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001) earlier in pea gravel (548 days) than in the three other materials, and earlier in the two wood chips (day 682 for beech, day 692 for spruce, P less then 0.05) than in soil (1,277 days). 4. Accumulation of ascarid eggs in the area close to the henhouse can be reduced by any of the tested litter materials compared to bare soil. Adding litter to this area is highly recommended for free-range layer farmers in order to reduce numbers of infective ascarid eggs.Fat embolism syndrome (FES) is a clinical entity occurring due to the presence of fat particles in the microcirculation, typically manifesting 12-72 hours after long bone trauma with respiratory distress, altered mental status, and petechial rash. Our case is that of a 17-year-old girl who suffered multiple orthopedic injuries without intracranial trauma after being a pedestrian struck by a vehicle. Despite presenting with a normal Glasgow Coma Score (GCS), within 4 hours of presentation, she was noted to have an acute mental status change to a GCS 7 with a normal computed tomography brain. Magnetic resonance imaging of the brain was suggestive of FES which, in this patient, had a rapidly progressing course with the development of severe cerebral edema and intracranial hypertension refractory to maximal medical therapy. Our patient required bilateral craniectomies for intracranial decompression and progressed over a 2-month hospital course to have subsequent cranioplasty and functional neurologic improvement. FES requires a high index of clinical suspicion in the presence of long bone fracture with unexplained altered mental status. The clinical course can be rapidly progressing with the development of intracranial hypertension which may benefit from surgical decompression with optimistic prognosis.Recurrent toxic shock syndrome (TSS) is uncommon. A certain level of clinical suspicion is indicated with a complex sepsis presentation in the postoperative kidney transplant patient. We present a case of presumed recurrent postoperative TSS in a living kidney transplant recipient. The patient was a 19-year-old Caucasian female with a 4-year prior single episode of toxin-mediated sepsis and chronic kidney disease (CKD) secondary to autosomal recessive Alport's syndrome (confirmed via renal biopsy and genetic testing). She received a human leukocyte antigen (HLA) 2A 2B 1DR MM, CMV -D/-R kidney from her 21-year-old friend. The patient received Campath and IV steroid induction after total cold ischemic time of 170 minutes with 40 minutes of revascularization. On postoperative day (POD) 5, she required re-exploration with reimplantation and stenting of the transplanted ureter. The patient subsequently spiked a fever of 101.6° with a generalized rash prompting collection of blood cultures which demonstrated no growth. Infectious Disease was consulted due to persistent fevers despite IV antibiotics. On POD 12, the patient returned to the operating room (OR) for evacuation of hematoma after decline in Hgb to 5.8 and CT confirmed perinephric hematomas. Kidney biopsy showed no rejection and donor specific antibodies (DSAs) were unremarkable. The patient underwent 1 treatment of empiric plasmapheresis for possible non-HLA antibodies followed by initiation of clindamycin. The patient's condition improved, and she was discharged home with a normal creatinine. Recurrent TSS is rare but should be added to the differential diagnoses of immuno-compromised patients undergoing kidney transplantation with a history of prior toxin-mediated sepsis.Bronchobiliary fistulas are exceedingly rare pathological connections between the biliary and the bronchial systems, which result from hepatobiliary neoplasms, abscesses, or thoracoabdominal trauma. Prompt recognition, diagnosis, and intervention is essential in order to prevent the high morbidity and mortality associated with this disease process. Multiple management strategies have been described in the literature; however, the optimal course has not been well defined. We present a case of a 31-year-old male who developed a bronchobiliary fistula 1 month after thoracoabdominal trauma. After conservative management with biliary stenting failed, he successfully underwent latissimus sparing right posterolateral thoracotomy, complete fistulectomy, right lower lobe wedge resection, and diaphragmatic reconstruction with subsequent resolution of his symptoms.

Laparoscopic liver resections can result in decreased length of stay. We looked at our hospital experience with 24 hours or less stay after minor laparoscopic liver resections.

Patients who underwent laparoscopic minor hepatectomy (less than 3 hepatic segments resection) and stayed 24 hours or less in the hospital were selected from prospectively kept hepatobiliary surgery database. All were managed according to the established enhanced recovery after surgery protocol.

