Single Reaction System Research Articles

Enhancing production of hydrogen and simultaneous degradation of ciprofloxacin over Sn doped SrTiO3 piezocatalyst

The combination of hydrogen production from water and degradation of organic pollutants into a single reaction system is an attractive and promising solution for renewable energy generation and wastewater treatment. Herein, the piezocatalytic production of hydrogen coupled with simultaneous piezocatalytic degradation of organic antibiotic (ciprofloxacin) was successfully achieved using Sn doped SrTiO3 as the highly efficient and robust piezocatalyst through harvesting vibration energy. Results showed that 5 mol% Sn doped SrTiO3 (SrSn0.05Ti0.95O3) showed the highest piezocatalytic production rate of hydrogen (101.46 μmol g−1h−1) in water. And SrSn0.05Ti0.95O3 also exhibited remarkable piezocatalytic activity in solution containing ciprofloxacin with 151.03 μmol g−1h−1 of H2 evolution rate and 77.5 % of ciprofloxacin degradation efficiency within 60 min. In this process, the doping of Sn largely enlarged the distorted structure and conductivity of SrTiO3 to improve the piezocatalytic activity, and the organic ciprofloxacin mainly acted as the electron donors to synergistically improve the reduction process for H2 evolution. This work establishes the relationships between the piezoelectric property and the piezocatalyst structure, and provides an approach of advanced piezocatalytic technology for wastewater treatment and renewable energy generation.

Synthesis of Solvent-Mediated Morphology-Controlled PdSn Alloy Nanocatalysts and their Application in Electrocatalysis of Ethylene Glycol and Ethanol.

2D nanodendrites (NDs) and nanosheets (NSs) have been regarded as efficient nanocatalysts for enhancing the electrocatalytic performance due to their low coordinated sites and abundant electrocatalytic centers. Nevertheless, it remains challenging to construct advanced NDs and NSs in a single reaction system. Herein, by tuning the volume ratios of mixed solvents, the reduction and diffusion rate of Sn2+ on Pd NSs template was rationally controlled to prepare PdSn NDs and PdSn NSs. Ascribed to the open 2D nanostructure, high specific surface area, and robust synergistic effect, the as-prepared PdSn NDs and PdSn NSs exhibited distinguished electrocatalytic activities for ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), as well as commendable electrocatalytic durability, which were far superior to the Pd NSs and commercial Pd/C. In addition, the PdSn NDs exhibited enhanced reaction kinetics because the characteristic branch structure exposed a high density of active sites. This work may provide significant guidance for preparing excellent nanocatalysts with various morphological features by simply optimizing the content of the coexisting solvents.

EFFICIENT PRODUCTION OF SMALL-SIZED SiO2 NANOPARTICLES AND THEIR APPLICATION IN A WATERBORNE ACRYLIC-AMINO VARNISH

In this study, we optimized the preparation of 100–160 nm monodispersed SiO2 nanoparticles and, through doping, investigated their effects on the physical properties of a water-based acrylic-amino varnish. First, using a non-fixed point feeding technique based on the half-batch sol-gel method, we enhanced the yield of small-sized monodispersed SiO2 nanoparticles. To reduce the cost of production and organic-matter pollution, we assessed certain solution parameters including tetraethyl orthosilicate (TEOS), ethanol (ETOH) and ammonia in a single-reaction system. We found that the gloss, clarity, hardness, adhesion, and other physical properties of the acrylic-amino varnish were successfully enhanced through an addition of 1.2 % SiO2 nanoparticles.

Rapid duplex flap probe-based isothermal assay to identify the Cryptococcus neoformans and Cryptococcus gattii.

Cryptococcosis is a life-threatening invasive fungal infection with significantly increasing mortality worldwide, which is mainly caused by Cryptococcus neoformans and Cryptococcus gattii. These two species complexes have different epidemiological and clinical characteristics, indicating the importance of accurate differential diagnosis. However, the clinically used culture method and cryptococcal capsular antigen detection couldn't achieve the above goals. Herein, we established a novel duplex flap probe-based isothermal assay to identify the Cryptococcus neoformans and Cryptococcus gattii within 1 hour. This assay combined the highly sensitive nucleic acid isothermal amplification and highly specific fluorescence probe method, which could effectively distinguish the sequence differences of the two species complexes using two different fluorescence flap probes in a single reaction system. This novel method showed excellent detection performance with sensitivity (10 copies/μL each) and specificity (100%) compared to traditional culture and sequencing methods. Furthermore, we applied this method to spiked clinical samples, 30 cerebrospinal fluids and 30 bronchoalveolar lavage fluids, which kept good detection performance. This novel rapid duplex flap probe-based isothermal assay is a promising and robust tool for applications in differential diagnosis of the Cryptococcus neoformans and Cryptococcus gattii in clinical settings, especially when clinical suspicion for cryptococcal disease is high and epidemiological studies.

