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1.
Crit Care Med ; 52(9): 1323-1332, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38713002

RESUMO

OBJECTIVES: To compare outcomes for 2 weeks vs. 1 week of maximal patient-intensivist continuity in the ICU. DESIGN: Retrospective cohort study. SETTING: Two U.S. urban, teaching, medical ICUs where intensivists were scheduled for 2-week service blocks: site A was in the Midwest and site B was in the Northeast. PATIENTS: Patients 18 years old or older admitted to a study ICU between March 1, 2017, and February 28, 2020. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: We applied target trial emulation to compare admission during an intensivist's first week (as a proxy for 2 wk of maximal continuity) vs. admission during their second week (as a proxy for 1 wk of maximal continuity). Outcomes included hospital mortality, ICU length of stay, and, for mechanically ventilated patients, duration of ventilation. Exploratory outcomes included imaging, echocardiogram, and consultation orders. We used inverse probability weighting to adjust for baseline differences and random-effects meta-analysis to calculate overall effect estimates. Among 2571 patients, 1254 were admitted during an intensivist's first week and 1317 were admitted during a second week. At sites A and B, hospital mortality rates were 25.8% and 24.2%, median ICU length of stay were 4 and 2 days, and median mechanical ventilation durations were 3 and 3 days, respectively. There were no differences in adjusted mortality (odds ratio [OR], 1.01 [95% CI, 0.96-1.06]) or ICU length of stay (-0.25 d [-0.82 d to +0.32 d]) for 2 weeks vs. 1 week of maximal continuity. Among mechanically ventilated patients, there were no differences in adjusted mortality (OR, 1.00 [0.87-1.16]), ICU length of stay (+0.06 d [-0.78 d to +0.91 d]), or duration of mechanical ventilation (+0.37 d [-0.46 d to +1.21 d]) for 2 weeks vs. 1 week of maximal continuity. CONCLUSIONS: Two weeks of maximal patient-intensivist continuity was not associated with differences in clinical outcomes compared with 1 week in two medical ICUs.


Assuntos
Mortalidade Hospitalar , Unidades de Terapia Intensiva , Tempo de Internação , Humanos , Masculino , Feminino , Unidades de Terapia Intensiva/organização & administração , Unidades de Terapia Intensiva/estatística & dados numéricos , Pessoa de Meia-Idade , Estudos Retrospectivos , Tempo de Internação/estatística & dados numéricos , Idoso , Fatores de Tempo , Respiração Artificial/estatística & dados numéricos , Continuidade da Assistência ao Paciente/organização & administração , Adulto
2.
BMC Health Serv Res ; 23(1): 698, 2023 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-37370059

RESUMO

COVID Watch is a remote patient monitoring program implemented during the pandemic to support home dwelling patients with COVID-19. The program conferred a large survival advantage. We conducted semi-structured interviews of 85 patients and clinicians using COVID Watch to understand how to design such programs even better. Patients and clinicians found COVID Watch to be comforting and beneficial, but both groups desired more clarity about the purpose and timing of enrollment and alternatives to text-messages to adapt to patients' preferences as these may have limited engagement and enrollment among marginalized patient populations. Because inclusiveness and equity are important elements of programmatic success, future programs will need flexible and multi-channel human-to-human communication pathways for complex clinical interactions or for patients who do not desire tech-first approaches.


Assuntos
Atitude do Pessoal de Saúde , Atitude Frente a Saúde , COVID-19 , Monitorização Ambulatorial , Pacientes , Telemedicina , Humanos , COVID-19/epidemiologia , COVID-19/terapia , Pandemias , Preferência do Paciente , Pacientes/psicologia , Pacientes/estatística & dados numéricos , Monitorização Ambulatorial/métodos , Avaliação de Programas e Projetos de Saúde , Pesquisa Qualitativa , Desenvolvimento de Programas , Masculino , Feminino , Pessoa de Meia-Idade , Adulto , Idoso
3.
Ann Intern Med ; 175(2): 179-190, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-34781715

