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1.
Pediatr Cardiol ; 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38916668

RESUMEN

The objective of this study is to describe interventions and outcomes of a quality improvement (QI) project to reduce red blood cell transfusion (RBCT) within 72 h of pediatric cardiac catheterization. Using Plan-Do-Study-Act (PDSA) methodology, we applied interventions including (1). Intraprocedural-to reduce hemodilution, blood loss, and excessive anticoagulation, (2). Standardization of institutional transfusion criteria, and (3). "Hard stop" requiring QI team consultation prior to elective post-catheterization RBCT. Primary outcome measures were frequency of RBCT from IMPACT quarterly reports and cases between transfusions (CBT). Length of stay (LOS) was the primary countermeasure. Characteristics of patients who did and did not receive RBCT were compared. 698 pediatric cardiac catheterizations occurred between 4/2017 and 8/2023. Intraprocedural interventions did not alter frequency of RBCT or CBT. Standardized transfusion guidelines followed by the "hard stop" decreased RBCT frequency from 10 to 1.9% and increased CBT without increasing LOS. Patients requiring RBCT were younger (medians 0.31 vs 2.4 years), smaller (5.2 vs 11.8 kg), and had longer procedures (2.24 vs 1.57 h) all p < 0.001. Single ventricle patients were more likely to have RBCT than simple biventricular patients (14.1% vs 3.1%; RR = 4.57, 95% CI 2.29-10.4; p < 0.001). Procedure type (diagnostic vs. intervention) and starting hemoglobin concentration were comparable between groups. Programmatic adherence to standardized peri-procedural transfusion guidelines successfully decreased RBCT without compromising patient care or increasing LOS. Younger age, lower weight, procedure length, and single ventricle physiology were all associated with RBCT risk.

2.
Acc Chem Res ; 55(14): 1879-1888, 2022 07 19.
Artículo en Inglés | MEDLINE | ID: mdl-35642792

RESUMEN

Photosensitized semiconducting nanomaterials have received considerable attention because of their applications in photocatalytic and photoelectronic devices. In such systems, photoexcited electrons with sufficiently high energies can be injected into the conduction band (CB) of an adjacent semiconductor. These excited electrons are subjected to various physical processes that can lead to their annihilation before exercising their catalytic/electric functions, and the efficiency of the photosensitized functions depends on the quantity of CB electrons produced and how long they remain near the surface region of the semiconductor. The rise and decay of photoexcited electrons in the semiconductor CB can be probed with transient IR absorption (TA), which was first demonstrated by Lian and co-workers. Results from various laboratories have since revealed that electrons appear in the CB following the excitation of the photosensitizer in tens to hundreds of femtoseconds and that the decay of the CB electrons typically exhibits multiple exponentials on varying ultrafast time scales. The size of the semiconductor nanoparticle appears to influence the diffusion of the CB electrons and thus their lifetimes. In all studies reported, the observed multiexponential decays have been analyzed and interpreted using purely phenomenological models, in which the individual decays were intuitively assigned to one specific relaxation or loss process. In reality, however, each exponential decay can be a convolution of multiple physical processes. In this Account, we report a universally applicable physical model, constructed by including all known electron dynamic processes, to quantitatively account for the multiexponential decays. We characterize the model as universal, as it can be used to analyze our own TA measurements, as well as data acquired in other laboratories. In our study of TiO2 nanorods photosensitized by Ag platelets, we demonstrate that each of the observed triple-exponential decays corresponds to a convolution of several physical decay processes occurring on similar time scales. The rate of each of the processes can be deconvoluted and determined to construct a complete, physically based model to assess the most important question: How many CB electrons are near the semiconductor surface region and what is their lifetime?The size of the semiconductor is an important consideration. Intuitively, as the semiconductor volume increases, there is more room for CB electrons to diffuse around, which increases their lifetime as annihilation occurs primarily at the surface. Indeed, Tachiya and co-workers previously reported that this lifetime increases with particle size. Nevertheless, while CB electrons live longer in the bulk of the particle, they are only useful when they are at the surface. Overall, what really matters is the CB electrons near the surface region, where the photosensitized functions actually occur. In applying our model to analyze the previously reported size-dependent Au/TiO2 results, we successfully reproduced the observation that larger semiconductor nanoparticles lengthen the lifetime of CB electrons because of diffusion into the bulk. More importantly, however, our model reveals that the size of the semiconductor has almost no influence on the retention of CB electrons near the semiconductor surface. This information is only revealed when all physical processes are quantitatively taken into account for the observed electron dynamics, which is not feasible with a phenomenological approach.


