Active learning of reactive Bayesian force fields applied to heterogeneous catalysis dynamics of H/Pt.

Atomistic modeling of chemically reactive systems has so far relied on either expensive ab initio methods or bond-order force fields requiring arduous parametrization. Here, we describe a Bayesian active learning framework for autonomous "on-the-fly" training of fast and accurate reactive many-body force fields during molecular dynamics simulations. At each time-step, predictive uncertainties of a sparse Gaussian process are evaluated to automatically determine whether additional ab initio training data are needed. We introduce a general method for mapping trained kernel models onto equivalent polynomial models whose prediction cost is much lower and independent of the training set size. As a demonstration, we perform direct two-phase simulations of heterogeneous H2 turnover on the Pt(111) catalyst surface at chemical accuracy. The model trains itself in three days and performs at twice the speed of a ReaxFF model, while maintaining much higher fidelity to DFT and excellent agreement with experiment.

Dynamical Study of Adsorbate-Induced Restructuring Kinetics in Bimetallic Catalysts Using the PdAu(111) Model System.

Dynamic restructuring of bimetallic catalysts plays a crucial role in their catalytic activity and selectivity. In particular, catalyst pretreatment with species such as carbon monoxide and oxygen has been shown to be an effective strategy for tuning the surface composition and morphology. Mechanistic and kinetic understanding of such restructuring is fundamental to the chemistry and engineering of surface active sites but has remained challenging due to the large structural, chemical, and temporal degrees of freedom. Here, we combine time-resolved temperature-programmed infrared reflection absorption spectroscopy, ab initio thermodynamics, and machine-learning molecular dynamics to uncover previously unidentified timescale and kinetic parameters of in situ restructuring in Pd/Au(111), a highly relevant model system for dilute Pd-in-Au nanoparticle catalysts. The key innovation lies in utilizing CO not only as a chemically sensitive probe of surface Pd but also as an agent that induces restructuring of the surface. Upon annealing in vacuum, as-deposited Pd islands became encapsulated by Au and partially dissolved into the subsurface, leaving behind isolated Pd monomers on the surface. Subsequent exposure to 0.1 mbar CO enabled Pd monomers to repopulate the surface up to 373 K, above which complete Pd dissolution occurred by 473 K, with apparent activation energies of 0.14 and 0.48 eV, respectively. These restructuring processes occurred over the span of ∼1000 s at a given temperature. Such a minute-timescale dynamics not only elucidates the fluxional nature of alloy catalysts but also presents an opportunity to fine-tune the surface under moderate temperature and pressure conditions.

Malignant transformation of nevus sebaceous to basal-cell carcinoma: Case series, literature review, and management algorithm.

Nevus sebaceous (NS) is a common congenital hamartoma of the skin composed predominantly of sebaceous glands. Although most NS are benign skin tumors, malignant transformations have been reported. There is still controversy about the lifetime risk of malignant degeneration and precise surgical criteria. This study reports cases of malignant degeneration and suggests a surgical treatment algorithm. The medical records of patients with basal-cell carcinoma (BCC) arising from NS between January 2001 and January 2021 were retrospectively reviewed. Patient demographics including lesion location, and tumor size were investigated. The symptoms, histological findings before and after excision, complications, and recurrence during 2-year follow-up periods were investigated. Ten patients were identified with BCC arising from NS lesions. All patients were female and the mean age was 52.11 years. All patients complained of sudden morphological changes, the most common type being rapid color changes. Two cases had histological findings that showed a miss-match between punch biopsy and excisional biopsy results. No recurrence was detected 2 years after surgeries in any patients. Cases after third stage, especially in over 40 years who report morphologic changes, should undergo total surgical excision as the first approach, with strong suspicion of malignant degeneration.

Evaluation of tongue mobility following release operation of ankyloglossia with genioglossus myotomy.

