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1.
Nature ; 592(7852): 49-53, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33790448

RESUMO

Impinging gas jets can induce depressions in liquid surfaces, a phenomenon familiar to anyone who has observed the cavity produced by blowing air through a straw directly above a cup of juice. A dimple-like stable cavity on a liquid surface forms owing to the balance of forces among the gas jet impingement, gravity and surface tension1,2. With increasing gas jet speed, the cavity becomes unstable and shows oscillatory motion, bubbling (Rayleigh instability) and splashing (Kelvin-Helmholtz instability)3,4. However, despite its scientific and practical importance-particularly in regard to reducing cavity instability growth in certain gas-blown systems-little attention has been given to the hydrodynamic stability of a cavity in such gas-liquid systems so far. Here we demonstrate the stabilization of such instabilities by weakly ionized gas for the case of a gas jet impinging on water, based on shadowgraph experiments and computational two-phase fluid and plasma modelling. We focus on the interfacial dynamics relevant to electrohydrodynamic (EHD) gas flow, so-called electric wind, which is induced by the momentum transfer from accelerated charged particles to neutral gas under an electric field. A weakly ionized gas jet consisting of periodic pulsed ionization waves5, called plasma bullets, exerts more force via electrohydrodynamic flow on the water surface than a neutral gas jet alone, resulting in cavity expansion without destabilization. Furthermore, both the bidirectional electrohydrodynamic gas flow and electric field parallel to the gas-water interface produced by plasma interacting 'in the cavity' render the surface more stable. This case study demonstrates the dynamics of liquids subjected to a plasma-induced force, offering insights into physical processes and revealing an interdependence between weakly ionized gases and deformable dielectric matter, including plasma-liquid systems.

2.
Nano Lett ; 24(14): 4224-4232, 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38557115

RESUMO

In this study, we identify the local structures of ex-solved nanoparticles using machine-learned potentials (MLPs). We develop a method for training machine-learned potentials by sampling local structures of heterointerface configurations as a training set with its efficacy tested on the Ni/MgO system, illustrating that the error in interface energy is only 0.004 eV/Å2. Using the developed scheme, we train an MLP for the Ni/La0.5Ca0.5TiO3 ex-solution system and identify the local structures for both exo- and endo-type particles. The established model aligns well with the experimental observations, accurately predicting a nucleation size of 0.45 nm. Lastly, the density functional theory calculations on the established atomistic model verify that the kinetic barrier for the dry reforming of methane are substantially reduced by 0.49 eV on the ex-solved catalysts compared to that on the impregnated catalysts. Our findings offer insights into the local structures, growth mechanisms, and underlying origin of the catalytic properties of ex-solved nanoparticles.

3.
J Am Chem Soc ; 146(2): 1337-1345, 2024 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-38165744

RESUMO

State-of-the-art methods in photoproximity labeling center on the targeted generation and capture of short-lived reactive intermediates to provide a snapshot of local protein environments. Diazirines are the current gold standard for high-resolution proximity labeling, generating short-lived aryl(trifluoromethyl) carbenes. Here, we present a method to access aryl(trifluoromethyl) carbenes from a stable diazo source via tissue-penetrable, deep red to near-infrared light (600-800 nm). The operative mechanism of this activation involves Dexter energy transfer from photoexcited osmium(II) photocatalysts to the diazo, thus revealing an aryl(trifluoromethyl) carbene. The labeling preferences of the diazo probe with amino acids are studied, showing high reactivity toward heteroatom-H bonds. Upon the synthesis of a biotinylated diazo probe, labeling studies are conducted on native proteins as well as proteins conjugated to the Os photocatalyst. Finally, we demonstrate that the conjugation of a protein inhibitor to the photocatalyst also enables selective protein labeling in the presence of spectator proteins and achieves specific labeling of a membrane protein on the surface of mammalian cells via a two-antibody photocatalytic system.