Asunto(s)
Nanocompuestos , Puntos Cuánticos , Difusión , Electrones , Humanos , Semiconductores
3.
Inorg Chem ; 62(16): 6274-6287, 2023 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-37039388

RESUMEN

Two-dimensional tin monoselenide (SnSe) and tin diselenide (SnSe2) materials were efficiently produced by the thermolysis of molecular compounds based on a new class of seleno-ligands. Main group metal chalcogenides are of fundamental interest due to their layered structures, thickness-dependent modulation in electronic structure, and small effective mass, which make them attractive candidates for optoelectronic applications. We demonstrate here the synthesis of stable tin selenide precursors by in situ reductive bond cleavage in the dimeric diselenide ligand (SeC2H4N(Me)C2H4Se)2 in the presence of SnCl4. New molecular precursors [SnIV(SeC2H4N(Me)C2H4Se)2], [SnIVCl2(SeC2H4N(Me)C2H4Se)], and [SnIV(SC2H4N(Me)C2H4S)(SeC2H4N(Me)C2H4Se)] were thoroughly characterized by multinuclear magnetic resonance studies and single-crystal X-ray diffraction analysis that revealed the Sn(IV) center to be octahedrally coordinated by two tridentate dianionic chelating ligands or trigonally pyramidally coordinated by one chelating ligand and two chlorido ligands. Preorganization of metal-selenium bonds in both compounds offered direct and reproducible synthetic access to two-dimensional tin chalcogenides (SnSe and SnSe2) via simple adjustment of the pyrolysis temperature. Additionally, SnSe2 and SnSxSe2-x particles could be successfully synthesized by microwave-assisted decomposition of the molecular precursors, which was unambiguously corroborated by both experimental and computational analyses that explained the formation of a selenium rich SnSxSe2-x phase from a single molecular precursor containing both Sn-Se and Sn-S bonds.

4.
J Pept Sci ; 29(8): e3481, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-36706052

RESUMEN

Bacterial biofilm formation remains a serious problem for clinical materials and often leads to implant failure. To counteract bacterial adhesion, which initiates biofilm formation, the development of antibiotic surface coating strategies is of high demand and warrants further investigations. In this study, we have created bifunctional chimeric peptides by fusing the recently developed antimicrobial peptide MGD2 (GLRKRLRKFFNKIKF) with different titanium-binding sequences. The novel peptides were investigated regarding their antibacterial potential against a set of different bacterial strains including drug-resistant Staphylococcus aureus. All peptides showed high antimicrobial activities both when in solution and when immobilized on titanium surfaces. Owing to the ease of synthesis and handling, the herein described peptides might be a true alternative to prevent bacterial biofilm formation.