Catalyst regulation of o-phenylenediamine-based carbon dots to achieve single red emission

Red fluorescence is of great significance in biomedicine because of its high tissue penetration and low photodamage to organisms. While the carbon dots (CDs) obtained from o-phenylenediamine (oPD) mainly emit yellow fluorescence in a single reaction system, which greatly limits its development in long-wavelength applications. Here, we design a strategy to control the color of oPD-based CDs by only adding catalyst without changing the materials and conditions. The addition of the catalyst made the mass proportion of the obtained red CDs from less than 1% to 95.6%, and the conversion rate was up to 61.7%. The red CDs with a photoluminescence quantum yield of 29.99% have been successfully applied to live cell imaging. It is well known that catalysts can selectively change the reaction pathway and improve the reaction activity. In the process of oPD-based CD formation, we propose that the catalyst can activate the amino functional group, further accelerate the dehydrogenation and polymerization process, thus effectively increasing the sp2-conjugated domain and graphitic N content, which finally realizes the conversion of mixed CDs to single red CDs. This work provides a new idea for how to regulate the fluorescence of CDs without changing the materials and conditions in the future.

Photocatalytic CO2 reduction to methanol integrated with the oxidative coupling of thiols for S–X (X = S, C) bond formation over an Fe3O4/BiVO4 composite

This work demonstrated a dual functional approach for CO2 reduction coupled with oxidative coupling of thiols in a single reaction system to get the co-production of high-value chemicals using light energy.

Multifunctional 3D electrodes for tunable high-performance hybrid zinc batteries

The high energy density and long cycling life of zinc-based batteries are restricted by the single electrochemical reaction system. To improve the electrochemical performance of batteries, electrode materials, electrolytes and membranes are regularly modified, while the construction of battery systems is often neglected. Herein, a multifunctional electrode was prepared via 3D printing, which successfully coupled the metal oxide/hydroxide-zinc battery (MZB) reaction and rechargeable zinc-air battery (RZAB) reaction. The ultrathick hierarchical 3D electrode provided a tunable capacity for the MZB system, which enabled the possibility for feasible output regulation of this hybrid system. The active material NiCoLDH was discovered to undergo structure reconstruction during cycling, which revealed the capacity fading mechanism. The delicate system design and discovery ensured a high-performance battery configuration and revealed the corresponding mechanism, opening a new avenue for developing high-performance zinc batteries.

Enhancement of the CO2 adsorption and hydrogenation to CH4 capacity of Ru–Na–Ca/γ–Al2O3 dual function material by controlling the Ru calcination atmosphere

Integrated CO2 capture and utilization (ICCU) technology requires dual functional materials (DFMs) to carry out the process in a single reaction system. The influence of the calcination atmosphere on efficiency of 4% Ru-8% Na2CO3-8% CaO/γ-Al2O3 DFM is studied. The adsorbent precursors are first co-impregnated onto alumina and calcined in air. Then, Ru precursor is impregnated and four aliquotes are subjected to different calcination protocols: static air in muffle or under different mixtures (10% H2/N2, 50% H2/N2 and N2) streams. Samples are characterized by XRD, N2 adsorption-desorption, H2 chemisorption, TEM, XPS, H2-TPD, H2-TPR, CO2-TPD and TPSR. The catalytic behavior is evaluated, in cycles of CO2 adsorption and hydrogenation to CH4, and temporal evolution of reactants and products concentrations is analyzed. The calcination atmosphere influences the physicochemical properties and, ultimately, activity of DFMs. Characterization data and catalytic performance discover the acccomodation of Ru nanoparticles disposition and basic sites is mostly influencing the catalytic activity. DFM calcined under N2 flow (RuNaCa-N2) shows the highest CH4 production (449 µmol/g at 370°C), because a well-controlled decomposition of precursors which favors the better accomodation of adsorbent and Ru phases, maximizing the specific surface area, the Ru-basic sites interface and the participation of different basic sites in the CO2 methanation reaction. Thus, the calcination in a N2 flow is revealed as the optimal calcination protocol to achieve highly efficient DFM for integrated CO2 adsorption and hydrogenation applications.

