Atomically thin iridium nanosheets for oxygen evolution electrocatalysis.

2D nanostructures of noble metals hold great potential for developing efficient electrocatalysts due to their high atom efficiency associated with their large specific surface area and abundant active sites. Here, we introduce a one-pot solvothermal synthesis method that can enable the fabrication of freestanding atomically thin Ir nanosheets. The thermal decomposition of a complex of Ir and a long-chain amine, which could readily be formed with the assistance of a strong base, under CO flow conditions successfully yielded Ir nanosheets consisting of 2-4 atomic layers. The prepared Ir nanosheets showed prominent activity and stability toward oxygen evolution electrocatalysis in acidic conditions, which can be attributed to their ultrathin 2D structure.

Freestanding Penta-Twinned Palladium Nanosheets.

Control over the morphology of nanomaterials to have a 2D structure and manipulating the surface strain of nanostructures through defect control have proved to be promising for developing efficient catalysts for sustainable chemical and energy conversion. Here a one-pot aqueous synthesis route of freestanding Pd nanosheets with a penta-twinned structure (PdPT NSs) is presented. The generation of the penta-twinned nanosheet structure can be succeeded by directing the anisotropic growth of Pd under the controlled reduction kinetics of Pd precursors. Experimental and computational investigations showed that the surface atoms of the PdPT NSs are effectively under a compressive environment due to the strain imposed by their twin boundary defects. Due to the twin boundary-induced surface strain as well as the 2D structure of the PdPT NSs, they exhibited highly enhanced electrocatalytic activity for oxygen reduction reaction compared to Pd nanosheets without a twin boundary, 3D Pd nanocrystals, and commercial Pd/C and Pt/C catalysts.

Advancements in the Application of Ribosomally Synthesized and Post-Translationally Modified Peptides (RiPPs).

Ribosomally synthesized and post-translationally modified peptides (RiPPs) represent a significant potential for novel therapeutic applications because of their bioactive properties, stability, and specificity. RiPPs are synthesized on ribosomes, followed by intricate post-translational modifications (PTMs), crucial for their diverse structures and functions. PTMs, such as cyclization, methylation, and proteolysis, play crucial roles in enhancing RiPP stability and bioactivity. Advances in synthetic biology and bioinformatics have significantly advanced the field, introducing new methods for RiPP production and engineering. These methods encompass strategies for heterologous expression, genetic refactoring, and exploiting the substrate tolerance of tailoring enzymes to create novel RiPP analogs with improved or entirely new functions. Furthermore, the introduction and implementation of cutting-edge screening methods, including mRNA display, surface display, and two-hybrid systems, have expedited the identification of RiPPs with significant pharmaceutical potential. This comprehensive review not only discusses the current advancements in RiPP research but also the promising opportunities that leveraging these bioactive peptides for therapeutic applications presents, illustrating the synergy between traditional biochemistry and contemporary synthetic biology and genetic engineering approaches.

Association of cranial base suture/synchondrosis fusion with severity of increased intracranial pressure in Crouzon syndrome.

This study investigated how the fusion states of the cranial base is related to the degree of increased intracranial pressure (ICP) in patients with Crouzon syndrome. This retrospective cohort study enrolled patients who were diagnosed with Crouzon syndrome between May 2007 and April 2022. We categorized the patients into three groups: A, B, and C, according to the severity of increased ICP and the number of cranial vault remodeling procedures for corrective operation. The preoperative fusion states of the cranial base sutures/synchondroses were examined using facial bone computed tomography and compared between groups. Overall, 22 patients were included in Groups A, B, and C, including 8, 7, and 7 patients, respectively. The preoperative average grades of the total cranial base suture/synchondrosis fusion appeared to significantly increase with severity, except for the frontoethmoidal suture, which showed the opposite tendency. In the subgroup analysis, frontosphenoidal, sphenoparietal, sphenosquamosal, parietomastoid, and occipitomastoid suture and petro-occipital synchondrosis were associated with earlier fusion in the more severe group. Premature closure of the cranial base sutures/synchodroses seems to be associated with increased ICP severity in patients with Crouzon syndrome. Precise evaluation of minor sutures/synchondroses at the first visit might help build subsequent operative plans and predict disease prognosis.