Asunto(s)
Antiinfecciosos , Staphylococcus aureus Resistente a Meticilina , Titanio/farmacología , Péptidos/farmacología , Antibacterianos/farmacología , Propiedades de Superficie , Biopelículas , Materiales Biocompatibles Revestidos
5.
J Phys Chem A ; 127(42): 8782-8793, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37846886

RESUMEN

Collisional relaxation of highly vibrationally excited acetylene, generated from the 193 nm photolysis of vinyl bromide with roughly 23,000 cm-1 of nascent vibrational energy, is studied via submicrosecond time-resolved Fourier transform infrared (FTIR) emission spectroscopy. IR emission from vibrationally hot acetylene during collisional relaxation by helium, neon, argon, and krypton rare-gas colliders is recorded and analyzed to deduce the acetylene energy content as a function of time. The average energy lost per collision, ⟨ΔE⟩, is computed using the Lennard-Jones collision frequency. Two distinct vibrational-to-translational (V-T) energy transfer regimes in terms of the acetylene energy are identified. At vibrational energies below 10,000-14,000 cm-1, energy transfer efficiency increases linearly with molecular energy content and is in line with typical V-T behavior in quantity. In contrast, above 10,000-14,000 cm-1, the V-T energy transfer efficiency displays a dramatic and rapid increase. This increase is nearly coincident with the acetylene-vinylidene isomerization limit, which occurs nearly 15,000 cm-1 above the acetylene zero-point energy. Combined quasi-classical trajectory calculations and Schwartz-Slawsky-Herzfeld-Tanczos theory point to a vinylidene contribution being responsible for the large enhancement. This observation illustrates the influence of energetically accessible structural isomers to greatly enhance the energy transfer rates of highly vibrationally excited molecules.

6.
J Chem Phys ; 159(15)2023 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-37846956

RESUMEN

The electronic and vibrational spectra of the meso-tetrakis(4-sulfonatophenyl)-porphyrins (TSPP) have been studied computationally using the PFD-3B functional with time-dependent density functional theory for the excited states. The calculated UV-vis absorption and emission spectra in aqueous solution are in excellent agreement with the experimental measurements of both H2TSPP-4 (monomer) at high pH and H4TSPP-2 (forming J-aggregate) at low pH. Moreover, our calculations reveal an infrared absorption at 1900 cm-1 in the singlet and triplet excited states that is absent in the ground state, which is chosen as a probe for transient IR absorption spectroscopy to investigate the vibrational dynamics of the excited state. Specifically, the S2 to S1 excited state internal conversion process time, the S1 state vibrational relaxation time, and the lifetime of the S1 excited electronic state are all quantitatively deduced.

7.
Phys Chem Chem Phys ; 24(36): 22206-22221, 2022 Sep 21.
Artículo en Inglés | MEDLINE | ID: mdl-36097852

RESUMEN

This paper investigates the accuracy of deriving the composite optical constants of binary mixtures from only the complex indices of refraction of the neat materials. These optical constants enable the reflectance spectra of the binary mixtures to be modeled for multiple scenarios (e.g., different substrates, thicknesses, volume ratios), which is important for contact and standoff chemical detection. Using volume fractions, each mixture's complex index of refraction was approximated via three different mixing rules. To explore the impact of intermolecular interactions, these predictions are tested by experimental measurements for two representative sets of binary mixtures: (1) tributyl phosphate combined with n-dodecane, a non-polar medium, to represent mixtures which primarily interact via dispersion forces and (2) tributyl phosphate and 1-butanol to represent mixtures with polar functional groups that can also interact via dipole-dipole interactions, including hydrogen bonding. The residuals and the root-mean-square error between the experimental and calculated index values are computed and demonstrate that for miscible liquids in which the average geometry of the cross-interactions can be considered isotropic (e.g., dispersion), the refractive indices of the mixtures can be modeled using composite n and k values derived from volume fractions of the neat liquids. Conversely, in spectral regions where the geometry of the cross-interactions is more restricted and anisotropic (e.g., hydrogen bonding), the calculated n and k values vary from the measured values. The impact of these interactions on the reflectance spectra are then compared by modeling a thin film of the binary mixtures on an aluminum substrate using both the measured and the mathematically computed indices of refraction.