14 cases were identified and included 3 bisegmentectomies and 11 segmental resections. Length of surgery was between 29 and 210 minutes (median 80.5 minutes), and median blood loss was 50 cc (range 20-400 cc). 4 patients were discharged home the same day with 10 staying overnight.

Selected group of patients undergoing minor laparoscopic hepatectomy can be discharged home the same day or less than 24 hours after surgery.

Selected group of patients undergoing minor laparoscopic hepatectomy can be discharged home the same day or less than 24 hours after surgery.

The incidence of alcoholic liver disease (ALD) has increased, causing it to become a primary indication for liver transplantation in the United States. We hypothesized an association between alcohol taxation and prevalence of ALD.

We conducted a retrospective study of united network for organ sharing (UNOS) waitlist additions for liver transplantation between January 2007 and December 2016. We also analyzed the average excise tax (2007-2016) for beer, wine, and spirits in listing states of liver transplant waitlist additions (LTWA).

There were 104 805 adult UNOS LTWA with assigned diagnoses, an annual increase from 22% to 28%. There were 24 316 LTWA with ALD diagnosis. The mean value for beer tax was significantly lower for ALD patients than for non-ALD patients across all age groups (

< .001). The analysis demonstrated significantly more ALD in waitlisted patients 35-54 years of age (30%), compared with 18-34 years (10%) and ≥55 years (20%),

< .001. The data confirmed significantly more ALD Medicaid patients in the 35-54 year age group (28%) compared with other age groups,

< .001.

Our research demonstrated an association between lower beer tax and higher ALD prevalence across all age groups. We found a larger percentage of middle-aged (35-54 years) Medicaid patients listed with ALD. These findings raise the need for further investigation of a potential public health concern for an association between ALD and beer tax, especially for middle-aged patients of lower socioeconomic status.