Reprogramming biocatalytic futile cycles through computational engineering of stereochemical promiscuity to create an amine racemase.

Repurposing the intrinsic properties of natural enzymes can offer a viable solution to current synthetic challenges through the development of novel biocatalytic processes. Although amino acid racemases are ubiquitous in living organisms, an amine racemase (AR) has not yet been discovered despite its synthetic potential for producing chiral amines. Here, we report the creation of an AR based on the serendipitous discovery that amine transaminases (ATAs) can perform stereoinversion of 2-aminobutane. Kinetic modeling revealed that the unexpected off-pathway activity results from stereochemically promiscuous futile cycles due to incomplete stereoselectivity for 2-aminobutane. This finding motivated us to engineer an S-selective ATA through in silico alanine scanning and empirical combinatorial mutations, creating an AR with broad substrate specificity. The resulting AR, carrying double point mutations, enables the racemization of both enantiomers of diverse chiral amines in the presence of a cognate ketone. This strategy may be generally applicable to a wide range of transaminases, paving the way for the development of new-to-nature racemases.

Upconversion Material-Plasmonic Metal-Semiconductor Ternary Heteronanostructures for Wide-Range Solar-to-Chemical Energy Conversion.

Harvesting full-spectrum solar energy is a critical issue for developing high-performance photocatalysts. Here, we report a hierarchical heteronanostructure consisting of upconverting, plasmonic, and semiconducting materials as a solar-to-chemical energy conversion platform that can exploit a wide range of sunlight (from ultraviolet (UV) to near-infrared). Lanthanide-doped NaYF4 nanorod-spherical Au nanocrystals-TiO2 ternary hybrid nanostructures with a well-controlled configuration and intimate contact between the constituent materials could be synthesized by a wet-chemical method. Notably, the prepared ternary hybrids exhibited high photocatalytic activity for the H2 evolution reaction under simulated solar and near-infrared light irradiation due to their broadband photoresponsivity and strong optical interaction between the constituents. Through systematic studies on the mechanism of energy transfer during the photocatalysis of the ternary hybrids, we revealed that upconverted photon energy from the upconversion domain transfers to the Au and TiO2 domains primarily through the Förster resonance energy transfer process, resulting in enhanced photocatalysis.

Orbital floor defect caused by invasive aspergillosis: a case report and literature review.

Fungal sinusitis is relatively rare, but it has become more common in recent years. When fungal sinusitis invades the orbit, it can cause proptosis, chemosis, ophthalmoplegia, retroorbital pain, and vision impairment. We present a case of an extensive orbital floor defect due to invasive fungal sinusitis. A 62-year-old man with hypertension and a history of lung adenocarcinoma, presented with right-side facial pain and swelling. On admission, the serum glucose level was 347 mg/dL, and hemoglobin A1c was 11.4%. A computed tomography scan and a Waters' view X-ray showed right maxillary sinusitis with an orbital floor defect. On hospital day 3, functional endoscopic sinus surgery was performed by the otorhinolaryngology team, and an aspergilloma in necrotic inflammatory exudate obtained during exploration. On hospital day 7, orbital floor reconstruction with a Medpor Titan surgical implant was done. In principle, the management of invasive sino- orbital fungal infection often begins with surgical debridement and local irrigation with an antifungal agent. Exceptionally, in this case, debridement and immediate orbital floor reconstruction were performed to prevent enophthalmos caused by the extensive orbital floor defect. The patient underwent orbital floor reconstruction and received intravenous and oral voriconazole. Despite orbital invasion, there were no ophthalmic symptoms or sequelae.

Intramuscular epidermal cyst in the masticator space: a case report.