8.
J Chem Phys ; 156(2): 024703, 2022 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-35032973

RESUMEN

The lifetime for injecting hot electrons generated in Ag nanoplatelets to nearby TiO2 nanorods was measured with ultrafast transient IR absorption to be 13.1 ± 1.5 fs, which is comparable to values previously reported for much smaller spherical Ag nanoparticles. Although it was shown that the injection rate decreases as the particle size increases, this observation can be explained by the facts that (1) the platelet has a much larger surface to bulk ratio and (2) the platelet affords a much larger surface area for direct contact with the semiconductor. These two factors facilitate strong Ag-TiO2 coupling (as indicated by the observed broadened surface plasmon resonance band of Ag) and can explain why Ag nanoplatelets have been found to be more efficient than much smaller Ag nanoparticles as photosensitizers for photocatalytic functions. The fast injection rate, together with a stronger optical absorption in comparison with Au and dye molecules, make Ag nanoplatelets a preferred photosensitizer for wide bandgap semiconductors.

9.
Angew Chem Int Ed Engl ; 61(42): e202205608, 2022 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-36037071

RESUMEN

Phase transitions of lipid bilayer membranes should affect passive transport of molecules. While this hypothesis has been used to design drug-releasing thermosensitive liposomes, the effect has yet to be quantified. Herein, we use time-resolved second harmonic light scattering to measure transport of a molecular cation across membranes of unilamellar liposomes composed of the total lipid extract of E. coli from 9 °C to 36 °C, in which two distinct phase transitions (gel to liquid-disordered phase) have been identified. While the transport rate slowly increases with temperature as a diffusion process, dramatic jumps are observed at 14.7 °C and 27.6 °C, the known phase transitions. The transport rate constant measured as (7.3±0.8)×10-3  s-1 in the liquid-disordered phase at 36 °C is 35-times faster than (2.1±0.2)×10-4  s-1 of the gel phase at 9 °C. For the mixed-phase between these two phases, the measured rates are consistent with a structure of gel domains among a liquid-disordered bulk.


Asunto(s)
Membrana Dobles de Lípidos , Liposomas , Membrana Celular , Difusión , Escherichia coli , Membrana Dobles de Lípidos/química , Liposomas/química , Temperatura , Liposomas Unilamelares
10.
Biophys J ; 120(12): 2461-2470, 2021 06 15.
Artículo en Inglés | MEDLINE | ID: mdl-33932437

RESUMEN

Bacterial surface charge is a critical characteristic of the cell's interfacial physiology that influences how the cell interacts with the local environment. A direct, sensitive, and accurate experimental technique capable of quantifying bacterial surface charge is needed to better understand molecular adaptations in interfacial physiology in response to environmental changes. We introduce here the method of second-harmonic light scattering (SHS), which is capable of detecting the number of molecular ions adsorbed as counter charges on the exterior bacterial surface, thereby providing a measure of the surface charge. In this first demonstration, we detect the small molecular cation, malachite green, electrostatically adsorbed on the surface of representative strains of Gram-positive and Gram-negative bacteria. Surprisingly, the SHS-deduced molecular transport rates through the different cellular ultrastructures are revealed to be nearly identical. However, the adsorption saturation densities on the exterior surfaces of the two bacteria were shown to be characteristically distinct. The negative charge density of the lipopolysaccharide coated outer surface of Gram-negative Escherichia coli (6.6 ± 1.3 nm-2) was deduced to be seven times larger than that of the protein surface layer of Gram-positive Lactobacillus rhamnosus (1.0 ± 0.2 nm-2). The feasibility of SHS-deduced bacterial surface charge density for Gram-type differentiation is presented.