Assuntos
Proteínas , Luz Vermelha , Animais , Proteínas/química , Metano/química , Diazometano/química , Mamíferos
4.
Anal Chem ; 96(4): 1725-1732, 2024 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-38240676

RESUMO

Various platforms for the accurate diagnosis of infectious diseases have been studied because of the emergence of coronavirus disease (COVID-19) in 2019. Recently, it has become difficult to distinguish viruses with similar symptoms due to the continuous mutation of viruses, and there is an increasing need for a diagnostic method to detect them simultaneously. Therefore, we developed a paper-based rapid antigen diagnostic test using DNA aptamers for the simultaneous detection of influenza A, influenza B, and COVID-19. Aptamers specific for each target viral antigen were selected and attached to AuNPs for application in a rapid antigen diagnosis kit using our company's heterogeneous sandwich-type aptamer screening method (H-SELEX). We confirmed that the three viruses could be detected on the same membrane without cross-reactivity based on the high stability, specificity, and binding affinity of the selected aptamers. Further, the limit of detection was 2.89 pg·mL-1 when applied to develop signal amplification technology; each virus antigen was detected successfully in diluted nasopharyngeal samples. We believe that the developed simultaneous diagnostic kit, based on such high accuracy, can distinguish various infectious diseases, thereby increasing the therapeutic effect and contributing to the clinical field.


Assuntos
Aptâmeros de Nucleotídeos , COVID-19 , Doenças Transmissíveis , Influenza Humana , Nanopartículas Metálicas , Humanos , Influenza Humana/diagnóstico , Ouro , Imunoensaio/métodos , Aptâmeros de Nucleotídeos/metabolismo , Doenças Transmissíveis/diagnóstico , COVID-19/diagnóstico , Técnica de Seleção de Aptâmeros
5.
Small ; 20(5): e2304746, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37726236

RESUMO

Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.

6.
J Org Chem ; 89(14): 9800-9809, 2024 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-38940361

RESUMO

A palladium-catalyzed/copper-mediated cross-coupling of S-pyrimidinyl thioesters with arylboronic acids to yield biaryls is described. The reaction is likely to proceed via cleavage of the S-C(O) bond and subsequent release of CO, rather than via cleavage of the S-C(pyrimidine) bond and release of SCO, as supported by the results of both experimental and computational studies. The investigation of the reaction scope with various S-pyrimidinyl thioesters and arylboronic acids showed that the reaction is significantly affected by the substituent of the thioester and the presence of a chelatable ortho substituent was found to increase reaction efficiency.

7.
J Bone Miner Metab ; 42(1): 115-121, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38195930

RESUMO

INTRODUCTION: Sarcopenia is a key predictor of prognosis in patients with hip fractures. This study utilized computed tomography (CT) scan (1) to determine the association between psoas muscle cross-sectional area (CSA) and mortality, along with other muscles, and (2) to confirm the correlation between muscle CSA and appendicular lean mass (ALM) measured using DXA in elderly patients with hip fracture. MATERIALS AND METHODS: Patients who were aged ≥ 50 years and underwent surgical treatment for hip fracture were eligible for this study. After a series of exclusion criteria, 217 female patients were included. Patient data, including clinical characteristics, such as body mass index (BMI), CSA, and ALM, were retrospectively collected. The Kaplan-Meier survival method and Cox proportional hazards regression analysis were used for the statistical analyses. The correlation between CSA/BMI and ALM was also assessed. RESULTS: Patients in the lowest quartile of psoas muscle CSA/BMI had shorter survival times than those in the other quartiles. When the Cox proportional hazards regression analysis was adjusted for multiple variables, the lowest quartile of the CSA/BMI of the psoas was a risk factor for mortality. The CSA/BMI of the psoas showed the highest correlation coefficient. The CSA/BMI ratio of the other muscles showed a moderately positive correlation with ALM. CONCLUSION: The CSA of the psoas is associated with prognosis in elderly patients with hip fractures and shows a moderately positive correlation with ALM. Hence, the CSA of psoas is useful for predicting survival and muscle mass in elderly patients with hip fractures.


Assuntos
Fraturas do Quadril , Sarcopenia , Idoso , Humanos , Feminino , Músculos Psoas/diagnóstico por imagem , Músculos Psoas/patologia , Estudos Retrospectivos , Fraturas do Quadril/diagnóstico por imagem , Fraturas do Quadril/complicações , Sarcopenia/complicações , Prognóstico
8.
J Med Internet Res ; 26: e56417, 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38509662