RESUMO

BACKGROUND: Although most patients with SARS-CoV-2 infection can be safely managed at home, the need for hospitalization can arise suddenly. OBJECTIVE: To determine whether enrollment in an automated remote monitoring service for community-dwelling adults with COVID-19 at home ("COVID Watch") was associated with improved mortality. DESIGN: Retrospective cohort analysis. SETTING: Mid-Atlantic academic health system in the United States. PARTICIPANTS: Outpatients who tested positive for SARS-CoV-2 between 23 March and 30 November 2020. INTERVENTION: The COVID Watch service consists of twice-daily, automated text message check-ins with an option to report worsening symptoms at any time. All escalations were managed 24 hours a day, 7 days a week by dedicated telemedicine clinicians. MEASUREMENTS: Thirty- and 60-day outcomes of patients enrolled in COVID Watch were compared with those of patients who were eligible to enroll but received usual care. The primary outcome was death at 30 days. Secondary outcomes included emergency department (ED) visits and hospitalizations. Treatment effects were estimated with propensity score-weighted risk adjustment models. RESULTS: A total of 3488 patients enrolled in COVID Watch and 4377 usual care control participants were compared with propensity score weighted models. At 30 days, COVID Watch patients had an odds ratio for death of 0.32 (95% CI, 0.12 to 0.72), with 1.8 fewer deaths per 1000 patients (CI, 0.5 to 3.1) (P = 0.005); at 60 days, the difference was 2.5 fewer deaths per 1000 patients (CI, 0.9 to 4.0) (P = 0.002). Patients in COVID Watch had more telemedicine encounters, ED visits, and hospitalizations and presented to the ED sooner (mean, 1.9 days sooner [CI, 0.9 to 2.9 days]; all P < 0.001). LIMITATION: Observational study with the potential for unobserved confounding. CONCLUSION: Enrollment of outpatients with COVID-19 in an automated remote monitoring service was associated with reduced mortality, potentially explained by more frequent telemedicine encounters and more frequent and earlier presentation to the ED. PRIMARY FUNDING SOURCE: Patient-Centered Outcomes Research Institute.


Assuntos
COVID-19/terapia , Consulta Remota/métodos , Envio de Mensagens de Texto , Adulto , Idoso , COVID-19/mortalidade , Pesquisa Comparativa da Efetividade , Serviço Hospitalar de Emergência , Feminino , Serviços de Assistência Domiciliar , Hospitalização , Humanos , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Estados Unidos/epidemiologia
4.
J Gerontol Nurs ; 49(8): 43-50, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37523333

RESUMO

The purpose of the current study was to assess the impact of the Stepping On fall prevention program on the incidence of falls and frailty measures in older adults. Participants completed pre- and post-fall prevention program questionnaires and the Frail Scale Assessment at baseline and post-program. They also completed a follow-up questionnaire and Frail Scale Assessment at 6- and 12-month intervals post-program. Univariate analysis was performed comparing robust (n = 11), pre-frail (n = 29), and frail (n = 7) participants. Frail participants were significantly older (mean age = 77.7 years [SD = 4.9 years] vs. 74 years [SD = 5.9 years] vs. 70.4 [SD = 3.9], respectively; p = 0.026) and more likely to live alone (71.4% vs. 65.5% vs. 18.2%, respectively; p = 0.017) compared to pre-frail and robust participants. At 12-month post-program, reported falls and frailty scores decreased compared to baseline (12.8% vs. 29.8%, p = 0.044 and 0.91 [SD = 1.1] vs. 1.3 [SD = 1.082], respectively; p = 0.009). Data show that 41.4% of pre-frail participants at baseline improved to robust. Participation in Stepping On led to a decrease in reported falls and frailty scores 12 months post-program, suggesting that participation in the program may help delay frailty progression. [Journal of Gerontological Nursing, 49(8), 43-50.].