Asunto(s)
Antibacterianos , Bacterias Gramnegativas , Adsorción , Bacterias Grampositivas , Iones , Propiedades de Superficie
11.
Inorg Chem ; 60(3): 1915-1921, 2021 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-33475356

RESUMEN

Chemical vapor deposition (CVD) of UO2 thin films from in situ reductive decomposition using a U(VI) precursor ([U(OtBu)6]) was performed under applied magnetic fields (up to 1 T). The molecular mechanism responsible for the formation of U(IV) oxide was determined by nuclear magnetic resonance (NMR) analysis of gaseous byproducts revealed a reductive transformation of uranium hexakis-tert-butoxide into urania. Thin films were grown under zero-field and applied magnetic field conditions that clearly showed the guiding influence of the magnetic field on altering the morphology and crystallographic orientation of grains in UO2 deposits produced under an external magnetic field. Application of magnetic fields was found to reduce the grain size. Whereas films with a ⟨111⟩ preferred orientation were observed under zero-field conditions, the application of magnetic fields (500 mT to 1 T) promoted a polycrystalline growth. X-ray photoelectron spectroscopy confirmed the formation of UO2 films with traces of U(VI) centers present on the surface, which was evidently due to the surface oxidation of coordinatively unsaturated U(IV) centers, which was found to be significantly reduced in the field-assisted process. These findings emphasize the positive effect of magnetic fields on controlling the texture and chemical homogeneity of CVD-grown films. The availability of a magnetic field as an extrinsic parameter for the CVD process adds to the conventional parameters, such as temperature, deposition time, and pressure, and expands the experimental space for thin-film growth.

12.
Nanotechnology ; 32(46)2021 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-34348241

RESUMEN

The catalytic conversion of nitrogen to ammonia remains an energy-intensive process, demanding advanced concepts for nitrogen fixation. The major obstacle of nitrogen fixation lies in the intrinsically high bond energy (941 kJ mol-1) of the N≡N molecule and the absence of a permanent dipole in N2. This kinetic barrier is addressed in this study by an efficient piezo-enhanced gold catalysis as demonstrated by the room temperature reduction of dinitrogen into ammonia. Au nanostructures were immobilized on thin film piezoelectric support of potassium sodium niobate (K0.5Na0.5NbO3, KNN) by chemical vapor deposition of a new Au(III) precursor [Me2Au(PyTFP)(H2O)]1(PyTFP = (Z)-3,3,3-trifluoro-1-(pyridin-2-yl)-prop-1-en-2-olate) that exhibited high volatility (60 °C, 10-3mbar) and clean decomposition mechanism to produce well adherent elemental gold films on KNN and Ti substrates. The gold-functionalized KNN films served as an efficient catalytic system for ammonia production with a Faradaic efficiency of 18.9% achieved upon ultrasonic actuation. Our results show that the spontaneous polarization of piezoelectric materials under external electrical fields augments the sluggish electron transfer kinetics by creating instant dipoles in adsorbed N2molecules to deliver a piezo-enhanced catalytic system promising for sustained activation of dinitrogen molecules.

13.
J Phys Chem A ; 125(41): 9065-9070, 2021 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-34613728

RESUMEN

Through coherent excitation of a pair of vibronically coupled eigenlevels, an oscillation of 130 kcal/mol in energy excitation between electronic and vibrational motions (on a time scale of 10-8 s) is created for the triatomic molecule, sulfur dioxide (SO2). The reactivity of the molecule can be influenced depending upon whether the molecule is vibrationally or electronically excited with this substantial amount of energy. The effect of excitation on reactivity is demonstrated through SO2 photodissociation as a function of time following coherent excitation, monitored by multiphoton ionization of the SO product.

