Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 79
Filter
1.
Nat Commun ; 15(1): 5773, 2024 Jul 10.
Article in English | MEDLINE | ID: mdl-38982057

ABSTRACT

Harnessing the power of cell biocatalysis for sustainable chemical synthesis requires rational integration of living cells with the modern synthetic catalysts. Here, we develop silica-tiling strategy that constructs a hierarchical, inorganic, protocellular confined nanospace around the individual living cell to accommodate molecularly accessible abiotic catalytic sites. This empowers the living microorganisms for new-to-nature chemical synthesis without compromising the cellular regenerative process. Yeast cell, a widely used biocatalyst, is upgraded via highly controlled self-assembly of 2D-bilayer silica-based catalytic modules on cell surfaces, opening the avenues for diverse chemobiotic reactions. For example, combining [AuPt]-catalyzed NADH regeneration, light-induced [Pd]-catalyzed C-C cross-coupling or lipase-catalyzed esterification reactions-with the natural ketoreductase activity inside yeast cell. The conformal silica bilayer provides protection while allowing proximity to catalytic sites and preserving natural cell viability and proliferation. These living nanobiohybrids offer to bridge cell's natural biocatalytic capabilities with customizable heterogeneous metal catalysis, enabling programmable reaction sequences for sustainable chemical synthesis.


Subject(s)
Biocatalysis , Saccharomyces cerevisiae , Silicon Dioxide , Silicon Dioxide/chemistry , Saccharomyces cerevisiae/metabolism , Catalysis , NAD/metabolism , Lipase/metabolism , Palladium/chemistry , Esterification
2.
Acc Chem Res ; 57(3): 413-427, 2024 02 06.
Article in English | MEDLINE | ID: mdl-38243820

ABSTRACT

The evolutionary complexity of compartmentalized biostructures (such as cells and organelles) endows life-sustaining multistep chemical cascades and intricate living functionalities. Relatively, within a very short time span, a synthetic paradigm has resulted in tremendous growth in controlling the materials at different length scales (molecular, nano, micro, and macro), improving mechanistic understanding and setting the design principals toward different compositions, configurations, and structures, and in turn fine-tuning their optoelectronic and catalytic properties for targeted applications. Bioorthogonal catalysis offers a highly versatile toolkit for biochemical modulation and the capability to perform new-to-nature reactions inside living systems, endowing augmented functions. However, conventional catalysts have limitations to control the reactions under physiological conditions due to the hostile bioenvironment. The present account details the development of bioapplicable multicomponent designer nanoreactors (NRs), where the compositions, morphologies, interfacial active sites, and microenvironments around different metal nanocatalysts can be precisely controlled by novel nanospace-confined chemistries. Different architectures of porous, hollow, and open-mouth silica-based nano-housings facilitate the accommodation, protection, and selective access of different nanoscale metal-based catalytic sites. The modular porosity/composition, optical transparency, thermal insulation, and nontoxicity of silica are highly useful. Moreover, large macropores or cavities can also be occupied by enzymes (for chemoenzymatic cascades) and selectivity enhancers (for stimuli-responsive gating) along with the metal nanocatalysts. Further, it is crucial to selectively activate and control catalytic reactions by a remotely operable biocompatible energy source. Integration of highly coupled plasmonic (Au) components having few-nanometer structural features (gaps, cavities, and junctions as electromagnetic hot-spots) endows an opportunity to efficiently harness low-power NIR light and selectively supply energy to the interfacial catalytic sites through localized photothermal and electronic effects. Different plasmonically integrated NRs with customizable plasmonic-catalytic components, cavities inside bilayer nanospaces, and metal-laminated nanocrystals inside hollow silica can perform NIR-/light-induced catalytic reactions in complex media including living cells. In addition, magnetothermia-induced NRs by selective growth of catalytic metals on a pre-installed superparamagnetic iron-oxide core inside a hollow-porous silica shell endowed the opportunity to apply AMF as a bioorthogonal stimulus to promote catalytic reactions. By combining "plasmonic-catalytic" and "magnetic-catalytic" components within a single NR, two distinct reaction steps can be desirably controlled by two energy sources (NIR light and AMF) of distinct energy regimes. The capability to perform multistep organic molecular transformations in harmony with the natural living system will reveal novel reaction schemes for in cellulo synthesis of active drug and bioimaging probes. Well-designed nanoscale discrete architectures of NRs can facilitate spatiotemporal control over abiotic chemical synthesis without adversely affecting the cell viability. However, in-depth understanding of heterogeneous surface catalytic reactions, rate induction mechanisms, selectivity control pathways, and targeted nanobio interactions is necessary. The broad field of biomedical engineering can hugely benefit from the aid of novel nanomaterials with chemistry-based designs and the synthesis of engineered NRs performing unique bioorthogonal chemistry functions.