RESUMO

BACKGROUND: Dysarthria is a common poststroke speech disorder affecting communication and psychological well-being. Traditional speech therapy is effective but often poses challenges in terms of accessibility and patient adherence. Emerging smartphone-based therapies may offer promising alternatives for the treatment of poststroke dysarthria. OBJECTIVE: This study aimed to assess the efficacy and feasibility of smartphone-based speech therapy for improving speech intelligibility in patients with acute and early subacute poststroke dysarthria. This study also explored the impact of the intervention on psychological well-being, user experience, and overall feasibility in a clinical setting. METHODS: Participants were divided into 2 groups for this randomized, evaluator-blinded trial. The intervention group used a smartphone-based speech therapy app for 1 hour per day, 5 days per week, for 4 weeks, with guideline-based standard stroke care. The control group received standard guideline-based stroke care and rehabilitation. Speech intelligibility, psychological well-being, quality of life, and user acceptance were assessed using repeated measures ANOVA. RESULTS: In this study, 40 patients with poststroke dysarthria were enrolled, 32 of whom completed the trial (16 in each group). The intervention group showed significant improvements in speech intelligibility compared with the control group. This was evidenced by improvements from baseline (F1,30=34.35; P<.001), between-group differences (F1,30=6.18; P=.02), and notable time-by-group interactions (F1,30=6.91; P=.01). Regarding secondary outcomes, the intervention led to improvements in the percentage of correct consonants over time (F1,30=5.57; P=.03). In addition, significant reductions were noted in the severity of dysarthria in the intervention group over time (F1,30=21.18; P<.001), with a pronounced group effect (F1,30=5.52; P=.03) and time-by-group interaction (F1,30=5.29; P=.03). Regarding quality of life, significant improvements were observed as measured by the EQ-5D-3L questionnaire (F1,30=13.25; P<.001) and EQ-VAS (F1,30=7.74; P=.009) over time. The adherence rate to the smartphone-based app was 64%, with over half of the participants completing all the sessions. The usability of the app was rated high (system usability score 80.78). In addition, the intervention group reported increased self-efficacy in using the app compared with the control group (F1,30=10.81; P=.003). CONCLUSIONS: The smartphone-based speech therapy app significantly improved speech intelligibility, articulation, and quality of life in patients with poststroke dysarthria. These findings indicate that smartphone-based speech therapy can be a useful assistant device in the management of poststroke dysarthria, particularly in the acute and early subacute stroke stages. TRIAL REGISTRATION: ClinicalTrials.gov NCT05146765; https://clinicaltrials.gov/ct2/show/NCT05146765.


Assuntos
Disartria , Estudos de Viabilidade , Smartphone , Fonoterapia , Acidente Vascular Cerebral , Humanos , Disartria/terapia , Disartria/etiologia , Fonoterapia/métodos , Masculino , Feminino , Projetos Piloto , Pessoa de Meia-Idade , Acidente Vascular Cerebral/complicações , Idoso , Qualidade de Vida , Reabilitação do Acidente Vascular Cerebral/métodos , Aplicativos Móveis , Resultado do Tratamento
9.
Clin Oral Investig ; 28(1): 83, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38195947

RESUMO

OBJECTIVES: The occurrence of implant-associated osteonecrosis of the jaw (ONJ) has been reported in osteoporotic patients, particularly in association with bisphosphonate therapy. This study aimed to investigate the risk of implant surgery and implant presence for ONJ occurrence in osteoporotic patients longitudinally. METHODS: Based on Korean National Health Information Database, subjects over the age of 65 who were diagnosed with osteoporosis between July 2014 and December 2016 were included. The implant group included subjects who had undergone dental implant surgery between January 2017 and December 2017, while the control group included those who had no history of dental implants. The primary outcome was the occurrence of ONJ, and the date of final follow-up was December 2020. RESULTS: A total of 332,728 subjects with osteoporosis were included in the analysis: 83,182 in the implant group and 249,546 in the control group. The risk of ONJ among those who had undergone implant surgery (risk of implant surgery-associated ONJ) was not higher than that among those without implant surgery. The risk of ONJ among those with implants (risk of implant presence-associated ONJ) was lower than that among those without implants. Even in subjects with a history of bisphosphonates, steroids, periodontitis, or tooth extraction, those who had undergone implant surgery or had implants did not have a higher ONJ risk than those who had not undergone surgery or did not have implants; rather, they showed a lower risk. CONCLUSIONS: The results may suggest that dental implants are not associated with an increased risk of ONJ. A further study on whether dental implants are associated with lower ONJ risk is needed. CLINICAL RELEVANCE: Dental implants did not increase the risk of ONJ development in osteoporotic patients, even with a history of bisphosphonates. This may suggest that the risk profiles for ONJ occurrence between selective insertion of dental implants and other dentoalveolar surgery associated with infectious conditions are different.