Target-allele-specific probe single-base extension (TASP-SBE): a novel MALDI-TOF-MS strategy for multi-variants analysis and its application in simultaneous detection of α-/β-thalassemia mutations.

Single-nucleotide variants (SNVs) and copy number variations (CNVs) are the most common genomic variations that cause phenotypic diversity and genetic disorders. MALDI-TOF-MS is a rapid and cost-effective technique for multi-variant genotyping, but it is challenging to efficiently detect CNVs and clustered SNVs, especially to simultaneously detect CNVs and SNVs in one reaction. Herein, a novel strategy termed Target-Allele-Specific Probe Single-Base Extension (TASP-SBE) was devised to efficiently detect CNVs and clustered SNVs with MALDI-TOF-MS. By comprehensive use of traditional SBE and TASP-SBE strategies, a MALDI-TOF-MS assay was also developed to simultaneously detect 28 α-/β-thalassemia mutations in a single reaction system, including 4 α-thalassemia deletions, 3 HBA and 21 HBB SNVs. The results showed that all 28 mutations were sensitively identified, and the CNVs of HBA/HBB genes were also accurately analyzed based on the ratio of peak height (RPH) between the target allele and reference gene. The double-blind evaluation results of 989 thalassemia carrier samples showed a 100% concordance of this assay with other methods. In conclusion,a one-tube MALDI-TOF-MS assay was developed to simultaneously genotype 28 thalassemia mutations. This novel TASP-SBE was also verified a practicable strategy for the detection of CNVs and clustered SNVs, providing a feasible approach for multi-variants analysis with MALDI-TOF-MS technique.

Development and clinical implications of a novel CRISPR-based diagnostic test for pulmonary Aspergillus fumigatus infection

Rapid and reliable diagnostic methods for Aspergillus fumigatus infection are urgently needed. Clustered regularly interspaced short palindromic repeat (CRISPR)-associated protein 13a (Cas13a) has high sensitivity and specificity in the diagnosis of viral infection. However, its potential use in detecting A. fumigatus remains unexplored. A highly sensitive and specific method using the CRISPR/Cas13a system was developed for the reliable and rapid detection of A. fumigatus.The conserved internal transcribed spacer (ITS) region of A. fumigatus was used to design CRISPR-derived RNA (crRNA) and the corresponding recombinase polymerase amplification (RPA) primer sequence with the T7 promoter for the CRISPR assay. Twenty-five clinical isolates and 43 bronchoalveolar lavage fluid (BALF) remaining from routine examinations of patients with confirmed pulmonary aspergillosis were collected to further validate the CRISPR assay.No amplification signal was observed when genomic DNA from closely clinically related Aspergillus species, such as Aspergillus flavus, Aspergillus niger, and Aspergillus terreus, as well as Monascus purpureus Went and Escherichia coli, was tested by this assay, and the detection limit for A. fumigatus was 3 copies in a single reaction system. Validation experiments using the 25 clinical isolates demonstrated 91.7% specificity for the A. fumigatus section, and the sensitivity was 100% when first-generation sequencing was used as the standard. There was no significant difference between the PCR and CRISPR methods (P = 1.0), and the diagnosis results of the two methods were consistent (Kappa = 0.459, P = 0.003).The study offers a new validated CRISPR/Cas13a technique for A. fumigatus detection, providing a simple, rapid and affordable test that is ready for application in the diagnosis of A. fumigatus infection.

A qPCR-duplex assay for sex determination in ancient DNA.

Molecular biology techniques are increasingly being used in sex identification of skeletal remains when traditional anthropometric analyzes are not successful in identifying sex of remains that are incomplete, fragmented and /or of immature individuals. In the present work, we investigated the possibility of determining sex by using the qPCR-duplex method for both ancient and modern DNA samples. This method involves the co-amplification of two genes in a single reaction system and the subsequent analysis of the fusion curves; the gene sequences used for the construction of suitable primers are those of steroid sulfatase (STS) and testis specific protein Y-linked 1 (TSPY) genes which turned out to be two sensitive markers as they have a detection limit of 60 pg and 20 pg respectively on modern DNA. The validity of the method was verified on modern DNA in which gender was identified in all the samples with 100% accuracy; thus, allowing for the same results as the classic method with amelogenin, but in a faster and more immediate way, as it allows for sex determination solely by analyzing the denaturation curves without having to perform an electrophoretic run. The proposed molecular technique proves to be sensitive and precise even on degraded DNA, in fact on 9 archaeological finds dating from the VII-XII century in which sex had been identified through anthropometric analysis, it confirmed the sex of 8 out of 9 finds correctly.

