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Secondary lymphoid organs (SLOs), including tonsils (TS), lymph nodes (LN), and Peyer's Patches, exhibit complementary immune functions. However, little is known about the spatial organization of immune cells and extracellular matrix (ECM) in the SLOs. Traditional imaging is limited to a few markers, confining our understanding of the differences between the SLOs. Herein, imaging mass cytometry addressed this gap by simultaneously profiling 25-plex proteins in SLO tissues at subcellular resolution. The antibody panel targeted immune, stromal, chemokine, epigenetic, and functional markers. For robust cell identification, a computational workflow SpatialVizPheno was developed to spatially phenotype 999,970 cells using two approaches, including manual gating and semi-supervised gating, iterative clustering, and annotation. LN exhibited the highest density of B cells while the intestinal tissues contained the highest proportion of regulatory and follicular helper T cells. SpatialVizPheno identified the most prevalent interaction between follicular dendritic cells and stromal cells (SCs), plasmablasts/plasma cells, and the SCs across the lymphoid tissues. Collagen-enriched regions were associated with the spatial orientation of B cell follicles in both TS and LN tissues, but not in intestinal lymphoid tissues. Such spatial differences of immunophenotypes and ECM in different SLO tissues can be used to quantify the relationship between cellular organization and ultimate immune responses.
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Multiple myeloma (MM), a cancer of bone marrow plasma cells, is the second-most common hematological malignancy. However, despite immunotherapies like chimeric antigen receptor (CAR)-T cells, relapse is nearly universal. The bone marrow (BM) microenvironment influences how MM cells survive, proliferate, and resist treatment. Yet, it is unclear which BM niches give rise to MM pathophysiology. Here, we present a 3D microvascularized culture system, which models the endosteal and perivascular bone marrow niches, allowing us to study MM-stroma interactions in the BM niche and model responses to therapeutic CAR-T cells. We demonstrated the prolonged survival of cell line-based and patient-derived multiple myeloma cells within our in vitro system and successfully flowed in donor-matched CAR-T cells. We then measured T cell survival, differentiation, and cytotoxicity against MM cells using a variety of analysis techniques. Our MM-on-a-chip system could elucidate the role of the BM microenvironment in MM survival and therapeutic evasion and inform the rational design of next-generation therapeutics. TEASER: A multiple myeloma model can study why the disease is still challenging to treat despite options that work well in other cancers.
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Multiplex imaging technologies allow the characterization of single cells in their cellular environments. Understanding the organization of single cells within their microenvironment and quantifying disease-status related biomarkers is essential for multiplex datasets. Here we proposed SNOWFLAKE, a graph neural network framework pipeline for the prediction of disease-status from combined multiplex cell expression and morphology in human B-cell follicles. We applied SNOWFLAKE to a multiplex dataset related to COVID-19 infection in humans and showed better predictive power of the SNOWFLAKE pipeline compared to other machine learning and deep learning methods. Moreover, we combined morphological features inside graph edge features to utilize attribution methods for extracting disease-relevant motifs from single-cell spatial graphs. The underlying subgraphs were further analyzed and associated with disease status across the dataset. We showed that SNOWFLAKE successfully extracted significant low dimensional embedding from subgraphs with a clear separation between disease status and helped characterize unique cellular interactions in the subgraphs. SNOWFLAKE is a generalizable pipeline for the analysis of multiplex imaging data modality by extracting disease-relevant subgraphs guided by graph-level prediction.
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Metabolic reprogramming in cancer and immune cells occurs to support their increasing energy needs in biological tissues. Here we propose Single Cell Spatially resolved Metabolic (scSpaMet) framework for joint protein-metabolite profiling of single immune and cancer cells in male human tissues by incorporating untargeted spatial metabolomics and targeted multiplexed protein imaging in a single pipeline. We utilized the scSpaMet to profile cell types and spatial metabolomic maps of 19507, 31156, and 8215 single cells in human lung cancer, tonsil, and endometrium tissues, respectively. The scSpaMet analysis revealed cell type-dependent metabolite profiles and local metabolite competition of neighboring single cells in human tissues. Deep learning-based joint embedding revealed unique metabolite states within cell types. Trajectory inference showed metabolic patterns along cell differentiation paths. Here we show scSpaMet's ability to quantify and visualize the cell-type specific and spatially resolved metabolic-protein mapping as an emerging tool for systems-level understanding of tissue biology.