Subject(s)
Metals , Nanostructures , Nanotechnology , Catalysis , Silicon Dioxide
3.
Angew Chem Int Ed Engl ; 63(5): e202316630, 2024 Jan 25.
Article in English | MEDLINE | ID: mdl-38063060

ABSTRACT

Controlled assembly of nanoparticles into well-defined assembled architectures through precise manipulation of spatial arrangement and interactions allows the development of advanced mesoscale materials with tailored structures, hierarchical functionalities, and enhanced properties. Despite remarkable advancements, the controlled assembly of highly anisotropic 2Dnanosheets is significantly challenging, primarily due to the limited availability of selective edge-to-edge connectivity compared to the abundant large faces. Innovative strategies are needed to unlock the full potential of 2D-nanomaterialsin self-assembled structures with distinct and desirable properties. This research unveils the discovery of controlled self-assembly of 2D-silica nanosheets (2D-SiNSs) into hollow micron-sized soccer ball-like shells (SA-SiMS). The assembly is driven by the physical flexibility of the 2D-SiNSs and the differential electricdouble-layer charge gradient creating electrostatic bias on the edge and face regions. The resulting SA-SiMS structures exhibit high mechanical stability, even at high-temperatures, and exhibit excellent performance as catalyst support in the dry reforming of methane. The SA-SiMS structures facilitate improved mass transport, leading to enhanced reaction rates, while the thin silica shell prevents sintering of small catalyst nanocrystals, thereby preventing coke formation. This discovery sheds light on the controllable self-assembly of 2D nanomaterials and provides insights into the design and synthesis of advanced mesoscale materials with tailored properties.

4.
Nat Commun ; 14(1): 7667, 2023 Nov 23.
Article in English | MEDLINE | ID: mdl-37996475

ABSTRACT

Metal nanoparticle-organic interfaces are common but remain elusive for controlling reactions due to the complex interactions of randomly formed ligand-layers. This paper presents an approach for enhancing the selectivity of catalytic reactions by constructing a skin-like few-nanometre ultrathin crystalline porous covalent organic overlayer on a plasmonic nanoparticle surface. This organic overlayer features a highly ordered layout of pore openings that facilitates molecule entry without any surface poisoning effects and simultaneously endows favourable electronic effects to control molecular adsorption-desorption. Conformal organic overlayers are synthesised through the plasmonic oxidative activation and intermolecular covalent crosslinking of molecular units. We develop a light-operated multicomponent interfaced plasmonic catalytic platform comprising Pd-modified gold nanoparticles inside hollow silica to achieve the highly efficient and selective semihydrogenation of alkynes. This approach demonstrates a way to control molecular adsorption behaviours on metal surfaces, breaking the linear scaling relationship and simultaneously enhancing activity and selectivity.