14.
J Toxicol Environ Health A ; 84(10): 418-439, 2021 05 19.
Artículo en Inglés | MEDLINE | ID: mdl-33622194

RESUMEN

The aim of this interdisciplinary research project in North Rhine-Westphalia (NRW), Germany, entitled "Elimination of pharmaceuticals and organic micropollutants from waste water" involved the conception of cost-effective and innovative waste-water cleaning methods. In this project in vitro assays, in vivo assays and chemical analyses were performed on three municipal waste-water treatment plants (WWTP). This publication focuses on the study of the in vitro bioassays. Cytotoxic, estrogenic, genotoxic and mutagenic effects of the original as well as enriched water samples were monitored before and after wastewater treatment steps using MTT and PAN I, ER Calux and A-YES, micronucleus and Comet assays as well as AMES test. In most cases, the measured effects were reduced after ozonation, but in general, the biological response depended upon the water composition of the WWTP, in particular on the formed by-products and concentration of micropollutants. In order to be able to assess the genotoxic and/or mutagenic potential of waste-water samples using bioassays like Ames test, Comet assay or micronucleus test an enrichment of the water sample via solid-phase extraction is recommended. This is in agreement with previous studies such as the "ToxBox"-Project of the Environmental Agency in Germany.


Asunto(s)
Ozono/química , Eliminación de Residuos Líquidos/instrumentación , Aguas Residuales/química , Contaminantes Químicos del Agua/análisis , Purificación del Agua/instrumentación , Alemania
15.
Pediatr Cardiol ; 41(8): 1704-1713, 2020 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-32734528

RESUMEN

Infants undergoing congenital heart surgery (CHS) with cardiopulmonary bypass (CPB) are at risk of acute kidney injury (AKI) and fluid overload. We hypothesized that placement of a passive peritoneal drain (PPD) can improve postoperative fluid output in such infants. We analyzed 115 consecutive patients, age birth to 60 days, admitted to the PICU after CHS with CPB between 2012 and 2018. Patients who needed postoperative ECMO were excluded. Linear and logistic regression models compared postoperative fluid balances, diuretics administration, AKI, vasoactive-inotropic scores (VIS), time intubated, and length of stay after adjusting for pre/operative predictors including STAT category, bypass time, age, weight, and open chest status. PPD patients had higher STAT category (p = 0.001), longer CPB times (p = 0.001), and higher VIS on POD 1-3 (p ≤ 0.005 daily). PPD patients also had higher AKI rates (p = 0.01) that did not reach significance in multivariable modeling. There were no postoperative deaths. Postoperative hours of intubation, hospital length of stay, and POD 1-5 fluid intake did not differ between groups. Over POD 1-5, PPD use accounted for 48.8 mL/kg increased fluid output (95% CI [2.2, 95.4], p = 0.043) and 3.41 mg/kg less furosemide administered (95% CI [1.69, 5.14], p < 0.001). No PPD complications were observed. Although PPD placement did not affect end-outcomes, it was used in higher acuity patients. PPD placement is associated with improved fluid output despite lower diuretic administration and may be a useful postoperative fluid management adjunct in some complex CHS patients.


Asunto(s)
Puente Cardiopulmonar/métodos , Drenaje/métodos , Cardiopatías Congénitas/cirugía , Cavidad Peritoneal , Desequilibrio Hidroelectrolítico/prevención & control , Lesión Renal Aguda/etiología , Puente Cardiopulmonar/efectos adversos , Diuréticos/uso terapéutico , Femenino , Furosemida/uso terapéutico , Cardiopatías Congénitas/terapia , Humanos , Lactante , Recién Nacido , Tiempo de Internación , Modelos Logísticos , Masculino , Complicaciones Posoperatorias/etiología , Periodo Posoperatorio , Estudios Retrospectivos , Resultado del Tratamiento , Equilibrio Hidroelectrolítico , Desequilibrio Hidroelectrolítico/etiología
16.
Pediatr Cardiol ; 41(7): 1473-1483, 2020 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-32620981