Optimization of platform conditions for simultaneous detection of multiple nutritional marker proteins by liquid protein microarray

To optimize the technical conditions for simultaneous detection of serum ferritin(SF), soluble transferrin receptor(sTfR), C-reactive protein(CRP)and retinol-binding protein four(RBP4)by liquid protein microarray. The trapping antibodies of the four proteins were coupled to magnetic beads with different codes, and the samples were added to the 96-well plate. The antibodies were detected by double antibody sandwich method. The serum of 5 patients were diluted with commercial diluent, 1% albumin from bovine serum(BSA) and phosphate buffer saline(PBS) to detect 4 target proteins, and the results were compared. The antibody specific binding ability was tested by antibody specific validation test. The interference between proteins was verified by the paired t test of the signal values of the single reaction system and the mixed reaction system. The lower limit of detection and the limit of biological detection of each protein were found by using multiple dilution method. The standard curve and regression equation were established. 1%BSA and PBS were selected to replace commercial diluent as diluents for the detection of 4 proteins in this experiment. The cross-reaction rate of the four antigens with other capture antibodies and detection antibodies was less than 2%. There was no significant difference in the signal value of each protein in the single reaction system and the mixed reaction system. The limit of detection and the limit of biological detection of SF were 1.155 and 1.625 ng/mL, respectively. The lower limit of detection and the limit of biological detection of sTfR were 2.682 and 5.208 ng/mL, respectively. The detection limit and biological detection limit of CRP were 0.302 and 0.391 ng/mL, respectively. The lower limit of detection and the limit of biological detection for RBP4 were 1.814 and 3.540 ng/mL, respectively. The standard curve and regression equation of the four proteins within the common linear range were as follows: SF y=172.5x-39.65, R~2=0.9968;sTfR y=60.10x+77.38, R~2=0.9972;CRP y=-6.000x~2+210.3x+246.1, R~2=0.9063;RBP4 y=-0.6998x~2+64.31x+134.8, R~2=0.9748. The conditions of the detection platform for four proteins such as SF, sTfR, CRP and RBP4 were optimized by using liquid protein chip technology.

Single-digit Salmonella detection with the naked eye using bio-barcode immunoassay coupled with recombinase polymerase amplification and a CRISPR-Cas12a system.

The ability to visually detect low numbers of Salmonella in food samples is highly valuable but remains a challenge. Here we present a novel platform for ultrasensitive and visual detection of Salmonella Typhimurium by integrating the bio-barcode immunoassay (BCA), recombinase polymerase amplification (RPA), and CRISPR-Cas12a cleavage in a single reaction system (termed as BCA-RPA-Cas12a). In the system, the target bacteria were separated by immunomagnetic nanoparticles and labeled with numerous barcode AuNPs, which carry abundant bio-barcode DNA molecules to amplify the signal. Afterwards, the bio-barcode DNA molecules were amplified by RPA and subsequently triggered the cleavage activity of Cas12a to generate the fluorescence signal. Due to this triplex signal amplification, the BCA-RPA-Cas12a system can selectively detect Salmonella Typhimurium at the single-digit level with the naked eye under blue light within 60 min. Meanwhile, this novel platform was successfully applied to detect Salmonella Typhimurium in spiked milk samples with a similar sensitivity and satisfactory recovery, indicating its potential application in real samples. Furthermore, in virtue of the versatility of the antibody in the stage of BCA, the BCA-RPA-Cas12a system can be extended to further application in other bacteria detection and food safety monitoring.

Rational Design of Multi-Color-Emissive Carbon Dots in a Single Reaction System by Hydrothermal.