5.
Angew Chem Int Ed Engl ; 62(52): e202312656, 2023 Dec 21.
Article in English | MEDLINE | ID: mdl-37702372

ABSTRACT

Advanced electrocatalysts can enable the widespread implementation of clean energy technologies. This paper reviews an emerging class of electrocatalytic materials comprising holey two-dimensional free-standing Pt-group metal (h-2D-PGM) nanosheets, which are categorically challenging to synthesize but inherently rich in all the qualities necessary to counter the kinetic and thermodynamic challenges of an electrochemical conversion process with high catalytic efficiency and stability. Although the 2D anisotropic growth of typical nonlayered metal crystals has succeeded and partly improved their atom-utilization efficiency, regularly distributed in-planar porosity can further optimize three critical factors that govern efficient electrocatalysis process: mass diffusion, electron transfer, and surface reactivity. However, producing such advanced morphological features within h-2D-PGMs is difficult unless they are specially engineered using approaches such as templating or kinetic ramification during 2D growth or controlled etching of preformed 2D-PGM solids. Therefore, this review highlighting the successful fabrication of various porous PGM nanosheets and their electrocatalytic benefits involving smart nanoscale features could inspire next-generation scientific and technological innovations toward securing a sustainable energy future.

6.
Angew Chem Int Ed Engl ; 62(31): e202307816, 2023 Aug 01.
Article in English | MEDLINE | ID: mdl-37335309

ABSTRACT

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D-Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer (e-Pd or e-Ni) was exclusively formed on the flat {110} surface of 2D-Pt, while a non-epitaxial Pd or Ni layer (n-Pd or n-Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D-2D interfaced e-Pd deposition and faster water dissociation on the edge-located n-Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n-Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

7.
Small ; 19(35): e2301190, 2023 08.
Article in English | MEDLINE | ID: mdl-37096899

ABSTRACT

Silicon nanostructures (SiNSs) can provide multifaceted bioapplications; but preserving their subhundred nm size during high-temperature silica-to-silicon conversion is the major bottleneck. The SC-SSR utilizes an interior metal-silicide stratum space at a predetermined radial distance inside silica nanosphere to guide the magnesiothermic reduction reaction (MTR)-mediated synthesis of hollow and porous SiNSs. In depth mechanistic study explores solid-to-hollow transformation encompassing predefined radial boundary through the participation of metal-silicide species directing the in-situ formed Si-phase accumulation within the narrow stratum. Evolving thin-porous Si-shell remains well protected by the in-situ segregated MgO emerging as a protective cast against the heat-induced deformation and interparticle sintering. Retrieved hydrophilic SiNSs (<100 nm) can be conveniently processed in different biomedia as colloidal solutions and endocytosized inside cells as photoluminescence (PL)-based bioimaging probes. Inside the cell, rattle-like SiNSs encapsulated with Pd nanocrystals can function as biorthogonal nanoreactors to catalyze intracellular synthesis of probe molecules through C-C cross coupling reaction.


Subject(s)
Nanospheres , Nanostructures , Silicon/chemistry , Nanostructures/chemistry , Silicon Dioxide/chemistry , Nanospheres/chemistry , Porosity
8.
Angew Chem Int Ed Engl ; 62(28): e202303890, 2023 Jul 10.
Article in English | MEDLINE | ID: mdl-37071554

ABSTRACT

Herein, by choosing few-nm-thin two-dimensional (2D) nanocrystals of MOF-5 containing in-planner square lattices as a modular platform, a crystal lattice-guided wet-chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)-shaped and fractal-patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical-shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion-limited etching process has been optimized to devise high-yield of size-tunable fractal-pores on the MOF surface that tenders for a compatibly high payload of catalytic ReI -complexes using the existing large edge area once modified into a free amine-group-exposed inner pore surface. Finally, on benefiting from the long-range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross-interface charge-transportation and well-exposure of immobilized ReI -catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO2 -to-CO reduction.