Ankyloglossia is a congenital anomaly characterized by a short lingual frenulum and severe form needs release surgery. Our goal in this study was to confirm the long-term safety and efficacy of Z-plasty with genioglossus myotomy compared with traditional Z-plasty alone and to develop a proper measurement tool to validate the postoperative results of release operations for ankyloglossia. Patients were divided in 2 groups, release with Z-plasty only group (group 1) and Z-plasty combined with genioglossus myotomy group (group 2) In group 2, the release of central longitudinal fiber of genioglossus muscle was added in the conventional Z-plasty operative procedure. To analyze the results of the surgery, we developed an objective assessment tool which is the direct length from the innermost point of the floor of mouth to the tip of the tongue, preoperatively and postoperatively, which is called "functional tongue length." A total of 101 patients with ankyloglossia ranging in age from 36 months to 8 years underwent release operation. Although there was no significant difference in terms of postoperative measurements between groups in Kotlow class II, group 2 patients in Class III and IV showed greater postoperative functional tongue length. Also, there was no significant complication requiring secondary surgery. Our study demonstrated that adding genioglossus myotomy to a simple Z-plasty is a safe and effective method for improving the tongue mobility required to make lingual sounds, especially in moderate to severe form of ankyloglossia, along with suggestion of a new measurement tool, which can objectively assess tongue mobility with possibility for universal utilization in ankyloglossia release operation.

Primary non-Hodgkin lymphoma of the parotid gland: a case report.

Most malignant lymphomas of the head and neck region are non-Hodgkin lymphomas (NHL), and diffuse large B-cell lymphoma is the most common subtype. The prevalence of malignant lymphoma among parotid tumors is low, approximately 1% to 4%. The most common symptom of parotid lymphoma is a unilateral, non-tender, firm mass that slowly grows in size over time. As its clinical manifestations are non-specific, a comprehensive assessment is required for an accurate diagnosis. The initial work-up includes imaging tools, such as computed tomography and magnetic resonance imaging. However, NHL of the parotid gland is difficult to distinguish from other types of benign tumors prior to biopsy; histopathological evaluation and subsequent immunohistochemical staining are needed for the final diagnosis. Once a definitive diagnosis is established, patients should be referred to an oncologist for staging. Treatment is mainly based on systemic chemotherapy, whereas radiotherapy is indicated for certain cases. Here, we report the case of a 53-year-old man who presented with a progressively enlarging mass in the right parotid area, which was later diagnosed as malignant lymphoma of the parotid gland after superficial parotidectomy.

Microbial Identification Using rRNA Operon Region: Database and Tool for Metataxonomics with Long-Read Sequence.

Recent development of long-read sequencing platforms has enabled researchers to explore bacterial community structure through analysis of full-length 16S rRNA gene (∼1,500 bp) or 16S-ITS-23S rRNA operon region (∼4,300 bp), resulting in higher taxonomic resolution than short-read sequencing platforms. Despite the potential of long-read sequencing in metagenomics, resources and protocols for this technology are scarce. Here, we describe MIrROR, the database and analysis tool for metataxonomics using the bacterial 16S-ITS-23S rRNA operon region. We collected 16S-ITS-23S rRNA operon sequences extracted from bacterial genomes from NCBI GenBank and performed curation. A total of 97,781 16S-ITS-23S rRNA operon sequences covering 9,485 species from 43,653 genomes were obtained. For user convenience, we provide an analysis tool based on a mapping strategy that can be used for taxonomic profiling with MIrROR database. To benchmark MIrROR, we compared performance against publicly available databases and tool with mock communities and simulated data sets. Our platform showed promising results in terms of the number of species covered and the accuracy of classification. To encourage active 16S-ITS-23S rRNA operon analysis in the field, BLAST function and taxonomic profiling results with 16S-ITS-23S rRNA operon studies, which have been reported as BioProject on NCBI are provided. MIrROR (http://mirror.egnome.co.kr/) will be a useful platform for researchers who want to perform high-resolution metagenome analysis with a cost-effective sequencer such as MinION from Oxford Nanopore Technologies. IMPORTANCE Metabarcoding is a powerful tool to investigate community diversity in an economic and efficient way by amplifying a specific gene marker region. With the advancement of long-read sequencing technologies, the field of metabarcoding has entered a new phase. The technologies have brought a need for development in several areas, including new markers that long-read can cover, database for the markers, tools that reflect long-read characteristics, and compatibility with downstream analysis tools. By constructing MIrROR, we met the need for a database and tools for the 16S-ITS-23S rRNA operon region, which has recently been shown to have sufficient resolution at the species level. Bacterial community analysis using the 16S-ITS-23S rRNA operon region with MIrROR will provide new insights from various research fields.

Decoding reactive structures in dilute alloy catalysts.

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts.

Guidelines to Achieving High Selectivity for the Hydrogenation of α,ß-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review.