Our research demonstrated an association between lower beer tax and higher ALD prevalence across all age groups. We found a larger percentage of middle-aged (35-54 years) Medicaid patients listed with ALD. These findings raise the need for further investigation of a potential public health concern for an association between ALD and beer tax, especially for middle-aged patients of lower socioeconomic status.Diabetic gastroparesis (DG) is a clinical syndrome characterized by delayed gastric emptying (DGE). Loss of nuclear factor erythroid 2-related factor 2 (Nrf2) is associated with reduced neuronal nitric oxide synthase-α (nNOSα)-mediated gastric motility and DGE. Previous studies have shown that nuclear exclusion and inactivation of Nrf2 is partly regulated by glycogen synthase kinase 3β (GSK-3β). In the current study, the molecular signaling of GSK-3β-mediated Nrf2 activation and its mechanistic role on DG were investigated in high-fat diet (HFD)-induced obese/Type 2 diabetes (T2D) female mice. Adult female C57BL/6J mice were fed with HFD or normal diet (ND) with or without GSK-3β inhibitor (SB 216763, 10 mg/kg body wt ip) start from the 14th wk and continued feeding mice for an additional 3-wk time period. Our results show that treatment with GSK-3β inhibitor SB attenuated DGE in obese/T2D mice. Treatment with SB restored impaired gastric 1) Nrf2 and phase II antioxidant enzymes through PI3K/ERK/AKT-mediated xide synthase-α expression, dimerization and nitrergic relaxation. SB 216763 normalized both serum estrogen and nitrate levels in female obese/Type 2 diabetes mice. SB 216763 reduced downstream signaling of GSK-3β in enteric neuronal cells in vitro.Obesity and type 2 diabetes are frequently complicated by excess fat accumulation in the liver, which is known as nonalcoholic fatty liver disease (NAFLD). In this context, liver steatosis develops as a result of the deregulation of pathways controlling de novo lipogenesis and fat catabolism. Recent evidences suggest the clinical relevance of a reduction in the activity of lysosomal acid lipase (LAL), which is a key enzyme for intracellular fat disposal, in patients with NAFLD. In this review, we provided a comprehensive overview of the critical steps in hepatic fat metabolism and alterations in these pathways in NAFLD, with a special focus on lipophagy and LAL activity. During NAFLD, hepatic fat metabolism is impaired at several levels, which is significantly contributed to by impaired lipophagy, in which reduced LAL activity may play an important role. For further research and intervention in NAFLD, targeting LAL activity may provide interesting perspectives.Nonalcoholic fatty liver disease (NAFLD) is the most common cause of liver-related mortality. NAFLD is associated with obesity, hepatic fat accumulation, and insulin resistance, all of which contribute to its pathophysiology. Weight-loss is the main therapy for NAFLD, and metabolic surgery is the most effective treatment for morbid obesity and its metabolic comorbidities. Although has been reported that Roux-en-Y gastric bypass can reverse NAFLD, it is unclear whether such effects result from reduced weight, from a lower calorie-intake, or from the direct influence of surgery on mechanisms contributing to NAFLD. We aimed to investigate whether gastrointestinal (GI) bypass surgery could induce direct effects on hepatic fat accumulation and insulin resistance, independently of weight reduction. Twenty Wistar rats on a high-fat diet underwent duodenal-jejunal-bypass (DJB) or sham operation and were pair fed (PF) for 15 wk after surgery to obtain a matched weight. Outcome measures include ectopic fat deposition, hway, in which perilipin-2 seems to be the main player. Our study supports further investigation into the role of proximal small intestine exclusion in the pathophysiology of nonalcoholic fatty liver disease to uncover less invasive treatments that mimic the effects of metabolic surgery and aims to prevent and treat metabolic liver disease.1. Leukocyte immunoglobulin-like receptor A5 (LILRA5) is a key molecule that regulates the immune system. However, the LILRA5 gene has not been characterised in avian species, including chickens. The present study aimed to identify and functionally characterise LILRA5 identified from two genetically disparate chicken lines, viz., Marek's disease (MD)-resistant (R) line 6.3 and MD-susceptible (S) line 7.2. 2. Multiple sequence alignment and phylogenetic analyses confirmed that the identity and similarity homologies of amino acids of LILRA5 in chicken lines 6.3 and 7.2 ranged between 93% and 93.7%, whereas those between chicken and mammals ranged between 20.9% and 43.7% and 21.1% to 43.9%, respectively. The newly cloned LILRA5 from chicken lines 6.3 and 7.2 revealed high conservation and a close relationship with other known mammalian LILRA5 proteins. 3. The results indicated that LILRA5 from chicken lines 6.3 and 7.2 was associated with phosphorylation of Src kinases and protein tyrosine phosphatase non-receptor type 11 (SHP2), which play a regulatory role in immune functions. Moreover, the results demonstrated that LILRA5 in these lines was associated with the activation of major histocompatibility complex (MHC) class I and β2-microglobulin and induced the expression of the transporter associated with antigen processing. In addition, LILRA5 in both chicken lines activated and induced Janus kinase (JAK)-signal transducer and the activator of transcription (STAT), nuclear factor kappa B (NF-κB), phosphoinositide-3-kinase (PI3K)/protein kinase B (AKT) and the extracellular signal-regulated kinase (ERK)1/2 signalling pathways; toll-like receptors; and Th1-, Th2-, and Th17- cytokines. 4. The data suggested that LILRA5 has innate immune receptors essential for macrophage immune response and provide novel insights into the regulation of immunity and immunopathology.

Studies have shown significant improvement in hepatocellular carcinoma (HCC) recurrence rates after liver transplantation since the united network of organ sharing (UNOS) implementation of a 6-month wait period prior to accrued exception model for end-stage liver disease (MELD) points enacted on October 8, 2015. However, few have examined the impact on HCC dropout rates for patients awaiting liver transplant. Our objective is to evaluate the outcomes of HCC dropout rates before and after the mandatory 6-month wait policy enacted.

We conducted a retrospective cohort study on adult patients added to the liver transplant wait list between January 1, 2012, and March 8, 2019 (n = 767). Information was obtained through electronic medical records and organ procurement and transplant network (OPTN) publicly available national data reports.

In response to the 2015 UNOS-mandated 6-month wait time, dropout rates in the HCC patient population at our center increased from 12% pre-mandate to 20.8% post-mandate This increase was similarly reflected in the national dropout rate, which also increased from 26.3% pre-mandate to 29.0% post-mandate.

