the elastic displacement field. Then, we calculate the dilatation of the interstitial sites due to the presence of the defect and the local hydrostatic stress acting on them. This local hydrostatic stress modifies the hydrogen solubility in the interstitial sites. Elastic distortions contribute to reduce the local solubility inside the vacancy core and the opposite out of it. Finally, we extract the elastic contribution of the trapping energy of hydrogen in the displacement field of the vacancy. We find that the elastic energy is significant only for the closest interstitial sites of the defect core and limits the attractive electronic contribution to the trapping energy. In addition, we show that the elastic anisotropy and the vacancy concentration have moderate effects on the local solubility in the displacement field close to the defect core.

Doped silicon nanocrystals from organic dopant precursor by a SiCl4-based high frequency nonthermal plasma

Doped silicon nanocrystals (Si NCs) are of great interest in demanding low-cost nanodevices because of the abundance and nontoxicity of Si. Here, we demonstrate a cost-effective gas phase approach to synthesize phosphorous (P)-doped Si NCs in which the precursors used, i.e., SiCl4, trimethyl phosphite (TMP), are both safe and economical. It is found that the TMP-enabled P-doping does not change the crystalline structure of Si NCs. The surface of P-doped Si NCs is terminated by both Cl and H. The Si–H bond density at the surface of P-doped Si NCs is found to be much higher than that of undoped Si NCs. The X-ray photoelectron spectroscopy and electron spin resonance results indicate that P atoms are doped into the substitutional sites of the Si-NC core and electrically active in Si NCs. Unintentional impurities, such as carbon contained in TMP, are not introduced into Si NCs.