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Neoplasias Pulmonares , Metabolómica , Femenino , Masculino , Humanos , Metabolómica/métodos , Biología de SistemasRESUMEN
Image-based spatial omics methods such as fluorescence in situ hybridization (FISH) generate molecular profiles of single cells at single-molecule resolution. Current spatial transcriptomics methods focus on the distribution of single genes. However, the spatial proximity of RNA transcripts can play an important role in cellular function. We demonstrate a spatially resolved gene neighborhood network (spaGNN) pipeline for the analysis of subcellular gene proximity relationships. In spaGNN, machine-learning-based clustering of subcellular spatial transcriptomics data yields subcellular density classes of multiplexed transcript features. The nearest-neighbor analysis produces heterogeneous gene proximity maps in distinct subcellular regions. We illustrate the cell-type-distinguishing capability of spaGNN using multiplexed error-robust FISH data of fibroblast and U2-OS cells and sequential FISH data of mesenchymal stem cells (MSCs), revealing tissue-source-specific MSC transcriptomics and spatial distribution characteristics. Overall, the spaGNN approach expands the spatial features that can be used for cell-type classification tasks.
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Perfilación de la Expresión Génica , Análisis de la Célula Individual , Hibridación Fluorescente in Situ/métodos , Análisis de la Célula Individual/métodos , Perfilación de la Expresión Génica/métodos , Redes Reguladoras de Genes , FibroblastosRESUMEN
Organelles play important roles in human health and disease, such as maintaining homeostasis, regulating growth and aging, and generating energy. Organelle diversity in cells not only exists between cell types but also between individual cells. Therefore, studying the distribution of organelles at the single-cell level is important to understand cellular function. Mesenchymal stem cells are multipotent cells that have been explored as a therapeutic method for treating a variety of diseases. Studying how organelles are structured in these cells can answer questions about their characteristics and potential. Herein, rapid multiplexed immunofluorescence (RapMIF) was performed to understand the spatial organization of 10 organelle proteins and the interactions between them in the bone marrow (BM) and umbilical cord (UC) mesenchymal stem cells (MSCs). Spatial correlations, colocalization, clustering, statistical tests, texture, and morphological analyses were conducted at the single cell level, shedding light onto the interrelations between the organelles and comparisons of the two MSC subtypes. Such analytics toolsets indicated that UC MSCs exhibited higher organelle expression and spatially spread distribution of mitochondria accompanied by several other organelles compared to BM MSCs. This data-driven single-cell approach provided by rapid subcellular proteomic imaging enables personalized stem cell therapeutics.
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Células Madre Mesenquimatosas , Proteómica , Humanos , Células de la Médula Ósea , Diferenciación Celular/fisiología , Cordón Umbilical , MitocondriasRESUMEN
Activated B-cell-like diffuse large B-cell lymphomas (ABC-DLBCLs) are characterized by constitutive activation of nuclear factor κB driven by the B-cell receptor (BCR) and Toll-like receptor (TLR) pathways. However, BCR-pathway-targeted therapies have limited impact on DLBCLs. Here we used >1,100 DLBCL patient samples to determine immune and extracellular matrix cues in the lymphoid tumour microenvironment (Ly-TME) and built representative synthetic-hydrogel-based B-cell-lymphoma organoids accordingly. We demonstrate that Ly-TME cellular and biophysical factors amplify the BCR-MYD88-TLR9 multiprotein supercomplex and induce cooperative signalling pathways in ABC-DLBCL cells, which reduce the efficacy of compounds targeting the BCR pathway members Bruton tyrosine kinase and mucosa-associated lymphoid tissue lymphoma translocation protein 1 (MALT1). Combinatorial inhibition of multiple aberrant signalling pathways induced higher antitumour efficacy in lymphoid organoids and implanted ABC-DLBCL patient tumours in vivo. Our studies define the complex crosstalk between malignant ABC-DLBCL cells and Ly-TME, and provide rational combinatorial therapies that rescue Ly-TME-mediated attenuation of treatment response to MALT1 inhibitors.