From these changes, it is evident that the UNOS mandate achieved its goal of increasing equity of liver organ allocation, but HCC patients are nonetheless dropping off of the wait list at an increased rate and are therefore disadvantaged.

From these changes, it is evident that the UNOS mandate achieved its goal of increasing equity of liver organ allocation, but HCC patients are nonetheless dropping off of the wait list at an increased rate and are therefore disadvantaged.

Pain control is an important aspect of rib fracture management. With a rise in multimodal care approaches, we hypothesized that transdermal lidocaine patches reduce opioid utilization in hospitalized patients with acute rib fractures not requiring continuous opioid infusion.

We performed a retrospective analysis of adult trauma patients with acute rib fractures admitted to the Trauma Service from January 2011 to October 2018. We compared patients who received transdermal lidocaine patches to those who did not and evaluated cumulative opioid consumption, expressed in morphine milligram equivalents (MMEs). Secondary outcomes included the rate of pulmonary complications and length of hospital stay.

Of the 21 190 trauma admissions, 3927 (18.5%) had rib fractures. Overall, 1555 patients who received continuous opioid infusion were excluded. Of the remaining 2372 patients, 725 (30.6%) patients received lidocaine patches. The mean total MME of patients who received lidocaine patches was 55.7 MME (30.7 MME on multivariate analysis) and was lower than that of patients who did not receive lidocaine patches (

≤ .01). There was no difference in hospital length of stay (no lidocaine patches vs received lidocaine patches 6.2 days vs 6.5 days,

= .34) or pulmonary complications (1.7% vs 2.8%,

= .08).

In admitted trauma patients with acute rib fractures not requiring continuous intravenous opiates, lidocaine patch use was associated with a significant decrease in opiate utilization during the patients' hospital course.