Selective hydrogenation of α,ß-unsaturated aldehydes to unsaturated alcohols is a challenging class of reactions, yielding valuable intermediates for the production of pharmaceuticals, perfumes, and flavorings. On monometallic heterogeneous catalysts, the formation of the unsaturated alcohols is thermodynamically disfavored over the saturated aldehydes. Hence, new catalysts are required to achieve the desired selectivity. Herein, the literature of three major research areas in catalysis is integrated as a step toward establishing the guidelines for enhancing the selectivity: reactor studies of complex catalyst materials at operating temperature and pressure, surface science studies of crystalline surfaces in ultrahigh vacuum, and first-principles modeling using density functional theory calculations. Aggregate analysis shows that bimetallic and dilute alloy catalysts significantly enhance the selectivity to the unsaturated alcohols compared to monometallic catalysts. This comprehensive review focuses primarily on the role of different metal surfaces as well as the factors that promote the adsorption of the unsaturated aldehyde via its C═O bond, most notably by electronic modification of the surface and formation of the electrophilic sites. Furthermore, challenges, gaps, and opportunities are identified to advance the rational design of efficient catalysts for this class of reactions, including the need for systematic studies of catalytic processes, theoretical modeling of complex materials, and model studies under ambient pressure and temperature.

Evolution of Metastable Structures at Bimetallic Surfaces from Microscopy and Machine-Learning Molecular Dynamics.

The restructuring of interfaces plays a crucial role in materials science and heterogeneous catalysis. Bimetallic systems, in particular, often adopt very different compositions and morphologies at surfaces compared to the bulk. For the first time, we reveal a detailed atomistic picture of long-time scale restructuring of Pd deposited on Ag using microscopy, spectroscopy, and novel simulation methods. By developing and performing accelerated machine-learning molecular dynamics followed by an automated analysis method, we discover and characterize previously unidentified surface restructuring mechanisms in an unbiased fashion, including Pd-Ag place exchange and Ag pop-out as well as step ascent and descent. Remarkably, layer-by-layer dissolution of Pd into Ag is always preceded by an encapsulation of Pd islands by Ag, resulting in a significant migration of Ag out of the surface and a formation of extensive vacancy pits within a period of microseconds. These metastable structures are of vital catalytic importance, as Ag-encapsulated Pd remains much more accessible to reactants than bulk-dissolved Pd. Our approach is broadly applicable to complex multimetallic systems and enables the previously intractable mechanistic investigation of restructuring dynamics at atomic resolution.

Eyeball deviation by orbital mucocele after midface sinus injury.

A mucocele is an epithelium-lined, mucus-filled cavity in the paranasal sinuses. Mucocele may develop due to scarring and obstruction of the sinus ostium caused by midface sinus trauma, such as orbital bone fracture or endoscopic sinus surgery. The authors report two cases of orbital mucocele as complications following midface sinus injury (endoscopic sinus surgery in one case, and orbital fracture repair in the other). In both cases, imaging studies showed a large orbital mucocele accompanied by bony erosion and orbital wall remodeling, compressing the ocular muscle. Using an open approach, the lesion was excised and marsupialized. The symptoms resolved, and the postoperative eyeball position was normal. Orbital mucocele may cause serious complications such as ocular symptoms, orbital cellulitis, osteomyelitis, and the formation of an abscess with the potential to invade the brain. Therefore, surgeons should consider the possibility of mucocele as a late complication of surgery and initiate an immediate work-up and surgical treatment if needed.

First-principles modeling of water permeation through periodically porous graphene derivatives.

Polyphenylene superhoneycomb network (PSN) and covalent triazine framework (CTF) are experimentally realized periodically porous graphene derivatives. Such ultrathin layers with homogeneously distributed pores of controllable sizes are highly desirable for applications in molecular separations such as water purification. The permeation energy barrier is expected to be a function of not only the pore size, but also the specific permeation trajectory as determined by hydrogen bonding interactions at the water-pore interface. Here, we report a detailed first-principles study of permeation of a single H2O molecule through a monolayer PSN and CTF-0, as well as its diffusion behavior inside a bilayer PSN. The calculated energy barrier of 1.44 eV indicates the infeasibility of using PSN as a water permeation membrane. However, the barrier decreases considerably to 0.94 eV when three C-H pairs at the pore are replaced with N atoms into CTF-0. Inside a bilayer PSN, we find facile interlayer sliding as well as interlayer expansion owing to out-of-plane reorientation of the H2O molecule. In all cases, the functional groups at the pore significantly alter the orientation of the H2O molecule and the corresponding barriers. Such atomistic insights at the porous interface would provide a valuable guidance in advancing rational pore design principles.