5.
J Urban Health ; 98(6): 822-831, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34014451

RESUMO

Spending time in nature is associated with numerous mental health benefits, including reduced depression and improved well-being. However, few studies examine the most effective ways to nudge people to spend more time outside. Furthermore, the impact of spending time in nature has not been previously studied as a postpartum depression (PPD) prevention strategy. To fill these gaps, we developed and pilot tested Nurtured in Nature, a 4-week intervention leveraging a behavioral economics framework, and included a Nature Coach, digital nudges, and personalized goal feedback. We conducted a randomized controlled trial among postpartum women (n = 36) in Philadelphia, PA between 9/9/2019 and 3/27/2020. Nature visit frequency and duration was determined using GPS data. PPD was measured using the Edinburgh Postnatal Depression Scale (EPDS). Participants were from low-income, majority Black neighborhoods. Compared to control, the intervention arm had a strong trend toward longer duration and higher frequency of nature visits (IRR 2.6, 95%CI 0.96-2.75, p = 0.059). When analyzing women who completed the intervention (13 of 17 subjects), the intervention was associated with three times higher nature visits compared to control (IRR 3.1, 95%CI 1.16-3.14, p = 0.025). No significant differences were found in the EPDS scores, although we may have been limited by the study's sample size. Nurture in Nature increased the amount of time postpartum women spent in nature, and may be a useful population health tool to leverage the health benefits of nature in majority Black, low-resourced communities.


Assuntos
Depressão Pós-Parto , Parques Recreativos , Depressão Pós-Parto/prevenção & controle , Feminino , Humanos , Projetos Piloto , Período Pós-Parto , População Urbana
7.
Ann Emerg Med ; 76(2): 206-214, 2020 08.
Artigo em Inglês | MEDLINE | ID: mdl-32376089

RESUMO

STUDY OBJECTIVE: Emergency department (ED) initiation of buprenorphine for patients with opioid use disorder increases treatment engagement but remains an uncommon practice. One important barrier to ED-initiated buprenorphine is the additional training requirement (X waiver). Our objective is to evaluate the influence of a financial incentive program on emergency physician completion of X-waiver training. Secondary objectives are to evaluate the program's effect on buprenorphine prescribing and to explore physician attitudes toward the incentive. METHODS: We conducted a prospective, observational cohort study set in 3 urban academic EDs before and after implementation of a financial incentive program providing $750 for completion of X-waiver training. We describe program participation as well as rates of buprenorphine prescribing per opioid use disorder-related encounter before and after the intervention period, using electronic health record data. We also completed a postintervention physician survey assessing attitudes about the incentive program. RESULTS: Overall, 89% of eligible emergency physicians (56/63) completed the X-waiver training during the 6-week incentive period. In the 5 months after the incentive, buprenorphine prescribing per opioid use disorder-related encounter increased from 0.5% to 16% (Δ 15%; 95% confidence interval 10.6% to 19.9%), with substantial variability across sites (range 8% to 22% of opioid use disorder-related encounters). In a postintervention survey, 67% of participating physicians indicated that they would have completed the training for a lower amount. CONCLUSION: A financial incentive paying approximately half the clinical rate was effective in promoting emergency physician X-waiver training. The effect on ED-based buprenorphine prescribing was positive but variable across sites, and likely dependent on the availability of additional supports.


Assuntos
Analgésicos Opioides/uso terapêutico , Buprenorfina/uso terapêutico , Medicina de Emergência/educação , Motivação , Transtornos Relacionados ao Uso de Opioides/tratamento farmacológico , Certificação , Humanos , Tratamento de Substituição de Opiáceos , Estudos Prospectivos
8.
Anesth Analg ; 131(1): 16-23, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32543802

RESUMO

The novel coronavirus disease 2019 (COVID-19) was first reported in China in December 2019. Since then, it has spread across the world to become one of the most serious life-threatening pandemics since the influenza pandemic of 1918. This review article will focus on the specific risks and nuanced considerations of COVID-19 in the cancer patient. Important perioperative management recommendations during this outbreak are emphasized, in addition to discussion of current treatment techniques and strategies available in the battle against COVID-19.