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Linfoma de Células B Grandes Difuso , Microambiente Tumoral , Humanos , Línea Celular Tumoral , Transducción de Señal , FN-kappa B/metabolismo , Linfoma de Células B Grandes Difuso/tratamiento farmacológico , Linfoma de Células B Grandes Difuso/metabolismo , Proteína 1 de la Translocación del Linfoma del Tejido Linfático Asociado a Mucosas/metabolismoRESUMEN
Protein-protein interaction networks are altered in multi-gene dysregulations in many disorders. Image-based protein multiplexing sheds light on signaling pathways to dissect cell-to-cell heterogeneity, previously masked by the bulk assays. Herein, we present a rapid multiplexed immunofluorescence (RapMIF) method measuring up to 25-plex spatial protein maps from cultures and tissues at subcellular resolution, providing combinatorial 272 pairwise and 1,360 tri-protein signaling states across 33 multiplexed pixel-level clusters. The RapMIF pipeline automated staining, bleaching, and imaging of the biospecimens in a single platform. RapMIF showed that WNT/ß-catenin signaling upregulated upon the inhibition of the AKT/mTOR pathway. Subcellular protein images demonstrated translocation patterns, spatial receptor discontinuity, and subcellular signaling clusters in single cells. Signaling networks exhibited spatial redistribution of signaling proteins in drug-responsive cultures. Machine learning analysis predicted the phosphorylated ß-catenin expression from interconnected signaling protein images. RapMIF is an ideal signaling discovery approach for precision therapy design.
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The Immunoscore is a method to quantify the immune cell infiltration within cancers to predict the disease prognosis. Previous immune profiling approaches relied on limited immune markers to establish patients' tumor immunity. However, immune cells exhibit a higher-level complexity that is typically not obtained by the conventional immunohistochemistry methods. Herein, we present a spatially variant immune infiltration score, termed as SpatialVizScore, to quantify immune cells infiltration within lung tumor samples using multiplex protein imaging data. Imaging mass cytometry (IMC) was used to target 26 markers in tumors to identify stromal, immune, and cancer cell states within 26 human tissues from lung cancer patients. Unsupervised clustering methods dissected the spatial infiltration of cells in tissue using the high-dimensional analysis of 16 immune markers and other cancer and stroma enriched labels to profile alterations in the tumors' immune infiltration patterns. Spatially resolved maps of distinct tumors determined the spatial proximity and neighborhoods of immune-cancer cell pairs. These SpatialVizScore maps provided a ranking of patients' tumors consisting of immune inflamed, immune suppressed, and immune cold states, demonstrating the tumor's immune continuum assigned to three distinct infiltration score ranges. Several inflammatory and suppressive immune markers were used to establish the cell-based scoring schemes at the single-cell and pixel-level, depicting the cellular spectra in diverse lung tissues. Thus, SpatialVizScore is an emerging quantitative method to deeply study tumor immunology in cancer tissues.
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OBJECTIVES: Repair of complete atrioventricular septal defect (cAVSD) is routinely performed at around 3 months of age with good results. However, some patients require earlier surgery due to heart failure or failure to thrive. It is uncertain whether cAVSD repair performed on patients ≤3.5 kg leads to increased mortality and reoperation on the left atrioventricular valve. METHODS: All patients who underwent cAVSD repair from 1990 to 2019 at a single institution were included in the study. Data were obtained from retrospective review of medical records and correspondence with cardiologists. RESULTS: Of 456 patients, 12.9% (59/456) weighed ≤3.5 kg at time of repair. This group was younger (P < .01) and had greater rates of heart failure (P < .01) and failure to thrive (P = .02). There was no significant difference in early mortality between the 2 groups (1.7% [1/59] vs 3.0% [12/397], P = 1.0). Survival at 20 years was 83.8% in those ≤3.5 kg, compared with 90.4% in those >3.5 kg, with no significant difference between the 2 groups (P = .68). Freedom from left atrioventricular valve reoperation at 20 years was 73.6% in those ≤3.5 kg, compared with 74.5% in those >3.5 kg, with no significant difference between the 2 groups (P = .45). CONCLUSIONS: Repair of cAVSD in children ≤3.5 kg appears to be safe, with similar overall survival and freedom from reoperation compared with those >3.5 kg. These findings add further support to an approach of early complete repair in children with severe heart failure or failure to thrive.