Reconstruction of the Three-Dimensional Mandibulofacial Defects Using a Single Cutaneous Perforator-Based Fibula Osteocutaneous Flap.

The reconstruction of the mandibulofacial defects is a difficult task when there are full-thickness cheek defects involving mandible, inner mucosa and outer skin. There are several reconstructive options for the coverage of large defects, but most of the methods are complicated, and time- and effort-consuming. We hereby present a case of fibula osteocutaneous flap based on a single peroneal artery perforator in the reconstruction of a three-dimensional mandibulofacial defects.

Immediate Near-Total Scalp Reconstruction with Artificial Dermis on Exposed Calvarium.

Scalp defect management is complicated secondary to reduced laxity in the scalp and forehead area. For reconstruction of larger defects with exposed bone and loss of the periosteal layer, free flap reconstruction is one option for single-stage surgery, although the procedure is lengthy and includes the possibility of flap loss. We successfully performed a single-stage reconstruction of a large scalp defect using a combination of artificial dermis, split-thickness skin graft, and full-thickness skin graft following wide excision of a cutaneous angiosarcoma, and present our method as one option for the treatment of large oncologic surgical defects in patients who are poor candidates for free flap surgery.

Recurrent Pleomorphic Adenoma of the Parotid Gland.

Pleomorphic adenoma is the most common type of salivary gland tumor and the most common tumor of the parotid gland. Because of its propensity for invasion, pleomorphic adenoma of the parotid requires superficial parotidectomy or total parotidectomy to minimize the risk of tumor recurrence. We report a case of pleomorphic adenoma of the parotid gland with repeated recurrences. A 23-year-old male patient presented with a protruding neck mass. Six years prior to this presentation, the patient had undergone superficial parotidectomy for the removal of pleomorphic adenoma of the right parotid gland at our institution. The patient experienced recurrence at 17 months after the initial resection, which required a total parotidectomy with partial resection of the facial nerve. Pathologic examination revealed histologic findings consistent with pleomorphic adenoma across the surgical specimen from all three of the operations. The patient suffered from facial nerve paralysis, with facial expressions partially recovered over a year.

Leiomyosarcoma of the Face.

Leiomyosarcoma is a rare form of soft tissue neoplasm, with only 1% to 5% occurring in the head and neck region. Current recommended treatment suggests surgical excision with a wide lateral margin, but no definite guidelines regarding excisional margin have been established yet. Recently, complete excision with a narrow surgical margin has been recommended, and the authors present a case of cutaneous leiomyosarcoma on the face that was successfully managed by complete removal with a narrow excisional margin. A 74-year-old woman presented with a 3 cm sized, rapidly growing cutaneous mass on her right preauricular area. Preoperative biopsy of the skin lesion suggested a cutaneous leiomyosarcoma. The authors performed complete surgical excision with a 1 cm lateral margin, and the resulting skin defect was repaired with bilateral V-Y advancement local flaps. Histopathology and immunohistochemistry evaluation confirmed a moderately differentiated cutaneous leiomyosarcoma, with negative margin involvement. The patient refused of any additional treatment, but showed no locoregional recurrence during the 1.5 years of postoperative follow-up period. With a regular postoperative follow-up, cutaneous leiomyosarcomas may be successfully treated with a narrow surgical margin.

Lipid emulsions enhance the norepinephrine-mediated reversal of local anesthetic-induced vasodilation at toxic doses.