RESUMEN

Truncal valve management in patients with truncus arteriosus is a clinical challenge, and indications for truncal valve intervention have not been defined. We sought to evaluate truncal valve dysfunction and primary valve intervention in patients with truncus arteriosus and determine risk factors for later truncal valve intervention. We conducted a retrospective cohort study of children who underwent truncus arteriosus repair at 15 centers between 2009 and 2016. Multivariable competing risk analysis was performed to determine risk factors for later truncal valve intervention. We reviewed 252 patients. Forty-two patients (17%) underwent truncal valve intervention during their initial surgery. Postoperative extracorporeal support, CPR, and operative mortality for patients who underwent truncal valve interventions were statistically similar to the rest of the cohort. Truncal valve interventions were performed in 5 of 64 patients with mild insufficiency; 5 of 16 patients with mild-to-moderate insufficiency; 17 of 35 patients with moderate insufficiency; 5 of 9 patients with moderate-to-severe insufficiency; and all 10 patients with severe insufficiency. Twenty patients (8%) underwent later truncal valve intervention, five of whom had no truncal valve intervention during initial surgical repair. Multivariable analysis revealed truncal valve intervention during initial repair (HR 11.5; 95% CI 2.5, 53.2) and moderate or greater truncal insufficiency prior to initial repair (HR 4.0; 95% CI 1.1, 14.5) to be independently associated with later truncal valve intervention. In conclusion, in a multicenter cohort of children with truncus arteriosus, 17% had truncal valve intervention during initial surgical repair. For patients in whom variable truncal valve insufficiency is present and primary intervention was not performed, late interventions were uncommon. Conservative surgical approach to truncal valve management may be justifiable.


Asunto(s)
Válvulas Cardíacas/fisiopatología , Tronco Arterial Persistente/cirugía , Niño , Preescolar , Femenino , Humanos , Lactante , Recién Nacido , Masculino , Recurrencia , Estudios Retrospectivos , Factores de Riesgo , Índice de Severidad de la Enfermedad
17.
Biochemistry ; 58(14): 1841-1844, 2019 04 09.
Artículo en Inglés | MEDLINE | ID: mdl-30912648

RESUMEN

We demonstrate that time-resolved second harmonic (SH) light scattering, when applied as an imaging modality, can be used to spatially resolve the adsorption and transport rates of molecules diffusing across the membrane in a living cell. As a representative example, we measure the passive transport of the amphiphilic ion, malachite green, across the plasma membrane in living human dermal fibroblast cells. Analysis of the time-resolved SH images reveals that membrane regions, which appear to be enduring higher stress, exhibit slower transport rates. It is proposed that this stress-transport relation may be a result of local enrichment of membrane rigidifiers as part of a response to maintain membrane integrity under strain.


Asunto(s)
Membrana Celular/metabolismo , Fibroblastos/metabolismo , Colorantes de Rosanilina/metabolismo , Microscopía de Generación del Segundo Armónico/métodos , Análisis de la Célula Individual/métodos , Imagen de Lapso de Tiempo/métodos , Adsorción , Transporte Biológico , Células Cultivadas , Dermis/citología , Difusión , Fibroblastos/citología , Humanos , Reproducibilidad de los Resultados , Colorantes de Rosanilina/química , Dispersión de Radiación
18.
J Phys Chem A ; 123(32): 6927-6936, 2019 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-31339307

RESUMEN

Collisional deactivation of vibrationally excited hydrogen isocyanide (HNC) by inert gas atoms was characterized using nanosecond time-resolved Fourier transform infrared emission spectroscopy. HNC, with an average nascent internal energy of 25.9 ± 1.4 kcal mol-1, was generated following the 193 nm photolysis of vinyl cyanide (CH2CHCN) and collisionally deactivated with the series of inert atomic gases: He, Ar, Kr, and Xe. Time-dependent IR emission allows simultaneous experimental observation of the ν1 NH and ν3 NC stretch emissions from vibrationally excited HNC. Subsequent spectral fit analysis enables direct determination of the average energy of HNC in each spectrum and therefore a measure of the average energy lost per collision, ⟨ΔE⟩, as a function of internal energy. Collisional deactivation of excited HNC is shown to be relatively efficient, exhibiting ⟨ΔE⟩ values more than an order of magnitude larger than comparably sized molecules at similar internal energies. Furthermore, the lighter inert gases are shown to be more efficient quenchers. Both observations can be qualitatively explained by the momentum gap law modeled through the repulsive force dominated vibration-to-translation energy transfer mechanism. The feasibility of efficient collisional deactivation as a contributing factor to the observed overabundance of astrophysical HNC is discussed.