Assuntos
Implantes Dentários , Osteonecrose , Osteoporose , Humanos , Estudos de Coortes , Implantes Dentários/efeitos adversos , Difosfonatos/efeitos adversos , Osteoporose/complicações , Osteoporose/tratamento farmacológico
10.
Sensors (Basel) ; 24(9)2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38732859

RESUMO

Vehicular ad hoc networks (VANETs) use multiple channels to communicate using wireless access in vehicular environment (WAVE) standards to provide a variety of vehicle-related applications. The current IEEE 802.11p WAVE communication channel structure is composed of one control channel (CCH) and several service channels (SCHs). SCHs are used for non-safety data transmission, while the CCH is used for broadcasting beacons, control, and safety. WAVE devices transmit data that alternate between CCHs and SCHs, and each channel is active for a duration called the CCH interval (CCHI) and SCH interval (SCHI), respectively. Currently, both intervals are fixed at 50 ms. However, fixed-length intervals cannot effectively respond to dynamically changing traffic loads. Additionally, when many vehicles are simultaneously using the limited channel resources for data transmission, the network performance significantly degrades due to numerous packet collisions. Herein, we propose an adaptive resource allocation technique for efficient data transmission. The technique dynamically adjusts the SCHI and CCHI to improve network performance. Moreover, to reduce data collisions and optimize the network's backoff distribution, the proposed scheme applies reinforcement learning (RL) to provide an intelligent channel access algorithm. The simulation results demonstrate that the proposed scheme can ensure high throughputs and low transmission delays.

11.
Cleft Palate Craniofac J ; : 10556656241261846, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38881285

RESUMO

OBJECTIVE: Narrowing of the palatal cleft is often observed in infants with Robin sequence (RS) treated with the Stanford Orthodontic Airway Plate treatment (SOAP) even though SOAP is utilized primarily to establish airway patency. The current study quantified dimensional changes of the cleft palate (CP) in infants with RS treated with SOAP. DESIGN: A retrospective chart review. PATIENTS: Infants with RS and CP who completed SOAP and had maxillary arch models at both pre- and post-treatment time points at a single tertiary referral hospital between September 2019 and July 2023. SETTING AND OUTCOME MEASURE: Maxillary arch models were measured and analyzed using Bivariate statistical analysis. RESULTS: Seventeen infants were included in the study. The median age (min, max) was 6.7 weeks (1.1, 21.9) at pre-treatment and 26.6 weeks (18.7, 37.0) at post-treatment. The median Obstructive Apnea Hypopnea Index was 36.2 events/hour (8.1, 103.1) at pre-treatment and 4.1 events/hour (1.9, 8.6) at post-treatment. The pre-treatment width of CP decreased by an average (± standard diviation) of 6.37 mm (± 3.55, p < 0.001) at post-treatment. The ratio of the posterior cleft width to the total maxillary arch width decreased from 40% (± 9.1) at pre-treatment to 22% (± 11) at post-treatment (p < 0.001). CONCLUSION: The dimensions of CP reduced significantly during SOAP in infants with RS and CP treated for their severe upper airway obstruction. The findings highlight a potential benefit of SOAP that may contribute favorably to the palate repair surgery.

12.
Medicina (Kaunas) ; 60(5)2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38792863

RESUMO

Introduction: Basicervical femoral neck fracture (FNF) is an uncommon type of femoral neck fracture and is associated with an increased risk of fixation failure due to its inherent instability. The purpose of this study was to compare the surgical parameters and reoperation rate between the use of a multiple cannulated screw (MCS) and fixed angle device (FAD) in treating basicervical FNFs. Methods: We retrospectively reviewed the records of 885 patients who underwent internal fixation between May 2004 and August 2019 to determine basicervical FNF with at least 12 months of follow-up. Among the identified 77 patients with basicervical FNF, 17 patients who underwent multiple cannulated screw (MCS) fixation and 36 patients who underwent fixed angle device (FAD) fixation were included. We compared the rates of fracture-site collapse and reoperations according to the fixation device. Results: Among the 53 patients with basicervical FNF, 13 patients (24.5%) sustained surgical complications (8 collapses of fracture site and 5 reoperations). The reoperation rate in the MCS group was significantly higher than that in the FAD group (23.5% vs. 2.8%, p = 0.016), without any significant difference in the collapse of the fracture site (11.8% vs. 16.7%, p = 0.642). Conclusions: Although basicervical FNF was rare among hip fractures, fracture site collapse was prevalent and prone to fixation failure. Surgeons should keep this in mind, and consider FAD for basicervical FNF.