Assuntos
Infecções por Coronavirus/complicações , Infecções por Coronavirus/terapia , Neoplasias/complicações , Neoplasias/terapia , Pneumonia Viral/complicações , Pneumonia Viral/terapia , COVID-19 , Surtos de Doenças , Humanos , Pandemias , Administração dos Cuidados ao Paciente
10.
Inorg Chem ; 56(2): 783-790, 2017 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-28004923

RESUMO

Two new zinc phosphides, La4Zn7P10 and La4Mg1.5Zn8.5P12, were synthesized via transport reactions, and their crystal structures were determined by single crystal X-ray diffraction. La4Zn7P10 and La4Mg1.5Zn8.5P12 are built from three-dimensional Zn-P and Zn-Mg-P anionic frameworks that encapsulate lanthanum atoms. The anionic framework of La4Zn7P10 is constructed from one-dimensional Zn4P6, Zn2P4, and ZnP4 chains. The Zn4P6 chains are also the main building units in La4Mg1.5Zn8.5P12. In La4Zn7P10, the displacement of a zinc atom from the origin of the unit cell causes the Zn4 position to split into two equivalent atomic sites, each with 50% occupancy. The splitting of the atomic position substantially modifies the electronic properties, as suggested by theoretical calculations. The necessity of splitting can be overcome by replacement of zinc with magnesium in La4Mg1.5Zn8.5P12. Investigation of the transport properties of a densified polycrystalline sample of La4Zn7P10 demonstrates that it is an n-type semiconductor with a small bandgap of ∼0.04 eV at 300 K. La4Zn7P10 also exhibits low thermal conductivity, 1.3 Wm-1 K-1 at 300 K, which mainly originates from the lattice thermal conductivity. La4Zn7P10 is stable in a sealed evacuated ampule up to 1123 K as revealed by differential scanning calorimetry.

11.
BMC Nephrol ; 18(1): 258, 2017 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-28764654

RESUMO

BACKGROUND: Objective of the study is to assess prevalence and survival among end stage renal disease patients with restless legs syndrome (RLS) within a national database (USRDS). METHODS: A case-control, retrospective analysis was performed. Differences in characteristics between the groups, RLS and those with no sleep disorder (NSD), were determined using χ2 tests. Cox proportional hazard regression was used to assess survival between those with RLS and propensity score matched controls. RESULTS: Cases of restless legs syndrome were defined as patients that had received an ICD-9 code of 333.94 at any point during their treatment (n = 372). RLS group demonstrated a significantly higher proportion of patients with major depressive disorder, dysthymic disorder, anxiety, depression, minor depressive disorder, and psychological disorder. The difference between the survival was not statistically significant in those without sleep disorder as compared to those with RLS (HR =1.16±0.14, p = 0.3). CONCLUSIONS: True prevalence of RLS in dialysis patients can only be estimated if knowledge gap for care providers in diagnosis of RLS is addressed. RLS patients also have increased incidence of certain psychological disorders which needs to be addressed.


Assuntos
Centers for Medicare and Medicaid Services, U.S. , Bases de Dados Factuais , Falência Renal Crônica/diagnóstico , Falência Renal Crônica/mortalidade , Síndrome das Pernas Inquietas/diagnóstico , Síndrome das Pernas Inquietas/mortalidade , Idoso , Estudos de Casos e Controles , Centers for Medicare and Medicaid Services, U.S./estatística & dados numéricos , Estudos de Coortes , Bases de Dados Factuais/estatística & dados numéricos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Mortalidade/tendências , Estudos Retrospectivos , Estados Unidos/epidemiologia
13.
J Am Chem Soc ; 137(10): 3622-30, 2015 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-25702752

RESUMO

A new ternary compound, Li(1-x)Sn(2+x)As2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R3̅m space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn atoms. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigation by synchrotron X-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, the local Li/Sn ordering was revealed by synergistic investigations via solid-state (6,7)Li NMR spectroscopy, HRTEM, STEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions, creating substantial inhomogeneity on the nanoscale. The inhomogeneous local structure has a high impact on the physical properties of the synthesized compounds: the local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li(1-x)Sn(2+x)As2.