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Insuficiencia Cardíaca , Defectos de los Tabiques Cardíacos , Enfermedades de las Válvulas Cardíacas , Niño , Insuficiencia de Crecimiento/cirugía , Insuficiencia Cardíaca/etiología , Insuficiencia Cardíaca/cirugía , Enfermedades de las Válvulas Cardíacas/cirugía , Humanos , Lactante , Reoperación , Estudios Retrospectivos , Resultado del TratamientoRESUMEN
OBJECTIVES: Left ventricular outflow tract obstruction (LVOTO) is a recognized complication after complete repair of atrioventricular septal defect (AVSD). This study reviewed the incidence and management of LVOTO following AVSD repair at a single institution. METHODS: From 1975 to 2019, 24 patients (3.3%, 24/730) underwent reoperation due to LVOTO following partial AVSD (pAVSD) and complete AVSD (cAVSD) repair. The data were retrospectively reviewed. RESULTS: The incidence of LVOTO following pAVSD and cAVSD repair was 4.4% (12/275) and 2.6% (12/455). Freedom from LVOTO reoperation following pAVSD and cAVSD repair at 25 years was 94.3% [95% confidence interval (CI); 89.7-96.7] and 95% (95% CI; 91.1-97.3). The median time from complete repair of pAVSD and cAVSD to LVOTO reoperation was 4.4 years [interquartile range (IQR): 3.4-6.7] and 2.6 years (IQR: 2.2-4.7). Freedom from second LVOTO reoperation at 5, 10 and 15 years was 83.7% (95% CI; 57.2-98.2), 59.2% (95% CI; 28.7, 80.3) and 39.5% (95% CI; 13.2-65.3). The median time between the first and the second LVOTO reoperation in the groups of pAVSD and cAVSD was 6.1 years (IQR: 3.4-8.9) and 8.6 years (IQR: 5.7-9.8). There was no significant difference regarding the first (P = 0.7406) and subsequent LVOTO (P = 0.7153) following complete repair of pAVSD and cAVSD. Combined access to the left ventricular outflow tract was not protective regarding LVOTO reoccurrence. Survival for both groups after LVOTO reoperation at 15 years was 95.6% (95% CI 99.4-72.9). CONCLUSIONS: Incidence of LVOTO after AVSD repair is low but the reoccurrence rate is high. Standard subaortic resection does not always provide definitive LVOTO relief. The survival after LVOTO reoperation is excellent.
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Procedimientos Quirúrgicos Cardíacos , Obstrucción del Flujo Ventricular Externo , Procedimientos Quirúrgicos Cardíacos/efectos adversos , Defectos de los Tabiques Cardíacos/cirugía , Humanos , Incidencia , Lactante , Reoperación , Estudios Retrospectivos , Resultado del Tratamiento , Obstrucción del Flujo Ventricular Externo/diagnóstico por imagen , Obstrucción del Flujo Ventricular Externo/epidemiología , Obstrucción del Flujo Ventricular Externo/etiología , Obstrucción del Flujo Ventricular Externo/cirugíaRESUMEN
BACKGROUND: Repair of complete atrioventricular septal defect (cAVSD) is achieved with low mortality. However, there is a high rate of reoperation on the left atrioventricular valve (LAVV), which is often attributed to nonclosure of the cleft. Although nonclosure of the cleft has been reported to be a risk factor for reoperation, no randomized controlled or propensity-matched trials have ever been performed. We investigated the effect of cleft closure on outcomes after cAVSD repair. METHODS: We reviewed 455 patients who underwent cAVSD repair between 1990 and 2019. To determine the effect of cleft closure, propensity score matching was performed on risk factors for reoperation after cAVSD repair. RESULTS: Median age was 3.6 months (mean, 9.6 ± 20.4 months), median weight was 4.3 kg (mean, 4.7 ± 4.3 kg) and 41.9% (191 of 455) were male. Early mortality was 2.9% (13 of 455), and survival was 89.8% ± 1.9% at 20 years. Early reoperation was a risk factor for mortality (P = .004). Freedom from reoperation was 72.5% ± 4.0% at 20 years. Freedom from LAVV reoperation was 74.1% ± 4.0% at 20 years. Preoperative severe LAVV regurgitation (P < .001) and early postoperative moderate or greater LAVV regurgitation (P = .007) were risk factors for reoperation, while trisomy 21 (P = .03) and recent era of surgery (P = .02) were protective. Propensity score matching yielded 106 pairs. There were no differences in long-term survival (P = .71) or reoperation (P = .26) between the 2 groups. CONCLUSIONS: Repair of cAVSD can be achieved with low mortality and good long-term survival, although the reoperation rate remains high. Similar freedom from reoperation can be achieved with or without closure of the LAVV cleft.