An epidermal cyst, also known as an epidermoid cyst or epidermal inclusion cyst, is the most prevalent type of cutaneous cyst. This noncancerous lesion can appear anywhere on the body, typically presenting as an asymptomatic dermal nodule with a visible central punctum. In the case presented herein, an epidermal cyst with uncommon features was misdiagnosed as a lymphatic malformation based on preoperative magnetic resonance imaging (MRI). A 61-year-old man came to us with a swollen left cheek that had been present for 11 months. The preoperative MRI revealed a 3 × 3.8 × 4.6 cm lobulated cystic lesion with thin rim enhancement in the left masticator space. The initial differential diagnosis pointed toward a lymphatic malformation. We proceeded with surgical excision of the lesion via an intraoral approach, and the specimen was sent to the pathology department. The pathological diagnosis revealed a ruptured epidermal cyst, indicating that the initial diagnosis of a lymphatic malformation based on preoperative MRI was incorrect. Epidermal cysts located under the muscle with no visible central punctum are uncommon, but should be considered if a patient presents with facial swelling.

Plasmonic Nanocrystal Assembly-Semiconductor Hybrids for Boosting Visible to Near-Infrared Photocatalysis.

Plasmonic metal-semiconductor hybrid photocatalysts have received much attention because of their wide light harvesting range and efficient charge carrier generation capability originating from plasmon energy transfer. Here, we introduce a plasmonic metal-semiconductor hybrid nanostructure consisting of a Au core-satellite assembly and crystalline TiO2. The formation of Au@TiO2-Au core-satellite assemblies using TiO2 as a spacer and the subsequent growth of outer TiO2 shells on the core-satellite assemblies, followed by calcination, successfully generated Au core-satellite assembly@TiO2 nanostructures. Exquisite control over the growth of the TiO2 interlayer enabled the regulation of the gap distance between the core and satellite Au nanocrystals within the same hybrid morphology. Due to the structural controllability of the present approach, the gap-distance-dependent plasmonic and photocatalytic properties of the hybrid nanostructures could be explored. The nanostructures possessing the most closely arranged Au nanocrystals showed high photocatalytic activity under visible to near-infrared light irradiation, which can be attributed to strong plasmon coupling between the core and satellite Au nanocrystals that can expedite the formation of intense plasmon energy and its transfer to TiO2.

Efficacy analysis of virtual reality-based training for activities of daily living and functional task training in stroke patients: A single-subject study.

INTRODUCTION: Virtual reality (VR)-based training for functions such as cognition, upper extremities, balancing, and activities of daily living (ADL) has been used on stroke patients, and its efficacy has been reported. However, no comparison has been made between the efficacy of VR-based training for daily activities that exactly reproduces ADL and functional training. Therefore, this study sought to analyze the difference in independency enhancement of VR-based training for daily activities compared to cognitive and motor functional training. PATIENT CONCERNS AND DIAGNOSIS: This study was conducted on 4 patients who have been diagnosed with stroke and are currently receiving rehabilitation therapy in G hospital located in the city of Gwangju, using A-B-A'-B' design from single-subject experimental designs. INTERVENTIONS: Intervention was performed in 2 ways: application of VR-based training for daily activities after the application of cognitive and motor function training; and application of cognitive and motor function training after the application of VR-based training for daily activities. The Assessment of Motor and Process Skills, Computer Cognitive Screening Assessment System, Box and Block Test, and Grip and Pinch Strength Test were used to measure the changes in the performance of daily activities, cognitive function, and upper extremities function. OUTCOMES: The results confirmed that the performance of daily activities, cognitive function, and upper extremities function was improved after the application of VR-based intervention. In addition, the efficacy of independency enhancement was maximized by the early approach of training for daily activities at the time of VR-based intervention in stroke patients. CONCLUSIONS: VR-based intervention of training for daily activities and functional training can be considered to benefit the improvement of the performance of daily activities, cognitive function, and upper extremities function in stroke patients. In addition, although functional training was also effective in enhancing independency and functional improvement in stroke patients, an early approach to training for ADL based on tasks with objectives was deemed to be more effective.