14.
Inorg Chem ; 54(3): 890-7, 2015 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-25347400

RESUMO

Two new lanthanum copper phosphides, LaCu(1+x)P(2) and LaCu(4)P(3), were synthesized from elements. Their crystal structures were determined by means of single-crystal X-ray diffraction. LaCu(1+x)P(2) crystallizes in a complex crystal structure, a derivative of the HfCuSi(2) structure type, in the space group Cmmm (No. 65) with unit cell parameters of a = 5.564(3) Å, b = 19.96(1) Å, c = 5.563(3) Å, and Z = 8. Its crystal structure features disordered Cu(2x)P(2) layers alternated with fully ordered PbO-like Cu(2)P(2) layers. The Cu-P layers are separated by La counter-cations. The Cu(2x)P(2) layers are composed of rectangular P(4) polyphosphide rings connected by partially occupied Cu atoms. Investigations of the electrical resistivity and Seebeck thermopower for LaCu(1+x)P(2) reveal metallic-type behavior with holes as the main charge carriers. LaCu(1+x)P(2) exhibits unexpectedly low thermal conductivity presumably because of disorder in the Cu(2x)P(2) layers. LaCu(4)P(3) crystallizes in a new structure type, in the tetragonal space group P4/nmm (No. 129) with unit cell parameters of a = 5.788(2) Å, c = 7.353(2) Å, and Z = 2. Its crystal structure features distorted square nets of Cu atoms within the Cu(4)P(3) slabs. Electron localization function analysis indicates that both P atoms in LaCu(4)P(3) have 1 + 4 coordination involving multicenter Cu-P bonding. According to the density of states and band structure, LaCu(4)P(3) is predicted to be a metallic conductor.

15.
Bioengineering (Basel) ; 11(8)2024 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-39199811

RESUMO

Cultivated meat, an advancement in cellular agriculture, holds promise in addressing environmental, ethical, and health challenges associated with traditional meat production. Utilizing tissue engineering principles, cultivated meat production employs biomaterials and technologies to create cell-based structures by introducing cells into a biocompatible scaffold, mimicking tissue organization. Among the cell sources used for producing muscle-like tissue for cultivated meats, primary adult stem cells like muscle satellite cells exhibit robust capabilities for proliferation and differentiation into myocytes, presenting a promising avenue for cultivated meat production. Evolutionarily optimized for growth in a 3D microenvironment, these cells benefit from the biochemical and biophysical cues provided by the extracellular matrix (ECM), regulating cell organization, interactions, and behavior. While plant protein-based scaffolds have been explored for their utilization for cultivated meat, they lack the biological cues for animal cells unless functionalized. Conversely, a decellularized bovine placental tissue ECM, processed from discarded birth tissue, achieves the biological functionalities of animal tissue ECM without harming animals. In this study, collagen and total ECM were prepared from decellularized bovine placental tissues. The collagen content was determined to be approximately 70% and 40% in isolated collagen and ECM, respectively. The resulting porous scaffolds, crosslinked through a dehydrothermal (DHT) crosslinking method without chemical crosslinking agents, supported the growth of bovine myoblasts. ECM scaffolds exhibited superior compatibility and stability compared to collagen scaffolds. In an attempt to make cultivate meat constructs, bovine myoblasts were cultured in steak-shaped ECM scaffolds for about 50 days. The resulting construct not only resembled muscle tissues but also displayed high cellularity with indications of myogenic differentiation. Furthermore, the meat constructs were cookable and able to sustain the grilling/frying. Our study is the first to utilize a unique bovine placentome-derived ECM scaffold to create a muscle tissue-like meat construct, demonstrating a promising and sustainable option for cultivated meat production.