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Procedimientos Quirúrgicos Cardíacos , Defectos de los Tabiques Cardíacos , Procedimientos Quirúrgicos Cardíacos/efectos adversos , Femenino , Defectos de los Tabiques Cardíacos/cirugía , Humanos , Lactante , Masculino , Complicaciones Posoperatorias/etiología , Complicaciones Posoperatorias/cirugía , Puntaje de Propensión , Reoperación , Estudios Retrospectivos , Resultado del TratamientoRESUMEN
Deep molecular profiling of biological tissues is an indicator of health and disease. We used imaging mass cytometry (IMC) to acquire spatially resolved 20-plex protein data in tissue sections from normal and chronic tonsillitis cases. We present SpatialViz, a suite of algorithms to explore spatial relationships in multiplexed tissue images by visualizing and quantifying single-cell granularity and anatomical complexity in diverse multiplexed tissue imaging data. Single-cell and spatial maps confirmed that CD68+ cells were correlated with the enhanced Granzyme B expression and CD3+ cells exhibited enrichment of CD4+ phenotype in chronic tonsillitis. SpatialViz revealed morphological distributions of cellular organizations in distinct anatomical areas, spatially resolved single-cell associations across anatomical categories, and distance maps between the markers. Spatial topographic maps showed the unique organization of different tissue layers. The spatial reference framework generated network-based comparisons of multiplex data from healthy and diseased tonsils. SpatialViz is broadly applicable to multiplexed tissue biology.
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Procesamiento de Imagen Asistido por Computador/métodos , Análisis de la Célula Individual/métodos , Tonsilitis/fisiopatología , Algoritmos , Humanos , Proteómica/métodos , Análisis Espacio-Temporal , Tonsilitis/metabolismoRESUMEN
Spatially resolved RNA and protein molecular analyses have revealed unexpected heterogeneity of cells. Metabolic analysis of individual cells complements these single-cell studies. Here, we present a three-dimensional spatially resolved metabolomic profiling framework (3D-SMF) to map out the spatial organization of metabolic fragments and protein signatures in immune cells of human tonsils. In this method, 3D metabolic profiles were acquired by time-of-flight secondary ion mass spectrometry to profile up to 189 compounds. Ion beams were used to measure sub-5-nanometer layers of tissue across 150 sections of a tonsil. To incorporate cell specificity, tonsil tissues were labeled by an isotope-tagged antibody library. To explore relations of metabolic and cellular features, we carried out data reduction, 3D spatial correlations and classifications, unsupervised K-means clustering, and network analyses. Immune cells exhibited spatially distinct lipidomic fragment distributions in lymphatic tissue. The 3D-SMF pipeline affects studying the immune cells in health and disease.
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Metaboloma , Metabolómica , Análisis por Conglomerados , Humanos , Metabolómica/métodos , Espectrometría de Masa de Ion SecundarioRESUMEN
OBJECTIVES: Complete atrioventricular septal defect (cAVSD) repair is usually performed between 3 and 6 months of age. However, some children present with early heart failure requiring intervention. It is unclear whether primary complete repair or initial pulmonary artery banding (PAB) provides better outcomes. METHODS: All patients (n = 194) who underwent surgery for cAVSD younger than 3 months of age between 1990 and 2019 were included. Propensity score matching was performed on risk factors for mortality. RESULTS: Primary complete repair was performed in 77.8% (151/194), whereas PAB was performed in 22.2% (43/194). Children who had PAB were younger (P < .01), had lower weight (P < .001), and less trisomy 21 (P = .04). Interstage mortality for PAB was 18.6% (8/43), whereas early mortality for primary repair was 3.3% (5/151). Survival at 20 years was 92.0% (95% confidence interval [CI], 85.6%-95.7%) for primary repair and 63.2% (95% CI, 42.5%-78.1%) for PAB (P < .001). There was no difference in left atrioventricular valve (LAVV) reoperation rates (P = .94). Propensity score matching produced 2 well-matched groups. Survival at 20 years was 94.2% (95% CI, 85.1%-98.8%) for primary repair, and 58.4% (95% CI, 33.5%-76.7%) for PAB (P = .001). There was no difference in LAVV reoperation rates (P = .71). Neonatal repair was achieved with no early deaths and 100% survival at 10 years. CONCLUSIONS: In children younger than 3 months of age, complete repair of cAVSD is associated with better survival than PAB. Both strategies have similar rates of LAVV reoperation. Neonatal repair of cAVSD can be achieved with excellent results. Primary repair of cAVSD should be the preferred strategy in children younger than 3 months of age.