As an emerging building unit, carbon dots (CDs) have been igniting the revolutionaries in the fields of optoelectronics, biomedicine, and bioimaging. However, the difficulty of synthesizing CDs in aqueous solution with full‐spectrum emission severely hinders further investigation of their emission mechanism and their extensive applications in white light emitting diodes (LEDs). Here, the full‐color‐emission CDs with a unique structure consisting of sp 3‐hybridized carbon cores with small domains of partially sp 2‐hybridized carbon atoms are reported. First‐principle calculations are initially used to predict that the transformation from sp 3 to sp 2 hybridization redshifts the emission of CDs. Guided by the theoretical predictions, a simple, convenient, and controllable route to hydrothermally prepare CDs in a single reaction system is developed. The prepared CDs have full‐spectrum emission with an unprecedented two‐photon emission across the whole visible color range. These full‐color‐emission CDs can be further nurtured by slight modifications of the reaction conditions (e.g., temperature, pH) to generate the emission color from blue to red. Finally a flexible LEDs with full‐color emission by using epoxy CDs films is developed, indicating that the strategy affords an industry translational potential over traditional fluorophores.

OpvCRISPR: One-pot visual RT-LAMP-CRISPR platform for SARS-cov-2 detection

The 2019 novel coronavirus disease (COVID-19) pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has affected all aspects of human life. Rapid, accurate, sensitive and user friendly detection method is urgently needed to facilitate early intervention and control the spread of SARS-CoV-2. Here, we propose a one-pot visual SARS-CoV-2 detection system named “opvCRISPR” by integrating reverse transcription loop-mediated isothermal amplification (RT-LAMP) and Cas12a cleavage in a single reaction system. We demonstrate that the collateral activity against single-stranded DNA (ssDNA) reporters of activated Cas12a triggered by RT-LAMP amplicon increases detection sensitivity and makes detection results observable with naked eye. The opvCRISPR enables detection at nearly single molecule level in 45 min. We validate this method with 50 SARS-CoV-2 potentially infected clinical samples. The opvCRISPR diagnostic results provide 100% agreement with the Centers for Disease Control and Prevention (CDC)-approved quantitative RT-PCR assay. The opvCRISPR holds great potential for SARS-CoV-2 detection in next-generation point-of-care molecular diagnostics.

Indole Carbonized Polymer Dots Boost Full-Color Emission by Regulating Surface State.

SummaryCarbonized polymer dots (CPDs) are impressive imaging probes with great potential for enriching the library of metal-free fluorescent materials, yet current strategies have struggled to achieve products that emit full-color light in a single reaction system. Establishing an efficient and robust synthesis approach that unlocks the color barrier to the luminescence centers of specific CPDs remains a challenge. Herein, the surface-state engineering of pyridine and amide in the indole system to create a palette of resolvable full-color light-emissive CPDs is reported. Detailed structural analysis revealed that cationic polymerization and oxidation reactions potentially contribute to the formation of the main frameworks and emission centers of the final CPDs, with emissive oxygen- and nitrogen-based centers fixed by cross-linked polymer structures. This study provides valuable insight into the energy absorbance and photoluminescence mechanism of CPDs and introduces additional reactants (benzo heterocycle) into CPD research.

Cas12aVDet: A CRISPR/Cas12a-Based Platform for Rapid and Visual Nucleic Acid Detection.

A rapid and sensitive method is crucial for nucleic acid detection. Recently, RNA-guided CRISPR/Cas12a nuclease-based methods present great promise for nucleic acid detection. In the present methods, however, DNA amplification and subsequent Cas12a cleavage is separated and the whole process takes as long as 2 h. Most importantly, the uncapping operation increases the risk of aerosol contamination. In this study, we propose a CRISPR/Cas12a-based method named "Cas12aVDet" for rapid nucleic acid detection. By integrating recombinase polymerase amplification (RPA) with Cas12a cleavage in a single reaction system, the detection can be accomplished in 30 min and uncapping contamination can be avoided. The detection signal can be observed by the naked eye under blue light. This method could detect DNA at single molecule level and demonstrated 100% accuracy for mycoplasma contamination detection, presenting great potential for a variety of nucleic acid detection applications.