Directing Energy Flow in Core-Shell Nanostructures for Efficient Plasmon-Enhanced Electrocatalysis.

Conjugating plasmonic metals with catalytically active materials with controlled configurations can harness their light energy harvesting ability in catalysis. Herein, we present a well-defined core-shell nanostructure composed of an octahedral Au nanocrystal core and a PdPt alloy shell as a bifunctional energy conversion platform for plasmon-enhanced electrocatalysis. The prepared Au@PdPt core-shell nanostructures exhibited significant enhancements in electrocatalytic activity for methanol oxidation and oxygen reduction reactions under visible-light irradiation. Our experimental and computational studies revealed that the electronic hybridization of Pd and Pt allows the alloy material to have a large imaginary dielectric function, which can efficiently induce the shell-biased distribution of plasmon energy upon illumination and, hence, its relaxation at the catalytically active region to promote electrocatalysis.

Monitoring hydrogen transport through graphene by in situ surface-enhanced Raman spectroscopy.

Exploring the atomic or molecular transport properties of two-dimensional materials is vital to understand their inherent functions and, thus, to expedite their use in various applications. Herein, a surface-enhanced Raman spectroscopy (SERS)-based in situ analytical tool for the sensitive and rapid monitoring of hydrogen transport through graphene is reported. In this method, a reducing agent, which can provide hydrogen species, and a Raman dye self-assembled on a SERS platform are separated by a graphene membrane, and the reduction of the Raman dye by hydrogen species transferred through graphene is monitored with SERS. For validating the efficacy of our method, the catalytic reduction of surface-bound 4-nitrothiophenol by sodium borohydride was chosen in this study. The experimental results distinctly demonstrate that the high sensitivity and rapid detection ability of SERS can allow the effective analysis of the hydrogen transport properties of graphene.

Field application of cost-effective sensors for the monitoring of NH3, H2S, and TVOC in environmental treatment facilities and the estimation of odor intensity.

Odor is usually a complex mixture of various compounds. In many countries, odor complaints have been addressed using the air dilution olfactory method (ADOM) to reduce their malodor complaint. In this study, continuous monitoring of ammonia, hydrogen sulfide, and total volatile organic compounds (TVOC) using sensors was conducted in facilities for municipal and livestock wastewater treatment (LWT), and for food waste composting (FWC). Odor intensity was modeled by multivariate linear regression using sensor monitoring data with air dilution measured by the ADOM. In testing the performance of sensors in the lab, all three sensors showed acceptable values for linearity, accuracy, repeatability, lowest detection limit, and response time, so the sensors were acceptable for application in the field. In on-site real-time monitoring, the three sensors functioned well in the three environmental facilities during the testing period. Average ammonia and hydrogen sulfide concentrations were high in the LWT facility, while TVOC showed the highest concentration in the FWC facility. A longer sampling time is necessary for ammonia monitoring. Odor intensity from individual sensor data correlated well to complex odor measured by the ADOM. Finally, we suggest a protocol for field application of sensor monitoring and odor data reproduction.Implications: We suggest a protocol for the field application of sensor monitoring and odor data estimation in this study. This study can be useful to a policy maker and field operator to reduce odor emission through the determination of a more effective treatment technology and removal pathway for individual odorants.

Role of Surface Strain at Nanocrystalline Pt{110} Facets in Oxygen Reduction Catalysis.

We have developed a synthesis method of rhombic dodecahedral Pd@Pt core-shell nanocrystals bound exclusively by {110} facets with controlled numbers of Pt atomic layers to study the surface strain-catalytic activity relationship of Pt{110} facets. Through control over growth kinetics, the epitaxial and conformal overgrowth of Pt shells on the {110} facets of rhombic dodecahedral Pd nanocrystals could be achieved. Notably, the electrocatalytic activity of the Pd@Pt nanocrystals toward oxygen reduction reaction decreased as their Pt shells became thinner and thus more in-plane compressive surface strain was applied, which is in sharp contrast to previous reports on Pt-based catalysts. Density functional theory calculations revealed that the characteristic strain-activity relationship of Pt{110} facets is the result of the counteraction of out-of-plane surface strain against the applied in-plane surface strain, which can effectively impose a tensile environment on the surface atoms of the Pd@Pt nanocrystals under the compressive in-plane strain.