9.
BMC Sports Sci Med Rehabil ; 15(1): 39, 2023 Mar 23.
Article in English | MEDLINE | ID: mdl-36959659

ABSTRACT

BACKGROUND: Previous studies have demonstrated a relationship between headaches and temporomandibular disorders (TMDs). Moreover, recent studies have shown functional, anatomical, and neurological associations between the temporomandibular joint (TMJ) and upper cervical spine. This study aimed to investigate the effectiveness of manual therapy and cervical spine stretching exercises for pain and disability in patients with myofascial TMDs accompanied by headaches. METHODS: Thirty-four patients recruited from Gyeryong Hospital with headaches and diagnosed with TMDs were randomly assigned to the experimental (n = 17) and control (n = 17) groups. Headache impact was assessed using the Korean Headache Impact Test-6. Masseter myofascial pain was measured using the visual analog scale, and TMJ pressure pain threshold levels were evaluated using an algometer. Neck pain intensity was assessed using the numerical rating scale. Once per week for 10 weeks, the experimental group received cervical spine-focused manual therapy and stretching exercises alongside conservative physical therapy, and the control group received conservative physical therapy alone. Patients were evaluated at baseline and 5 and 10 weeks post-intervention. RESULTS: After the intervention, the experimental group exhibited significant reductions in the cervical kyphotic angle, Korean Headache Impact Assessment score, neck pain intensity, TMJ pain pressure threshold, Neck Disability Index score, and Jaw Functional Limitation Scale level compared with the control group (p < 0.01). CONCLUSION: Manual therapy and stretching exercises could help resolve TMDs accompanied by headaches through biomechanical changes in the cervical spine. These findings may guide protocols and clinical trials involving manual therapy that align morphological structures.

10.
ACS Nano ; 16(12): 21111-21119, 2022 Dec 27.
Article in English | MEDLINE | ID: mdl-36445197

ABSTRACT

Nanoscale optimization of late transition-metal oxides for fixing the reversible lithiation/delithiation mechanism with an in-depth mechanistic understanding of nanocrystal (NC) conversion chemistry is important for furthering next-generation Li-ion battery (LIB) technologies. Herein, 1 nm-thin Ni3CoOx (1 nm-NCO) nanosheets synthesized through isomorphic transformation of NiCo layered double hydroxides within a two-dimensional (2D)-SiO2 envelope are chosen. The interconversion of metal/metal-oxide NCs under redox-switching thermal treatment, while retaining reversibility, inspired the accomplishment of identical consequences under the harsh operational conditions of LIB redox cycles by application of the thin-NCO-defined 2D nanospace. During charge/discharge cycles, 1 nm-NCO covered with an in situ formed solid-electrolyte-interphase layer enables fully reversible interconversion between the reactive NC redox pairs, as evidenced by detailed morphological and electrochemical analyses, thus providing high-rate capability with a specific capacity of 61.2% at 5.0 C relative to 0.2 C, outstanding cycle stability delivering a reversible capacity of 1169 mAh g-1, and 913 mAh g-1 with high average Coulombic efficiency (>99.2%) at 3.0 and 5.0 C for 1000 cycles, respectively, which has not been achieved with other transition-metal oxides. Such a nanospace-confinement effect on sustainability of reactive NCs to follow-up a highly reversible conversion reaction at fast charging in LIBs is operative within a slit-like ultrathin 2D nanogap from 1 nm-NCO only, as a relatively thicker 7 nm-NCO anode, with accompanying larger space available, has evidenced poor reversibility of NCs and inadequate cyclic stability under potential high-power density LIB application.

11.
Nano Lett ; 22(15): 6428-6434, 2022 08 10.
Article in English | MEDLINE | ID: mdl-35748753

ABSTRACT

In tandem catalytic systems, controlling the reaction steps and side reactions is extremely challenging. Here, we demonstrate a nanoreactor platform comprising magnetic- and plasmonic-coupled catalytic modules that synchronizes reaction steps at unconnected neighboring reaction sites via decoupled nanolocalized energy harvested using distinct antennae reactors while minimizing the interconflicting effects. As was desired, the course of the reaction and product yields can be controlled by a convenient remote operation of alternating magnetic field (AMF) and near-infrared light (NIR). Following this strategy, a tandem reaction involving [Pd]-catalyzed Suzuki-Miyaura C-C cross-coupling and [Pt]-catalyzed aerobic alcohol oxidation enabled an excellent yield of cinnamaldehyde (ca. 95%) by overcoming the risk of side reactions. The customization scope for using different catalytic metals (Pt, Pd, Ru, and Rh) with in situ control over product release through remotely operable benign energy sources opens avenues for designing diverse catalytic schemes for targeted applications.