Assuntos
Parafusos Ósseos , Fraturas do Colo Femoral , Fixação Interna de Fraturas , Humanos , Fraturas do Colo Femoral/cirurgia , Feminino , Masculino , Estudos Retrospectivos , Fixação Interna de Fraturas/métodos , Fixação Interna de Fraturas/instrumentação , Fixação Interna de Fraturas/estatística & dados numéricos , Idoso , Pessoa de Meia-Idade , Resultado do Tratamento , Reoperação/estatística & dados numéricos , Idoso de 80 Anos ou mais , Complicações Pós-Operatórias/epidemiologia
13.
J Am Chem Soc ; 145(47): 25824-25833, 2023 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-37972034

RESUMO

The nature of the electron-binding forces in the dipole-bound states (DBS) of anions is interrogated through experimental and theoretical means by investigating the autodetachment dynamics from DBS Feshbach resonances of ortho-, meta-, and para-bromophenoxide (BrPhO-). Though the charge-dipole electrostatic potential has been widely regarded to be mainly responsible for the electron binding in DBS, the effect of nonclassical electron correlation has been conceived to be quite significant in terms of its static and/or dynamic contributions toward the binding of the excess electron to the neutral core. State-specific real-time autodetachment dynamics observed by picosecond time-resolved photoelectron velocity-map imaging spectroscopy reveal that the autodetachment processes from the DBS Feshbach resonances of BrPhO- anions cannot indeed be rationalized by the conventional charge-dipole potential. Specifically, the autodetachment lifetime is drastically lengthened depending on differently positioned Br-substitution, and this rate change cannot be explained within the framework of Fermi's golden rule based on the charge-dipole assumption. High-level ab initio quantum chemical calculations with EOM-EA-CCSD, which intrinsically takes into account electron correlations, generate more reasonable predictions on the binding energies than density functional theory (DFT) calculations, and semiclassical quantum dynamics simulations based on the EOM-EA-CCSD data excellently predict the trend in the autodetachment rates. These findings illustrate that static and dynamic properties of the excess electron in the DBS are strongly influenced by correlation interactions among electrons in the nonvalence orbital of the dipole-bound electron and highly polarizable valence orbitals of the bromine atom, which, in turn, dictate the interesting chemical fate of exotic anion species.

14.
Mol Microbiol ; 117(5): 1023-1047, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-35191101

RESUMO

Agrobacterium tumefaciens is a member of the Alphaproteobacteria that pathogenises plants and associates with biotic and abiotic surfaces via a single cellular pole. A. tumefaciens produces the unipolar polysaccharide (UPP) at the site of surface contact. UPP production is normally surface-contact inducible, but elevated levels of the second messenger cyclic diguanylate monophosphate (cdGMP) bypass this requirement. Multiple lines of evidence suggest that the UPP has a central polysaccharide component. Using an A. tumefaciens derivative with elevated cdGMP and mutationally disabled for other dispensable polysaccharides, a series of related genetic screens have identified a large number of genes involved in UPP biosynthesis, most of which are Wzx-Wzy-type polysaccharide biosynthetic components. Extensive analyses of UPP production in these mutants have revealed that the UPP is composed of two genetically, chemically, and spatially discrete forms of polysaccharide, and that each requires a specific Wzy-type polymerase. Other important biosynthetic, processing, and regulatory functions for UPP production are also revealed, some of which are common to both polysaccharides, and a subset of which are specific to each type. Many of the UPP genes identified are conserved among diverse rhizobia, whereas others are more lineage specific.