Polymorphs Co hydroxides formed between hydrazine and Co2+ as Liesegang bands in semisolid agar gel

Co hydroxide polymorphs (green α-Co(OH)2, red β-Co(OH)2 and brown β-Co(OH)3) formed at separate positions in a test-tube. Diffusion of hydrazine hydrate downward in agar gel facilitated the reaction between hydrazine and Co2+ leading a dilatational wave of reactant concentration. The resulting periodic Liesegang bands of α-Co(OH)2 were observed due to the diffusion hindrance of reactants. It can be deduced that the high concentration of Co2+ causes formation of α-Co(OH)2 while the low concentrations produce β-Co(OH)2. β-Co(OH)2 is oxidized readily to form brown β-Co(OH)3 at the upper area of agar gel with high alkali condition and O2 distribution. This study is helpful to learn the formation of more than one product and prepare multiple materials in single chemical reaction system. In addition, the obtained α-Co(OH)2 has been stabilized in the gel medium for at least 3 months. It may facilitate its application in many areas especially in electrochemical area since α-Co(OH)2 typically exhibits higher conductivity and electrocatalysis than β-Co(OH)2 while in the past its application often is limited by thermodynamically instability.

Activation of manganese dioxide with bisulfite for enhanced abiotic degradation of typical organophosphorus pesticides: Kinetics and transformation pathway

Organophosphorus pesticides (OPPs), a kind of effective insecticide, have attracted extensive attention of researchers because of the high toxicity and refractory character of their degradation products. Given the ubiquity of manganese dioxide (MnO2) and bisulfite (HSO3−) in environmental media, the abiotic degradation of several typical OPPs by the MnO2-HSO3- reaction system was investigated in batch experiments. As a representative OPP, methyl parathion (MP) was chosen to be the focus of the study. The removal rate of MP was remarkably improved by adding bisulfite (HSO3−) to the MnO2 single-reaction system, and the oxidation product methyl paraoxon was below the detection limit. The primary active substances generated from the reaction system were determined to be Mn(III) species by adding excess radical scavengers or complexants (methanol and pyrophosphate) to the reaction system. On the basis of the metabolic products of MP identified by liquid chromatography–high-resolution mass spectrometry (LC/HRMS) and gas chromatography–mass spectrometry (GC/MS), the transformation pathway of MP in the MnO2-HSO3- reaction system was elicited, which included the predominant processes of hydrolysis and oxidation. Furthermore, the typical OPPs with different structures were also degraded efficiently by the reaction system because of the oxidative degradation of Mn(III). This study offers significative information related to the abiotic oxidation of manganese minerals and the fate and dissipation of OPPs in the actual environment.

Unprecedented Variety of Outcomes in the Oxygenation of Dinuclear Alkylzinc Derivatives of an N,N-Coupled Bis(β-diketimine).

Reactions between O2 and organometallics with non-redox-active metal centers have received continuous interest for over 150 years, although significant uncertainties concerning the character and details of the actual mechanism of these reactions persist. Harnessing dinuclear three-coordinate alkylzinc derivatives of an N,N-coupled bis(β-diketimine) proligand (LH2 ) as a model system, we demonstrate for the first time that a slight modification of the reaction conditions might have a dramatic influence on the oxygenation reaction outcomes, leading to an unprecedented variety of products originating from a single reaction system, that is, partially and fully oxygenated zinc alkoxides, zinc alkylperoxides, and zinc hydroxide compounds. Our studies indicate that accessibility of the three-coordinate zinc center by the O2 molecule, coupled with the lower reactivity of Zn-Me vs. Zn-Et units towards dioxygen, are key factors in the oxygenation process, providing a novel tetranuclear methyl(methoxy)zinc {[L][ZnMe][Zn(μ-OMe]}2 and zinc ethoxide {[L][Zn(μ-OEt)]2 }2 . Remarkably, oxygenation of three-coordinate alkylzinc [L][ZnR]2 complexes at ambient temperature afforded a unique hydroxide {[L][Zn(μ-OH)]2 }2 . Oxygenation of the [L][ZnEt]2 complex in the presence of 4-methylpyridine (py-Me) at low temperature led to the isolation of a dinuclear zinc ethylperoxide [L][Zn(OOEt)(py-Me)]2 , which nicely substantiates the intermediacy of an unstable zinc alkylperoxide in the formation of the subsequent zinc alkoxide and hydroxide compounds. Finally, our investigations provide compelling evidence that a non-redox-active metal center plays a crucial role in the oxygenation process through assisting in single-electron transfer from an M-C bond to an O2 molecule. Although the oxygenation of zinc alkyls occurs by radical pathways, the reported results stand in clear contradiction to the widely accepted free-radical chain mechanism.