16.
Gels ; 10(8)2024 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-39195017

RESUMO

Cultivated meat, also known as cell-based or clean meat, utilizes mesenchymal stem cells to cultivate mature cell types like adipocytes, which are pivotal for imparting the desired taste and texture. The delivery of differentiated cells, crucial in cultivated meat production, is facilitated through extensive exploration of 3D culturing techniques mimicking physiological environments. In this study, we investigated the adipogenic differentiation potential of bovine umbilical cord stem cells (BUSCs), sourced from discarded birth tissue, and assessed the feasibility of delivering differentiated cells for cultivated meat using gelatin methacrylate (GelMA) as a carrier for adipose tissue. Various adipogenic inducers, previously reported to be effective for human mesenchymal stem cells (hMSCs), were evaluated individually or in combination for their efficacy in promoting the adipogenesis of BUSCs. Surprisingly, while the traditional adipogenic inducers, including insulin, dexamethasone, isobutylmethylxantine (IBMX), indomethacin, and rosiglitazone, showed no significant effect on the adipogenic differentiation of BUSCs, efficient differentiation was achieved in the presence of a fatty acid cocktail. Furthermore, we explored methods for the delivery of BUSCs. Differentiated cells were delivered either encapsulated in GelMA hydrogel or populated on the surface of GelMA microparticles (MPs) as the adipose component of cultivated meat. Our findings reveal that after adipogenic induction, the lipid production per cell was comparable when cultured either within hydrogel or on MPs. However, GelMA-MPs supported better cell growth compared to hydrogel encapsulation. Consequently, the overall lipid production is higher when BUSCs are delivered via GelMA-MPs rather than encapsulation. This study not only systematically evaluated the impact of common adipogenic inducers on BUSCs, but also identified GelMA-MPs as a promising carrier for delivering bovine adipocytes for cultivated meat production.

17.
Gels ; 10(2)2024 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-38391427

RESUMO

The demand for innovative therapeutic interventions to expedite wound healing, particularly in vulnerable populations such as aging and diabetic patients, has prompted the exploration of novel strategies. Mesenchymal stem cell (MSC)-based therapy emerges as a promising avenue for treating acute and chronic wounds. However, its clinical application faces persistent challenges, notably the low survivability and limited retention time of engraftment in wound environments. Addressing this, a strategy to sustain the viability and functionality of human MSCs (hMSCs) in a graft-able format has been identified as crucial for advanced wound care. Hydrogel microparticles (HMPs) emerge as promising entities in the field of wound healing, showcasing versatile capabilities in delivering both cells and bioactive molecules/drugs. In this study, gelatin HMPs (GelMPs) were synthesized via an optimized mild processing method. GelMPs with distinct diameter sizes were sorted and characterized. The growth of hMSCs on GelMPs with various sizes was evaluated. The release of wound healing promoting factors from hMSCs cultured on different GelMPs were assessed using scratch wound assays and gene expression analysis. GelMPs with a size smaller than 100 microns supported better cell growth and cell migration compared to larger sizes (100 microns or 200 microns). While encapsulation of hMSCs in hydrogels has been a common route for delivering viable hMSCs, we hypothesized that hMSCs cultured on GelMPs are more robust than those encapsulated in hydrogels. To test this hypothesis, hMSCs were cultured on GelMPs or in the cross-linked methacrylated gelatin hydrogel (GelMA). Comparative analysis of growth and wound healing effects revealed that hMSCs cultured on GelMPs exhibited higher viability and released more wound healing activities in vitro. This observation highlights the potential of GelMPs, especially those with a size smaller than 100 microns, as a promising carrier for delivering hMSCs in wound healing applications, providing valuable insights for the optimization of advanced therapeutic strategies.