Assuntos
Agrobacterium tumefaciens , Vias Biossintéticas , Adesivos/metabolismo , Agrobacterium tumefaciens/genética , Agrobacterium tumefaciens/metabolismo , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Vias Biossintéticas/genética , Regulação Bacteriana da Expressão Gênica/genética , Polissacarídeos Bacterianos/metabolismo
15.
Acc Chem Res ; 55(13): 1821-1831, 2022 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-35713467

RESUMO

ConspectusAlloying, or mixing of multiple metallic elements, is the classical way of novel materials development since the Bronze age. Increased numbers of principal elements expand the compositional space for alloy design vastly, leading to nearly endless possibilities of unexpected and unique materials properties. In contrast to bulk alloying processes represented by casting of molten metal mixtures, the fabrication of multicomponent alloy (MCA) nanostructures such as nanoparticles and nanofoams with more than three elements is often challenging, and a few methodologies for directly synthesizing alloy nanostructures up to denary systems have been suggested recently. However, forming alloy nanoparticles inside another metal matrix, instead of inside aqueous media in wet-chemical synthesis, is a fairly well understood strategy in terms of physical metallurgy. Extracting those alloy nanophases from the matrix could provide an alternative way to fabricate novel MCA nanostructures.In this Account, we describe a hybrid approach of metallurgical bottom-up and chemical top-down processes for fabricating MCA nanostructures including nanoparticles and nanofoams. The former utilizes a liquid-state phase separation process that resembles "oil and water" but occurs at the nanoscale due to thermodynamic mixing relations among alloying elements and a rapid quenching process. Thermodynamic prediction of the immiscible boundary in a temperature-composition space (miscibility gap) plays a key role in designing precursor alloys for MCA nanostructures. Selective leaching, the chemical top-down process for extracting the alloy nanostructures from the precursors, uses the chemical reactivity difference between the embedded nanostructures and the matrix phase against a certain chemical solution. We discuss here that the precise control of alloy composition and cooling rate based on thermodynamic assessments enables researchers to prepare phase-separating precursor alloys for fabricating both nanoparticles and nanofoams with a broad size range from a few nanometers to a few hundred nanometers. Depending on the alloy systems, the atomic structure of alloy nanostructures could be controlled from fully amorphous to nanocrystalline and even to quasicrystalline structure. We demonstrate how the different sizes of alloy nanostructures fabricated by a single hybrid procedure can be effectively exploited for investigating size-dependent physical properties. The future and potential research directions for this hybrid approach are also briefly discussed. This unique approach for fabricating nanosized alloys provides an extended methodology to discover novel metallic nanomaterials with promising properties in diverse compositional spaces of MCA systems.

16.
Acc Chem Res ; 55(20): 3032-3042, 2022 10 18.
Artigo em Inglês | MEDLINE | ID: mdl-36206486

RESUMO

Nonvalence bound states (NBS) are anionic states where the excess electron is extremely loosely bound to the neutral core through long-range potentials. In contrast to the valence orbitals of which the electron occupancy determines the molecular structure, as well as the chemical reactivity, the nonvalence orbital is quite diffuse and located far from the neutral core. The NBS can be classified into the dipole-bound state (DBS), quadruple-bound state (QBS), or correlation-bound state (CBS) according to the nature of the electron-neutral interaction, although their interaction potentials may cooperatively contribute. The NBS is ubiquitous in nature and has the strong implications in atmospheric, interstellar, or biological chemistry. Accordingly, NBS has long been conceived to play the role of the doorway into the formation of a stable anion or dissociative electron attachment (DEA). Despite intensive and extensive studies, however, the quantum-mechanical nature of NBS is still far from being thorough understanding. Herein, we describe a new aspect of state-specific NBS-mediated chemical dynamics, which has been revealed through a series of recent studies by our group. We have employed picosecond time-resolved pump-probe spectroscopy combined with cryogenically cooled ion trap and velocity-map imaging techniques to study closed-shell anions generated by electrospray ionization. DBS vibrational Feshbach resonances are prepared by the optical excitation of phenoxide, for instance, and their individual lifetimes have been precisely measured in a state-specific manner to reveal the strong mode-dependency of the autodetachment rate. Fermi's golden rule turns out to be extremely useful for a rational explanation of the experiment, although the more sophisticated theoretical model is desirable for the more quantitative analysis. For the DBS of para-chlorophenoxide or para-bromophenoxide where the polarizability of neutral core is substantial, the Fermi's golden rule based on the charge-dipole potential needs to be significantly modified to include the correlation effects to explain the exceptionally slow autodetachment rates. For the QBS of 4-cyanophenoxide, the mode-specific behavior of the quadrupole ellipsoid tensor explains the strong mode-dependent autodetachment rate. Meanwhile, the nonadiabatic transition of the excess electron into the valence orbital can result in stable anion formation or immediate chemical bond rupture. In the DBS of ortho-, meta-, or para-iodophenoxide, the transformation of the loosely bound excess electron into the πσ* antibonding orbital occurs to give I- as a final fragment. The fragmentation mediated by DBS occurs competitively with the concomitant autodetachment, paving a new way of the reaction control by tuning the quantum-mechanical nature of the DBS Feshbach resonance. This experimental observation provides the foremost evidence for the dynamic role of the DBS as a doorway into anion chemistry, such as DEA. The ponderomotive force on the electron in the nonvalence orbital has been demonstrated for the first time in a strong optical field, giving great promise for the manipulation of polyatomic molecules in terms of the spatial location, as well as the AC-Stark control of the chemical reaction.