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Procedimientos Quirúrgicos Cardíacos , Defectos de los Tabiques Cardíacos , Arteria Pulmonar/cirugía , Adulto , Procedimientos Quirúrgicos Cardíacos/efectos adversos , Procedimientos Quirúrgicos Cardíacos/métodos , Procedimientos Quirúrgicos Cardíacos/mortalidad , Niño , Defectos de los Tabiques Cardíacos/mortalidad , Defectos de los Tabiques Cardíacos/cirugía , Humanos , Lactante , Recién Nacido , Puntaje de Propensión , Tiempo de Tratamiento , Adulto JovenRESUMEN
The Coronavirus Disease 2019 (COVID-19), caused by the severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), outbreak from Wuhan City, Hubei province, China in 2019 has become an ongoing global health emergency. The emerging virus, SARS-CoV-2, causes coughing, fever, muscle ache, and shortness of breath or dyspnea in symptomatic patients. The pathogenic particles that are generated by coughing and sneezing remain suspended in the air or attach to a surface to facilitate transmission in an aerosol form. This review focuses on the recent trends in pandemic biology, diagnostics methods, prevention tools, and policies for COVID-19 management. To meet the growing demand for medical supplies during the COVID-19 era, a variety of personal protective equipment (PPE) and ventilators have been developed using do-it-yourself (DIY) manufacturing. COVID-19 diagnosis and the prediction of virus transmission are analyzed by machine learning algorithms, simulations, and digital monitoring. Until the discovery of a clinically approved vaccine for COVID-19, pandemics remain a public concern. Therefore, technological developments, biomedical research, and policy development are needed to decipher the coronavirus mechanism and epidemiological characteristics, prevent transmission, and develop therapeutic drugs.
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BACKGROUND: Regional nerve blocks are commonly used to manage postoperative pain after arthroscopic shoulder procedures. The interscalene brachial plexus block (ISB) is commonly used; however, because of the reported side effects of ISB, the use of a suprascapular nerve block (SSNB) has been described as an alternative strategy with fewer reported side effects. PURPOSE: To examine the efficacy of SSNB for pain control after shoulder arthroscopy compared with ISB as well as anesthesia without a nerve block. STUDY DESIGN: Systematic review; Level of evidence, 1. METHODS: Three databases (PubMed, MEDLINE, and EMBASE) were searched on April 20, 2018, to systematically identify and screen the literature for randomized controlled trials (RCTs). A meta-analysis of standard mean differences (SMDs) was performed to pool the estimated effects of the nerve blocks. RESULTS: The search identified 14 RCTs that included 1382 patients, with a mean age of 54 years (SD, 13 years). The mean follow-up time was 3 days (range, 24 hours to 6 weeks). Postoperative pain control was significantly more effective in the SSNB groups compared with the control groups within 1 hour (SMD, -0.76; 95% CI, -1.45 to -0.07; P = .03) and 4 to 6 hours (SMD, -0.81; 95% CI, -1.53 to -0.09; P = .03) postoperatively. However, pain control was significantly less effective in the SSNB groups compared with ISB within 1 hour (SMD, 0.87; 95% CI, 0.28 to 1.46; P = .004). No major complications were noted in the SSNB groups, and minor complications such as hoarseness and prolonged motor block were significantly less common for SSNB compared with ISB. CONCLUSION: Although not more efficacious than ISB in terms of pain control for patients undergoing shoulder arthroscopy, SSNB provides significantly improved pain control in comparison with analgesia without a nerve block. Moreover, few major and minor complications are associated with SSNB reported across the literature.