19.
J Chem Phys ; 150(10): 104705, 2019 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-30876365

RESUMEN

We present an experimental study, using the surface sensitive technique, second harmonic light scattering (SHS), to examine the influence of structure on the propensity of a molecule to passively diffuse across a phospholipid membrane. Specifically, we monitor the relative tendency of the structurally similar amphiphilic cationic dyes, malachite green (MG) and crystal violet (CV), to transport across membranes in living cells (E. coli) and biomimetic liposomes. Despite having nearly identical molecular structures, molecular weights, cationic charges, and functional groups, MG is of lower overall symmetry and consequently has a symmetry allowed permanent dipole moment, which CV does not. The two molecules showed drastically different interactions with phospholipid membranes. MG is observed to readily cross the hydrophobic interior of the bacterial cytoplasmic membrane. Conversely, CV does not. Furthermore, experiments conducted with biomimetic liposomes, constructed from the total lipid extract of E. coli and containing no proteins, show that while MG is able to diffuse across the liposome membrane, CV does not. These observations indicate that the SHS results measured with bacteria do not result from the functions of efflux pumps, but suggests that MG possesses an innate molecular property (which is absent in CV) that allows it to passively diffuse across the hydrophobic interior of a phospholipid membrane.

20.
Cardiol Young ; 29(6): 787-792, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-31169104

RESUMEN

INTRODUCTION: Reliable predictors of extubation readiness are needed and may reduce morbidity related to extubation failure. We aimed to examine the relationship between changes in pre-extubation near-infrared spectroscopy measurements from baseline and extubation outcomes after neonatal cardiac surgery. MATERIALS AND METHODS: In this retrospective cross-sectional multi-centre study, a secondary analysis of prospectively collected data from neonates who underwent cardiac surgery at seven tertiary-care children's hospitals in 2015 was performed. Extubation failure was defined as need for re-intubation within 72 hours of the first planned extubation attempt. Near-infrared spectroscopy measurements obtained before surgery and before extubation in patients who failed extubation were compared to those of patients who extubated successfully using t-tests. RESULTS: Near-infrared spectroscopy measurements were available for 159 neonates, including 52 with single ventricle physiology. Median age at surgery was 6 days (range: 1-29 days). A total of 15 patients (9.4 %) failed extubation. Baseline cerebral and renal near-infrared spectroscopy measurements were not statistically different between those who were successfully extubated and those who failed, but pre-extubation cerebral and renal values were significantly higher in neonates who extubated successfully. An increase from baseline to time of extubation values in cerebral oximetry saturation by ≥ 5 % had a positive predictive value for extubation success of 98.6 % (95%CI: 91.1-99.8 %). CONCLUSION: Pre-extubation cerebral near-infrared spectroscopy measurements, when compared to baseline, were significantly associated with extubation outcomes. These findings demonstrate the potential of this tool as a valuable adjunct in assessing extubation readiness after paediatric cardiac surgery and warrant further evaluation in a larger prospective study.


Asunto(s)
Extubación Traqueal , Procedimientos Quirúrgicos Cardíacos , Circulación Cerebrovascular/fisiología , Cuidados Posoperatorios/métodos , Espectroscopía Infrarroja Corta/métodos , Estudios Transversales , Femenino , Cardiopatías Congénitas/cirugía , Humanos , Recién Nacido , Masculino , Oximetría , Valor Predictivo de las Pruebas , Estudios Retrospectivos , Insuficiencia del Tratamiento , Desconexión del Ventilador/métodos
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