Assuntos
Elétrons , Ânions/química , Físico-Química , Estrutura Molecular , Análise Espectral
17.
Mol Pharm ; 20(11): 5532-5542, 2023 11 06.
Artigo em Inglês | MEDLINE | ID: mdl-37774674

RESUMO

Drug delivery systems (DDS) have evolved in the last decades with the development of hydrogels and particles. However, challenges such as high systemic uptake, side effects, low bioavailability, and encapsulation efficiency continue to be significant hurdles faced by such DDSs. Particles and hydrogels can be specifically designed for targeted DDSs to mitigate some of these problems. This study developed chitosan (Cs) particles (Ps) and composite films using poly(ethylene glycol) diacrylate (PEGDA) as a copolymer to encapsulate gentamicin (GtS) for drug delivery. We demonstrated that lysozyme degrades the chitosan ß-1,4 glycosidic bonds to release GtS. PEGDA increased drug encapsulation efficiency by shielding the repelling forces of like charges between Cs and GtS. The data show that PEGDA does not hinder enzymatic degradation while increasing drug encapsulation efficiency and producing more homogeneous particles. Additionally, we utilized Michael's reaction to cross-link Cs, CsPs, and PEGDA to produce a film designed for drug delivery. The film is an anchor for CsPs to prevent premature drug release. The cross-linking of Cs and PEGDA does not affect lysozyme activity, and CsPs could successfully release GtS without affecting GtS activity.


Assuntos
Quitosana , Quitosana/química , Muramidase , Polietilenoglicóis/química , Hidrogéis/química
18.
Oral Dis ; 2023 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-37927178

RESUMO

INTRODUCTION: Medication-related osteonecrosis of the jaw (MRONJ) is uncommon but can result in severe destruction of the jaw. This case-control study investigated the therapeutic effects of daily or weekly administration of teriparatide in the management of MRONJ using a cohort for osteonecrosis of the jaw. METHODS: Patients who were diagnosed with MRONJ and consented to teriparatide administration were assigned either to a group of daily injection or of weekly injection and completed a 4-week course of injection preoperatively and at least an 8-week course postoperatively. The control group received either the intraoperative rhBMP treatment (CG_BMP) or no additional perioperative treatment (CG_noBMP). The state of MRONJ was evaluated 2 months (T1) and 6 months (T2) postoperatively for all participants. RESULTS: Either group of daily injection (8.35 weeks ± 1.58; n = 17) or weekly injection (9.17 ± 3.79; n = 12) showed significantly faster healing than those of CG_BMP (14.40 ± 6.08; n = 25) or CG_noBMP (15.79 ± 9.79; n = 39). MRONJ was resolved completely in 24 out of 29 participants who completed the course of teriparatide injections, whereas 46.9% of CG showed delayed resolution. Multiple regression analysis indicated 7.50 times (95% CI, 1.77-31.82) more likelihood of complete resolution of MRONJ for participants with teriparatide injections. CONCLUSION: A course of daily or weekly administration of teriparatide injections may improve treatment outcomes for patients with MRONJ.