Subject(s)
Metals , Nanotechnology , Catalysis , Magnetic Phenomena , Physical Phenomena
12.
Chem Rev ; 122(15): 12748-12863, 2022 08 10.
Article in English | MEDLINE | ID: mdl-35715344

ABSTRACT

Nanomaterials (NMs) with unique structures and compositions can give rise to exotic physicochemical properties and applications. Despite the advancement in solution-based methods, scalable access to a wide range of crystal phases and intricate compositions is still challenging. Solid-state reaction (SSR) syntheses have high potential owing to their flexibility toward multielemental phases under feasibly high temperatures and solvent-free conditions as well as their scalability and simplicity. Controlling the nanoscale features through SSRs demands a strategic nanospace-confinement approach due to the risk of heat-induced reshaping and sintering. Here, we describe advanced SSR strategies for NM synthesis, focusing on mechanistic insights, novel nanoscale phenomena, and underlying principles using a series of examples under different categories. After introducing the history of classical SSRs, key theories, and definitions central to the topic, we categorize various modern SSR strategies based on the surrounding solid-state media used for nanostructure growth, conversion, and migration under nanospace or dimensional confinement. This comprehensive review will advance the quest for new materials design, synthesis, and applications.


Subject(s)
Nanostructures , Nanostructures/chemistry , Phototherapy
13.
J Am Chem Soc ; 144(20): 9033-9043, 2022 May 25.
Article in English | MEDLINE | ID: mdl-35486818

ABSTRACT

Despite the Pt-catalyzed alkaline hydrogen evolution reaction (HER) progressing via oxophilic metal-hydroxide surface hybridization, maximizing Pt reactivity alongside operational stability is still unsatisfactory due to the lack of well-designed and optimized interface structures. Producing atomically flat two-dimensional Pt nanodendrites (2D-PtNDs) through our 2D nanospace-confined synthesis strategy, this study tackles the insufficient interfacial contact effect during HER catalysis by realizing an area-maximized and firmly bound lateral heterointerface with NiFe-layered double hydroxide (LDH). The well-oriented {110} crystal surface exposure of Pt promotes electronic interplay that bestows strong LDH binding. The charge-relocated interfacial bond in 2D-PtND/LDH accelerates the hydrogen generation steps and achieves nearly the highest reported Pt mass activity enhancement (∼11.2 times greater than 20 wt % Pt/C) and significantly improved long-term operational stability. This work uncovers the importance of the shape and facet of Pt to create heterointerfaces that provide catalytic synergy for efficient hydrogen production.

14.
Nano Lett ; 22(3): 1159-1166, 2022 Feb 09.
Article in English | MEDLINE | ID: mdl-35088595

ABSTRACT

Despite the enormous applications of and fundamental scientific interest in amorphous hollow-silica nanostructures (h-SiNSs), their synthesis in crystal-like nonspherical polygonal architectures is challenging. Herein, we present a facile one-shot synthetic procedure for various unconventional h-SiNSs with controllable surface curvatures (concave, convex, or angular), symmetries (spherical, polygonal, or Janus), and interior architectures (open or closed walls) by the addition of a metal salt and implementing kinetic handles of silica precursor (silanes/ammonia) concentrations and reverse-micellar volume. During the silica growth, we identified the key role of transiently in situ crystallized metal coordination complexes as a nanopolyhedral "ghost template", which provides facet-selective interactions with amino-silica monomers and guides the differential silica growth that produces different h-SiNSs. Additionally, crystal-like well-defined polygonal h-SiNSs with flat surfaces, assembled as highly ordered close-packed octahedral mesoscale materials (ca. 3 µm) where h-SiNSs with different nanoarchitectures act as building units (ca. 150 nm) to construct customizable cavities and nanospaces, differ from conventionally assembled materials.