18.
J Am Chem Soc ; 135(51): 19111-4, 2013 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-24299423

RESUMO

Fragments of the superconducting FeSe layer, FeSe2 tetrahedral chains, were stabilized in the crystal structure of a new mixed-valent compound Fe3Se4(en)2 (en = ethylenediamine) synthesized from elemental Fe and Se. The FeSe2 chains are separated from each other by means of Fe(en)2 linkers. Mössbauer spectroscopy and magnetometry reveal strong magnetic interactions within the FeSe2 chains which result in antiferromagnetic ordering below 170 K. According to DFT calculations, anisotropic transport and magnetic properties are expected for Fe3Se4(en)2. This compound offers a unique way to manipulate the properties of the Fe-Se infinite fragments by varying the topology and charge of the Fe-amino linkers.


Assuntos
Complexos de Coordenação/química , Etilenodiaminas/química , Ferro/química , Magnetismo , Modelos Moleculares , Selênio/química , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Etilenodiaminas/síntese química , Temperatura
19.
J Am Chem Soc ; 135(33): 12313-23, 2013 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-23862668

RESUMO

A novel clathrate phase, Ba8Au16P30, was synthesized from its elements. High-resolution powder X-ray diffraction and transmission electron microscopy were used to establish the crystal structure of the new compound. Ba8Au16P30 crystallizes in an orthorhombic superstructure of clathrate-I featuring a complete separation of gold and phosphorus atoms over different crystallographic positions, similar to the Cu-containing analogue, Ba8Cu16P30. Barium cations are trapped inside the large polyhedral cages of the gold-phosphorus tetrahedral framework. X-ray diffraction indicated that one out of 15 crystallographically independent phosphorus atoms appears to be three-coordinate. Probing the local structure and chemical bonding of phosphorus atoms with (31)P solid-state NMR spectroscopy confirmed the three-coordinate nature of one of the phosphorus atomic positions. High-resolution high-angle annular dark-field scanning transmission electron microscopy indicated that the clathrate Ba8Au16P30 is well-ordered on the atomic scale, although numerous twinning and intergrowth defects as well as antiphase boundaries were detected. The presence of such defects results in the pseudo-body-centered-cubic diffraction patterns observed in single-crystal X-ray diffraction experiments. NMR and resistivity characterization of Ba8Au16P30 indicated paramagnetic metallic properties with a room-temperature resistivity of 1.7 mΩ cm. Ba8Au16P30 exhibits a low total thermal conductivity (0.62 W m(-1) K(-1)) and an unprecedentedly low lattice thermal conductivity (0.18 W m(-1) K(-1)) at room temperature. The values of the thermal conductivity for Ba8Au16P30 are significantly lower than the typical values reported for solid crystalline compounds. We attribute such low thermal conductivity values to the presence of a large number of heavy atoms (Au) in the framework and the formation of multiple twinning interfaces and antiphase defects, which are effective scatterers of heat-carrying phonons.

20.
Inorg Chem ; 52(12): 7061-7, 2013 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-23734787

RESUMO

Barium gold polyphosphide BaAu2P4 was synthesized from elements and structurally characterized by single crystal X-ray diffraction. BaAu2P4 crystallizes in a new structure type, in the orthorhombic space group Fddd (No. 70) with a = 6.517(1) Å, b = 8.867(2) Å, c = 21.844(5) Å. The crystal structure of BaAu2P4 consists of Au­P layers separated by layers of Ba atoms. Each Au­P layer is composed of infinite ∞(1)(P­) chains of unique topology linked together by almost linearly coordinated Au atoms. According to Zintl­Klemm formalism, this compound is charge balanced assuming closed shell d10 configuration for Au: Ba2+(Au+)2(P­)4. Magnetic and solid state NMR measurements together with quantum-chemical calculations reveal diamagnetic and semiconducting behavior for the investigated polyphosphide, which is as expected for the charged balanced Zintl phase. Electron localization function and crystal orbital Hamilton population analyses reveal strong P­P and Au­P bonding and almost nonbonding Au­Au interactions in BaAu2P4.

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