Direct strain correlations at the single-atom level in three-dimensional core-shell interface structures.

Nanomaterials with core-shell architectures are prominent examples of strain-engineered materials. The lattice mismatch between the core and shell materials can cause strong interface strain, which affects the surface structures. Therefore, surface functional properties such as catalytic activities can be designed by fine-tuning the misfit strain at the interface. To precisely control the core-shell effect, it is essential to understand how the surface and interface strains are related at the atomic scale. Here, we elucidate the surface-interface strain relations by determining the full 3D atomic structure of Pd@Pt core-shell nanoparticles at the single-atom level via atomic electron tomography. Full 3D displacement fields and strain profiles of core-shell nanoparticles were obtained, which revealed a direct correlation between the surface and interface strain. The strain distributions show a strong shape-dependent anisotropy, whose nature was further corroborated by molecular statics simulations. From the observed surface strains, the surface oxygen reduction reaction activities were predicted. These findings give a deep understanding of structure-property relationships in strain-engineerable core-shell systems, which can lead to direct control over the resulting catalytic properties.

Evolutionary origin and functional diversification of aminotransferases.

Aminotransferases (ATs) are pyridoxal 5'-phosphate-dependent enzymes that catalyze the transamination reactions between amino acid donor and keto acid acceptor substrates. Modern AT enzymes constitute ∼2% of all classified enzymatic activities, play central roles in nitrogen metabolism, and generate multitude of primary and secondary metabolites. ATs likely diverged into four distinct AT classes before the appearance of the last universal common ancestor and further expanded to a large and diverse enzyme family. Although the AT family underwent an extensive functional specialization, many AT enzymes retained considerable substrate promiscuity and multifunctionality because of their inherent mechanistic, structural, and functional constraints. This review summarizes the evolutionary history, diverse metabolic roles, reaction mechanisms, and structure-function relationships of the AT family enzymes, with a special emphasis on their substrate promiscuity and multifunctionality. Comprehensive characterization of AT substrate specificity is still needed to reveal their true metabolic functions in interconnecting various branches of the nitrogen metabolic network in different organisms.

Microbiome engineering for sustainable agriculture: using synthetic biology to enhance nitrogen metabolism in plant-associated microbes.

Plants benefit from symbiotic relationships with their microbiomes. Modifying these microbiomes to further promote plant growth and improve stress tolerance in crops is a promising strategy. However, such efforts have had limited success, perhaps because the original microbiomes quickly re-establish. Since the complex biological networks involved are little understood, progress through conventional means is time-consuming. Synthetic biology, with its practical successes in multiple industries, could speed up this research considerably. Some fascinating candidates for production by synthetic microbiomes are organic nitrogen metabolites and related pyridoxal-5'-phosphate-dependent enzymes, which have pivotal roles in microbe-microbe and plant-microbe interactions. This review summarizes recent studies of these metabolites and enzymes and discusses prospective synthetic biology platforms for sustainable agriculture.

Aromatic L-amino acid decarboxylases: mechanistic features and microbial applications.

Aromatic L-amino acid decarboxylases (AADCs) catalyze the conversion of aromatic L-amino acids into aromatic monoamines that play diverse physiological and biosynthetic roles in living organisms. For example, dopamine and serotonin serve as major neurotransmitters in animals, whereas tryptamine and tyramine are essential building blocks for synthesizing a myriad of secondary metabolites in plants. In contrast to the vital biological roles of AADCs in higher organisms, microbial AADCs are found in rather a limited range of microorganisms. For example, lactic acid bacteria are known to employ AADCs to achieve intracellular pH homeostasis and engender accumulation of tyramine, causing a toxic effect in fermented foods. Owing to the crucial pharmaceutical implications of aromatic monoamines and their derivatives, synthetic applications of AADCs have attracted growing attention. Besides, recent studies have uncovered that AADCs of human gut microbes influence host physiology and are involved in drug availability of Parkinson's disease medication. These findings bring the bacterial AADCs into a new arena of extensive research for biomedical applications. Here, we review catalytic features of AADCs and present microbial applications and challenges for biotechnological exploitation of AADCs. KEY POINTS: • Aromatic monoamines and their derivatives are increasingly important in the drug industry. • Aromatic L-amino acid decarboxylases are the only enzyme for synthesizing aromatic monoamines. • Microbial applications of aromatic L-amino acid decarboxylases have drawn growing attention.