In admitted trauma patients with acute rib fractures not requiring continuous intravenous opiates, lidocaine patch use was associated with a significant decrease in opiate utilization during the patients' hospital course.The use of spin waves (SWs) as data carriers in spintronic and magnonic logic devices offers operation at low power consumption, free of Joule heating. Nevertheless, the controlled emission and propagation of SWs in magnetic materials remains a significant challenge. Here, we propose that skyrmion-antiskyrmion bilayers form topological charge dipoles and act as efficient sub-100 nm SW emitters when excited by in-plane ac magnetic fields. The propagating SWs have a preferred radiation direction, with clear dipole signatures in their radiation pattern, suggesting that the bilayer forms a SW antenna. Bilayers with the same topological charge radiate SWs with spiral and antispiral spatial profiles, enlarging the class of SW patterns. We demonstrate that the characteristics of the emitted SWs are linked to the topology of the source, allowing for full control of the SW features, including their amplitude, preferred direction of propagation, and wavelength.Excited-state electron transfer (ET) across molecules/transition metal dichalcogenide crystal (TMDC) interfaces is a critical process for the functioning of various organic/TMDC hybrid optoelectronic devices. Therefore, it is important to understand the fundamental factors that can facilitate or limit the ET rate. Here it is found that an undesirable combination of the interfacial band offset and the spatial dimensionality of the delocalized electron wave function can significantly slow down the ET process. Specifically, it is found that whereas the ET rate from TMDCs (MoS2 and WSe2) to fullerenes is relative insensitive to the band offset, the ET rate from TMDCs to perylene molecules can be reduced by an order of magnitude when the band offset is large. For the perylene crystal, the sensitivity of the ET rate on the band offset is explained by the 1D nature of the electronic wave function, which limits the availability of states with the appropriate energy to accept the electron.Advances in quantum information science (QIS) require the development of new molecular materials to serve as microwave addressable qubits that can be read out optically. Laser photoexcitation of organic π-conjugated molecules often results in spin-polarized phosphorescent triplet states that can be readily observed and manipulated using time-resolved electron paramagnetic resonance (EPR) techniques. Photoexcitation of N-mesityl-1,8-naphthalimide (M-NMI) and its phosphorus analogues, 2-mesitylbenzoisophosphinoline (M-BIPD) and 2-mesitylbenzoisophosphinoline oxide (M-BIPDO) results in ultrafast spin-orbit charge-transfer intersystem crossing to form the corresponding phosphorescent triplet states M- 3* NMI, M- 3* BIPD and M- 3* BIPDO. The ultrafast triplet formation dynamics, phosphorescence, and spin-polarized EPR spectra of these triplet states were examined. The most promising qubit candidate, M- 3* BIPD, was examined using pulse-EPR to measure its spin relaxation times, and pulse electron-nuclear double resonance spectroscopy to perform a two-qubit CNOT gate using the phosphorus nuclear spin.The Consortium for Top-Down Proteomics (www.topdownproteomics.org) launched the present study to assess the current state of top-down mass spectrometry (TD MS) and middle-down mass spectrometry (MD MS) for characterizing monoclonal antibody (mAb) primary structures, including their modifications. To meet the needs of the rapidly growing therapeutic antibody market, it is important to develop analytical strategies to characterize the heterogeneity of a therapeutic product's primary structure accurately and reproducibly. The major objective of the present study is to determine whether current TD/MD MS technologies and protocols can add value to the more commonly employed bottom-up (BU) approaches with regard to confirming protein integrity, sequencing variable domains, avoiding artifacts, and revealing modifications and their locations. We also aim to gather information on the common TD/MD MS methods and practices in the field. A panel of three mAbs was selected and centrally provided to 20 laboratories worldwide for the analysis Sigma mAb standard (SiLuLite), NIST mAb standard, and the therapeutic mAb Herceptin (trastuzumab). Various MS instrument platforms and ion dissociation techniques were employed. The present study confirms that TD/MD MS tools are available in laboratories worldwide and provide complementary information to the BU approach that can be crucial for comprehensive mAb characterization. The current limitations, as well as possible solutions to overcome them, are also outlined. A primary limitation revealed by the results of the present study is that the expert knowledge in both experiment and data analysis is indispensable to practice TD/MD MS.Solvent-free chemistry has been used to streamline synthesis, reduce waste, and access novel reactivity, but the physical nature of the reaction medium in the absence of solvent is often poorly understood. Here we reveal the phase behavior that enables the solvent-free carboxylation reaction in which carbonate, furan-2-carboxylate (furoate), and CO2 react to form furan-2,5-dicarboxylate (FDCA2-). This transformation has no solution-phase analogue and can be applied to convert lignocellulose into performance-advantaged plastics. Using operando powder X-ray diffraction and thermal analysis to elucidate the temperature- and conversion-dependent phase composition, we find that the reaction medium is a heterogeneous mixture of a ternary eutectic molten phase, solid Cs2CO3, and solid Cs2FDCA. During the reaction, the amounts of molten phase and solid Cs2CO3 diminish as solid Cs2FDCA accumulates. These insights are critical for increasing the scale of furoate carboxylation and provide a framework for guiding the development of other solvent-free transformations.Flavin-mediated electron transfer is an important pathway for Fe(III) reduction by dissimilatory iron-reducing bacteria. Although the mechanisms and kinetics of Fe(III) reduction by reduced flavins have been widely studied, the reaction between Fe(II) and oxidized flavins is rarely investigated. Results of this study show that under anoxic conditions, Fe(II) can be oxidized by the oxidized forms of