PURPOSE: Intravenous lipid emulsions have been used to treat the systemic toxicity of local anesthetics. The goal of this in vitro study was to examine the effects of lipid emulsions on the norepinephrine-mediated reversal of vasodilation induced by high doses of levobupivacaine, ropivacaine, and mepivacaine in isolated endothelium-denuded rat aorta, and to determine whether such effects are associated with the lipid solubility of local anesthetics. MATERIALS AND METHODS: The effects of lipid emulsions (0.30, 0.49, 1.40, and 2.61%) on norepinephrine concentration-responses in high-dose local anesthetic (6×10(-4) M levobupivacaine, 2×10(-3) M ropivacaine, and 7×10(-3) M mepivacaine)-induced vasodilation of isolated aorta precontracted with 60 mM KCl were assessed. The effects of lipid emulsions on local anesthetic- and diltiazem-induced vasodilation in isolated aorta precontracted with phenylephrine were also assessed. RESULTS: Lipid emulsions (0.30%) enhanced norepinephrine-induced contraction in levobupivacaine-induced vasodilation, whereas 1.40 and 2.61% lipid emulsions enhanced norepinephrine-induced contraction in both ropivacaine- and mepivacaine-induced vasodilation, respectively. Lipid emulsions (0.20, 0.49 and 1.40%) inhibited vasodilation induced by levobupivacaine and ropivacaine, whereas 1.40 and 2.61% lipid emulsions slightly attenuated mepivacaine (3×10(-3) M)-induced vasodilation. In addition, lipid emulsions attenuated diltiazem-induced vasodilation. Lipid emulsions enhanced norepinephrine-induced contraction in endothelium-denuded aorta without pretreatment with local anesthetics. CONCLUSION: Taken together, these results suggest that lipid emulsions enhance the norepinephrine-mediated reversal of local anesthetic-induced vasodilation at toxic anesthetic doses and inhibit local anesthetic-induced vasodilation in a manner correlated with the lipid solubility of a particular local anesthetic.

One-stage nipple and breast reconstruction following areola-sparing mastectomy.

BACKGROUND: Skin-sparing mastectomy with immediate breast reconstruction is increasingly becoming a proven surgical option for early-stage breast cancer patients. Areola-sparing mastectomy (ASM) has also recently become a popular procedure. The purpose of this article is to investigate the reconstructive and aesthetic issues experienced with one-stage nipple and breast reconstruction using ASM. METHODS: Among the patients who underwent mastectomy between March 2008 and March 2010, 5 women with a low probability of nipple-areolar complex malignant involvement underwent ASM and immediate breast reconstruction with simultaneous nipple reconstruction using the modified C-V flap. The cosmetic outcomes of this series were reviewed by plastic surgeons and patient self-assessment and satisfaction were assessed via telephone interview. RESULTS: During the average 11-month follow-up period, there were no cases of cancer recurrence, the aesthetic outcomes were graded as excellent to very good, and all of the patients were satisfied. Two patients developed a gutter-like depression around the reconstructed nipple, and one patient developed skin erosion in a small area of the areola, which healed with conservative dressing. The other complications, such as necrosis of the skin flap or areola, seroma, hematoma, or fat necrosis did not occur. CONCLUSIONS: Since one-stage nipple and breast reconstruction following ASM is an oncologically safe, cost-effective, and aesthetically satisfactory procedure, it is a good surgical option for early breast cancer patients.

Minimal subdermal shaving by means of sclerotherapy using absolute ethanol: a new method for the treatment of axillary osmidrosis.

BACKGROUND: Axillary osmidrosis is characterized by unpleasant odors originating from the axillary apocrine glands, resulting in psychosocial stress. The main treatment modality is apocrine gland removal. Until now, of the various surgical techniques have sometimes caused serious complications. We describe herein the favorable outcomes of a new method for ablating apocrine glands by minimal subdermal shaving using sclerotherapy with absolute ethanol. METHODS: A total of 12 patients underwent the procedure. The severity of osmidrosis was evaluated before surgery. Conventional subdermal shaving was performed on one side (control group) and ablation by means of minimal subdermal shaving and absolute ethanol on the other side (study group). Postoperative outcomes were compared between the study and control groups. RESULTS: The length of time to removal of the drain was 1 day shorter in the study group than in the control group. There were no serious complications, such as hematoma or seroma, in either group, but flap margin necrosis and flap desquamation occurred in the control group, and were successfully managed with conservative treatment. Six months after surgery, we and our patients were satisfied with the outcomes. CONCLUSIONS: Sclerotherapy using absolute ethanol combined with minimal subdermal shaving may be useful for the treatment of axillary osmidrosis. It can reduce the incidence of seroma and hematoma and allow the skin flap to adhere to its recipient site. It can degrade and ablate the remaining apocrine glands and eliminate causative organisms. Furthermore, since this technique is relatively simple, it takes less time than the conventional method.