19.
BMC Musculoskelet Disord ; 24(1): 506, 2023 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-37344858

RESUMO

BACKGROUND: Femoral neck fractures are a common injury in older adults and their management presents a significant challenge for orthopedic surgeons. The Femoral Neck System (FNS) was recently introduced for the fixation of femur neck fractures. Although neck shortening was reduced with the FNS, the complication rates were not reduced. Thus, improvements to enhance fixation stability should be made for the FNS. We hypothesized that (1) the pre-sliding technique and (2) the use of longer anti-rotation screw would increase fracture stability. This study aimed to determine the change in fracture stability using the pre-sliding technique and long anti-rotation screw in the FNS for fixation of Pauwels type III femoral neck fractures. METHODS: Finite element models of Pauwels type III femoral neck fracture fixed with pre-sliding FNS and 5-mm longer anti-rotation screw were established. The models were subjected to normal walking load. The material properties of the elements belonging to the bone were mapped by assigning the formulation with the computed tomography Hounsfield unit. RESULTS: Pauwels type III femoral neck fractures fixed with pre-slided FNS showed better fracture stability, decreasing fracture gap and sliding by 14% and 12%, respectively, under normal walking load. No element of cortical bone in any of the models had an absolute value of principal strain that exceeded 1%. The peak von Mises stress (VMS) of the implants ranged from 260 to 289 MPa, and the highest peak VMS value was 50% lower than the yield strength of the titanium alloy (800 MPa). The longer anti-rotation screw did not affect fracture stability. CONCLUSIONS: The pre-sliding technique using the FNS showed higher fracture stability than the standard fixation technique for a Pauwels type III femoral neck fracture. The longer anti-rotation screw did not contribute significantly to fixation stability. As this finite element analysis considered the inhomogeneous mechanical property of the bone, it offered equivalent mechanical conditions to investigate the components of interest.


Assuntos
Fraturas do Colo Femoral , Colo do Fêmur , Fixação Interna de Fraturas , Idoso , Humanos , Fenômenos Biomecânicos , Parafusos Ósseos , Fraturas do Colo Femoral/diagnóstico por imagem , Fraturas do Colo Femoral/cirurgia , Análise de Elementos Finitos , Fixação Interna de Fraturas/métodos
20.
BMC Musculoskelet Disord ; 24(1): 449, 2023 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-37268896

RESUMO

BACKGROUND: The purpose of the Korean Hip Fracture Registry (KHFR) Study is to establish a nationwide, hospital-based prospective cohort study of adults with hip fracture to explore the incidence and risk factors of second osteoporotic fractures for a Fracture Liaison Service (FLS) model. METHODS: The KHFR, a prospective multicenter longitudinal study, was launched in 2014. Sixteen centers recruited participants who were treated for hip fracture. The inclusion criteria were patients, who were treated for proximal femur fracture due to low-energy trauma and aged 50 or more at the time of injury. Until 2018, 5,841 patients were enrolled in this study. Follow-up surveys were conducted annually to determine occurrence of second osteoporotic fracture, and 4,803 participants completed at least one follow-up survey. DISCUSSION: KHFR is a unique resource of individual level on osteoporotic hip fracture with radiological, medical, and laboratory information including DXA (dual energy x-ray absorptiometry), bone turnover marker, body composition, and hand grip strength for future analyses for FLS model. Modifiable factors for mortality after hip surgery is planned to be identified with nutritional assessment and multi-disciplinary interventions from hospitalization to follow-ups. The proportions of femoral neck, intertrochanteric, and subtrochanteric fractures were 517 (42.0%), 730 (53.6%), and 60 (4.4%), respectively, from 2014 to 2016, which was similar in other studies. Radiologic definition of atypical subtrochanteric fracture was adopted and 17 (1.2%) fractures among 1,361 proximal femoral fractures were identified. Internal fixation showed higher reoperation rate compared to arthroplasty in unstable intertrochanteric fractures (6.1% vs. 2.4%, p = 0.046) with no significant difference in mortality. The KHFR plans to identify outcomes and risk factors associated with second fracture by conducting a 10-year cohort study, with a follow-up every year, using 5,841 baseline participants. TRIAL REGISTRATION: Present study was registered on Internet-based Clinical Research and Trial management system (iCReaT) as multicenter prospective observational cohort study (Project number: C160022, Date of registration: 22th, Apr, 2016).


Assuntos
Fraturas do Quadril , Fraturas por Osteoporose , Adulto , Humanos , Estudos Prospectivos , Estudos de Coortes , Força da Mão , Estudos Longitudinais , Fraturas do Quadril/diagnóstico por imagem , Fraturas do Quadril/epidemiologia , Fraturas do Quadril/cirurgia , Fraturas por Osteoporose/diagnóstico por imagem , Fraturas por Osteoporose/epidemiologia , Fraturas por Osteoporose/cirurgia , Sistema de Registros , República da Coreia/epidemiologia
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