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The hemicellulose composition of a pulp significantly affects its chemical and physical properties and thus represents an important process control variable. However, complicated steps of sample preparation make standard methods for the carbohydrate analysis of pulp samples, such as high performance liquid chromatography (HPLC), expensive and time-consuming. In contrast, pulp analysis by attenuated total internal reflection Fourier transform infrared spectroscopy (ATR FT-IR) requires little sample preparation. Here we show that ATR FT-IR with discrete wavelet transform (DWT) and standard normal variate (SNV) spectral preprocessing offers a convenient means for the qualitative and quantitative analysis of hemicelluloses in bleached kraft pulp and alkaline treated kraft pulp. The pulp samples investigated include bleached softwood kraft pulps, bleached hardwood kraft pulps, and their mixtures, as obtained from Canadian industry mills or blended in a lab, and bleached kraft pulp samples treated with 0-6% NaOH solutions. In the principal component analysis (PCA) of these spectra, we find the potential both to differentiate all pulps on the basis of hemicellulose compositions and to distinguish bleached hardwood pulps by species. Partial least squares (PLS) multivariate analysis gives a 0.442 wt% root mean square errors of prediction (RMSEP) for the prediction of xylan content and 0.233 wt% RMSEP for the prediction of mannan content. These data all support the idea that ATR FT-IR has a great potential to rapidly and accurately predict the content of xylan and mannan for bleached kraft pulps (softwood, hardwood, and their mixtures) in industry. However, the prediction of xylan and mannan concentrations presented a difficulty for pulp samples with modified cellulose crystalline structure.
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The glucuronoxylan composition of a pulp affects the bonding between cellulosic fibres, and thus correlates with such network properties as tensile strength. Here, we demonstrate the promise of attenuated total-internal-reflection (ATR) FTIR spectroscopy as a rapid means for classifying the xylan contained in commercial bleached kraft pulps. This study draws upon samples composed of bleached eucalyptus kraft pulps and combinations of eucalyptus with other commercial bleached kraft pulps. We subject these pulp samples to systematic extraction by sodium hydroxide solutions with concentrations ranging from 0.5% to 6% to build a standard sample library with varying xylan content, quantified by acid hydrolysis, HPLC carbohydrate separation and titration. This pulp chemistry of mild alkaline extraction removes up to two-thirds of the xylan. In the NaOH concentration regime of 0.5-4%, the infrared spectral variance reflects the decrease in hemicellulose concentration as well as the cellulose crystallinity. A residual xylan component remains resistant to base solutions of higher concentrations. Principal component analysis of infrared spectra distinguishes this residual xylan as structurally variant. Both partial least squares multivariate analysis and univariate analysis confined to a feature at 964 cm(-1) in normalized second derivative IR spectra show a very good correlation with xylan content quantified by HPLC.
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To learn more about the bleaching action of pulps by (hydroxymethyl)phosphines, lignin chromophores, such as the alpha,beta-unsaturated aromatic aldehydes, sinapaldehyde, coniferylaldehyde, and coumaraldehyde, were reacted with the tertiary phosphines R2R'P [R = R' = Me, Et, (CH2)3OH, iPr, cyclo-C6H11, (CH2)2CN; R = Me or Et, R' = Ph; R = Ph, R' = Me, m-NaSO3-C6H4] in water at room temperature under argon. In all cases, initial nucleophilic attack of the phosphine occurs at the activated C=C bond to form a zwitterionic monophosphonium species. With the phosphines PR3 [R = Me, Et, (CH2)3OH] and with R2R'P (R = Me or Et, R' = Ph), the zwitterion undergoes self-condensation to give a bisphosphonium zwitterion that can react with aqueous HCl to form the corresponding dichloride salts (as a mixture of R,R- and S,S-enantiomers); X-ray structures are presented for the bisphosphonium chlorides synthesized from the Et3P and Me3P reactions with sinapaldehyde. With the more bulky phosphines, iPr3P, MePPh2, (cyclo-C6H11)3P, and Na[Ph2P(m-SO3-C6H4)], only an equilibrium of the monophosphonium zwitterion with the reactant aldehyde is observed. The weakly nucleophilic [NC(CH2)2]3P does not react with sinapaldehyde. An analysis of some exceptional 1H NMR data within the prochiral phosphorus centers of the bisphosphonium chlorides is also presented.