Surface Engineering of Palladium Nanocrystals: Decoupling the Activity of Different Surface Sites on Nanocrystal Catalysts.

The existence of various surface active sites within a nanocrystal (NC) catalyst complicates understanding their respective catalytic properties and designing an optimal catalyst structure for a desired catalytic reaction. Here, we developed a novel approach that allows unequivocal investigation on the intrinsic catalytic reactivity of the edge and terrace atoms of NCs. Through the comparison of the catalytic behaviors of edge-covered Pd NCs, which were prepared by the selective deposition of catalytically inactive Au atoms onto the edge sites of rhombic dodecahedral (RD) Pd NCs, with those of the pristine RD Pd NCs toward alkyne hydrogenation and Suzuki-Miyaura coupling reactions, we could decouple the activity of the edge and {110}-plane atoms of the Pd NCs without uncertainties. We expect that this study will provide an opportunity to scrutinize the surface properties of various NC catalysts to a more precise level and devise ideal catalysts for intended catalytic reactions.

Exploiting Plasmonic Hot Spots in Au-Based Nanostructures for Sensing and Photocatalysis.

ConspectusLocalized surface plasmon resonance is a unique property appearing in certain metal nanostructures, which can generate hot carriers (electrons and holes) and bring about an intense electromagnetic field localized near the surface of nanostructures. Specific locations, such as the rough surfaces and gaps in nanostructures, where a strong electromagnetic field is formed are referred to as hot spots. Hot-spot-containing plasmonic nanostructures have shown great promise in molecular sensing and plasmon-induced catalytic applications by exploiting the unique optical properties of hot spots. In this Account, we will review our recent developments in the synthesis of Au nanostructures consisting of multiple hot spots and Au-based heteronanostructures combining secondary active metals or semiconductors with Au nanostructures as promising plasmonic platforms for hot-spot-induced sensing and photocatalysis. We first provide a brief introduction to Au nanocrystals and Au nanoparticle assemblies with multiple hot spots. High-index-faceted hexoctahedral Au nanocrystals having multiple high-curvature vertices and edges are beneficial for the generation of an intense and reproducible electromagnetic field, which can enhance the performance of surface-enhanced Raman scattering-based molecular sensing. In addition, the engineering of interparticle gaps in Au nanoparticle assemblies to have a controlled size and a certain number of gaps can lead to the enhancement of plasmonic properties due to the significant amplification of the electromagnetic field at interparticle gaps. We then discuss hot-spot-containing Au-based heteronanostructures prepared by growing secondary components on the aforementioned Au nanostructures. With a combination of merit from strong plasmon energy formed by hot spots and catalytically active secondary materials, Au-based heteronanostructures have emerged as an attractive and versatile catalyst platform for various photocatalytic reactions. Through the control of key factors governing the photocatalysis of Au-based heteronanostructures, such as the coupling manner, shell thickness of secondary materials, and intimacy of contact, the plasmon energy formation of heteronanostructures and its transfer to catalytically active materials can be optimized, leading to the promotion of photocatalysis, such as photocatalytic hydrogen evolution. The rational design of Au nanostructures and Au-based heteronanostructures with multiple hot spots not only could realize enhanced sensing and photocatalysis but also could enable the understanding of the geometry-performance relationship. It is envisioned that the developed strategies can offer new opportunities for the design of various high-efficiency catalytic platforms.