15.
Small ; 17(34): e2102851, 2021 08.
Article in English | MEDLINE | ID: mdl-34263553

ABSTRACT

Here, lamellar confinement strategy is introduced for "sheet-to-nanocrystals (NCs)" conversion within a 2D-SiO2 envelope, which constructs a catalytic nanocartridge holding a platoon of isolated and in-plane-aligned ultrasmall Ni-NCs, performing as a robust and coking-resistant catalytic system for dry reforming of methane. Overcoming the problem of unavoidable bulk crystal growth from multiple sheets-stack or sheet-on-open-support, silica bilayer-encasing tightly clamps the atomic-thin Ni(OH)2 -nanosheet during thermal conversion and further hinders the migratory fusion of the resultant Ni-NCs. Upon heating-cooling cycle, the flapping silica envelope clutches the Ni-NCs like "eggs in a carton," subsequently, ensuring their thermal stability. Owing to the unique 2D-enveloped rigid architecture, Ni-NCs can circumvent sintering and coke deposition while tolerating the high temperatures (>700 °C) for long operation (>100 h), affording high conversions to syngas.


Subject(s)
Methane , Nanoparticles , Catalysis , Nickel , Silicon Dioxide
16.
J Am Chem Soc ; 143(28): 10582-10589, 2021 Jul 21.
Article in English | MEDLINE | ID: mdl-34213897

ABSTRACT

Despite the enormous application potential, methods for conformal few-atomic-layer deposition on colloidal nanocrystals (NCs) are scarce. Similar to the process of lamination, we introduce a "confine and shine" strategy to homogeneously modify the different surface curvatures of plasmonic NCs with ultrathin conformal layers of diverse catalytic noble metals. This self-limited epitaxial skinlike metal growth harvests the localized surface plasmon resonance to induce reduction chemistry directly on the NC surface, confined inside hollow silica. This strategy avoids any kinetic anisotropic metal deposition. Unlike the conventional thick, anisotropic, and dendritic shells, which show severe nonradiative damping, the skinlike metal lamination preserves the key plasmonic properties of the core NCs. Consequently, the plasmonic-catalytic hybrid nanoreactors can carry out a variety of organic reactions with impressive rates.

17.
Angew Chem Int Ed Engl ; 60(32): 17579-17586, 2021 08 02.
Article in English | MEDLINE | ID: mdl-34107153

ABSTRACT

Nanostructures converting chemical energy to mechanical work by using benign metabolic fuels, have huge implications in biomedical science. Here, we introduce Au/Pt-based Janus nanostructures, resembling to "egg-in-nest" morphology (Au/Pt-ENs), showing enhanced motion as a result of dual enzyme-relay-like catalytic cascade in physiological biomedia, and in turn showing molecular-laden transport to living cells. We developed dynamic-casting approach using silica yolk-shell nanoreactors: first, to install a large Au-seed fixing the silica-yolk aside while providing the anisotropically confined concave hollow nanospace to grow curved Pt-dendritic networks. Owing to the intimately interfaced Au and Pt catalytic sites integrated in a unique anisotropic nest-like morphology, Au/Pt-ENs exhibited high diffusion rates and displacements as the result of glucose-converted oxygen concentration gradient. High diffusiophoresis in cell culture media increased the nanomotor-membrane interaction events, in turn facilitated the cell internalization. In addition, the porous network of Au/Pt-ENs facilitated the drug-molecule cargo loading and delivery to the living cells.


Subject(s)
Drug Carriers/chemistry , Glucose/metabolism , Nanoparticles/chemistry , Nanotechnology/methods , Adsorption , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Biological Transport , Catalysis , Cell Line, Tumor , Doxorubicin/chemistry , Doxorubicin/pharmacology , Drug Liberation , Glucose/chemistry , Gold/chemistry , Humans , Motion , Oxidation-Reduction , Platinum/chemistry , Porosity , Silicon Dioxide/chemistry
18.
Angew Chem Int Ed Engl ; 60(30): 16337-16342, 2021 07 19.
Article in English | MEDLINE | ID: mdl-34041834

ABSTRACT

Nanodevices, harvesting the power of synthetic catalysts and enzymes to perform enantioselective synthesis inside cell, have never been reported. Here, we synthesized round bottom jar-like silica nanostructures (SiJARs) with a chemo-responsive metal-silicate lid. This was isolated as an intermediate structure during highly controlled solid-state nanocrystal-conversion at the arc-section of silica shell. Different catalytic noble metals (Pt, Pd, Ru) were selectively modified on the lid-section through galvanic reactions. And, lid aperture-opening was regulated by mild acidic conditions or intracellular environment which accommodated the metal nanocrystals and enzymes, and in turn created an open-mouth nanoreactor. Distinct from the free enzymes, SiJARs performed asymmetric aldol reactions with high activity and enantioselectivity (yield >99 %, ee=95 %) and also functioned as the artificial catalytic organelles inside living cells. This work bridges the enormous potential of sophisticated nanocrystal-conversion chemistry and advanced platforms for new-to-nature catalysis.


Subject(s)
Biomimetic Materials/chemistry , Enzymes/chemistry , Metal Nanoparticles/chemistry , Metals/chemistry , Silicon Dioxide/chemistry , Aldehydes/chemistry , Catalysis , Hot Temperature , Manganese Compounds/chemistry , Oxides/chemistry , Palladium/chemistry , Platinum/chemistry , Ruthenium/chemistry , Stereoisomerism
19.
J Colloid Interface Sci ; 597: 94-103, 2021 Sep.
Article in English | MEDLINE | ID: mdl-33862450

ABSTRACT

In this study, a Janus Fe/C3N4 micromotor driven by a chromate-hydrogen peroxide (Cr(VI)/H2O2) redox system was developed and its movement was analyzed. The motion of the micromotor was tracked via nanoparticle tracking analysis (NTA) and the corresponding diffusion coefficients (D) were determined. The NTA results revealed that D = 0 in water in the absence of additives (Cr(VI) or H2O2). The addition of H2O2 resulted in an increase in D from 0 to 12 × 106 nm2 s-1, which further increased to 20 × 106, 26.5 × 106, 29 × 106, and 44 × 106 nm2 s-1 with the addition of 0.5, 1, 2, and 5 ppm of Cr(VI), respectively. Cr(VI) alone did not efficiently propel the Fe/C3N4-based micromotor. Therefore, it was proposed that the Cr(VI)/H2O2 redox system generates O2, which plays a major role in the movement of the C3N4-based micromotor. In addition, the formation of reactive species, such as OH and 1O2, was confirmed through electron spin resonance experiments. The reactive species efficiently degraded sulfamethaxazole (SMX), an organic pollutant, as demonstrated through degradation studies and product analyses. The effects of various parameters, such as H2O2 concentration, Cr(VI) concentration, and initial pH on the movement of micromotor and degradation of SMX were also documented.

20.
Nano Lett ; 21(1): 279-287, 2021 01 13.
Article in English | MEDLINE | ID: mdl-33306397

ABSTRACT

Next-generation catalysts are urgently needed to tackle the global challenge of antimicrobial resistance. Existing antimicrobials cannot function in the complex and stressful chemical conditions found in biofilms, and as a result, they are unable to infiltrate, diffuse into, and eradicate the biofilm and its associated matrix. Here, we introduce mixed-FeCo-oxide-based surface-textured nanostructures (MTex) as highly efficient magneto-catalytic platforms. These systems can produce defensive ROS over a broad pH range and can effectively diffuse into the biofilm and kill the embedded bacteria. Because the nanostructures are magnetic, biofilm debris can be scraped out of the microchannels. The key antifouling efficacy of MTex originates from the unique surface topography that resembles that of a ploughed field. These are captured as stable textured intermediates during the oxidative annealing and solid-state conversion of ß-FeOOH nanocrystals. These nanoscale surfaces will advance progress toward developing a broad array of new enzyme-like properties at the nanobio interface.


Subject(s)
Anti-Infective Agents , Metal Nanoparticles , Biofilms , Oxides , Reactive Oxygen Species
SELECTION OF CITATIONS
SEARCH DETAIL
...