riboflavin (RBF) and flavin mononucleotide (FMN) at pH 7-9. For instance, at pH 9, 73% of 17.8 μM Fe(II) was oxidized by 10 μM RBF within 20 min. Both the rate and extent of oxidation increased with increasing concentrations of oxidized flavins and increasing solution pH. Thermodynamic calculations and kinetic analyses implied that the oxidation of Fe(II) proceeded predominantly via the autodecomposition of Fe2+-RBF- and Fe2+-FMN- complexes, along with minor contributions from direct oxidation of Fe(II) by flavins and flavin radicals. Our findings suggest that the reoxidation of Fe(II) by oxidized flavins may be a rate-controlling factor in microbial Fe(III) reduction via flavin-mediated electron transfer.Low-dimensional nanostructures are expected to play an important role in spintronics. However, in low-dimensional systems, thermal fluctuations become more significant, which makes long-range magnetic ordering thermodynamically unfavorable. For example, as predicted by the Ising model, 1D magnetic order cannot survive, even at an arbitrary low finite temperature. In this study, utilizing a nanoproximity effect, we design a MoS2 nanoribbon material to stabilize 1D magnetic order without requiring the explicit application of an external magnetic field. The designed MoS2 nanoribbon has a new edge-reconstruction pattern, which is much more stable than previously reported structures. As a novel electronic property, one edge is nonmagnetic but conductive, and the opposite edge contains a magnetic moment in the predicted reconstruction pattern. Therefore, a bias voltage can drive a current along the former edge, which then generates a magnetic field at the opposite edge to stabilize the 1D magnetic order there. This result opens a new avenue to realize the integrated electrical control of magnetism.Isotopic partition-function ratios (IPFRs) computed for transition structures (TSs) of the methyl-transfer reaction catalyzed by catechol O-methyltransferase and modeled by hybrid QM/MM methods are analyzed. The ability of smaller Hessians to reproduce trends in α-3H3 and 14Cα IPFRs as obtained using the much larger subset QM/MM Hessians from which they are extracted is investigated critically. A 6-atom-extracted Hessian reproduces perfectly the α-T3 IPFR values from the full-subset Hessians of all the TSs but not the α-14CIPFRs. Average AM1/OPLS-AA harmonic frequencies and mean-square amplitudes are presented for the 12 normal modes of the α-CH3 moiety within the active site of several enzymic transition structures, together with QM/MM potential energy scans along each of these modes to assess the degree of anharmonicity. A novel investigation of ponderal effects upon IPFRs suggests that the value for α-14C tends toward a limiting minimum whereas that for α-T3 tends toward a limiting maximum as the mass of the rest of the system increases. The transition vector is dominated by motions of atoms within the donor and acceptor moieties and is very well described as a simple combination of Walden-inversion "umbrella" bending and asymmetric stretching of the SCα and CαO bonds. The contribution of atoms of the protein residues Met40, Tyr68, and Asp141 to the transition vector is extremely small. Average valence force constants for the COMT TS show significant differences from early BEBOVIB estimates which were used in support of the compression hypothesis for catalysis. There is no correlation between TS IPFRs and the nonbonded distances for close contacts between the S atom of SAM and Tyr68 or between any of the H atoms of the transferring methyl group and either Met40 or Asp141.When electrosprayed from typical native MS solution conditions, RNA hairpins and kissing complexes acquire charge states at which they get significantly more compact in the gas phase than their initial structure in solution. Here, we also show the limits of using force field molecular dynamics to interpret the structures of nucleic acid complexes in the gas phase, as the predicted CCS distributions do not fully match the experimental ones. We suggest that higher level calculation levels should be used in the future.Uniform field drift tube ion mobility-mass spectrometry (DTIM-MS) has emerged as a valuable tool for a range of analytical applications. In focus here are standardized collisional cross section values from DTIM-MS (DTCCS) as a candidate identification point for various analytical workflows. Of critical importance in establishing this parameter as a valid identification point is a rugged estimation of uncertainties according to the procedures used for their derivation. Relying on the assumption of the zero-field limit, the primary method of measurement for DTCCS values involves experimental determination of arrival times of an ion measured at several different field strengths transiting a drift tube filled with high purity drift gas, while a method using measurements of external calibrants at a single field strength is employed to allow for online measurements of transient signals (e.g., chromatographic peaks). Both approaches are here considered with respect to the uncertainty of input experimental variables (temperature, pressure, voltages, physical constants) and the steps of the calibration function employed. Estimations of uncertainty were performed according to EURACHEM with Monte Carlo simulations and reveal that existing consensus calibration standards from experimental stepped-field IM-MS determinations have estimated expanded uncertainties in the range of 2.7 to 4.6% (k = 2). Application of these standards for calibration considering these input uncertainties reveals uncertainty estimates of 4.7-9.1% (k = 2) for measured values using an established single-field calibration approach. Finally, directions for improving this situation via new experimental efforts toward standard reference and calibration materials are presented.The use of machine learning for multivariate spectroscopic data analysis in applications related to process monitoring has become very popular since non-linearities in the relationship between signal and predicted variables are commonly observed. In this regard, the use of artificial neural networks (ANN) to develop calibration models has demonstrated to be more appropriate and flexible than classical multivariate linear methods. The most frequently reported type of ANN is the so-called multilayer perceptron (MLP). Nevertheless, the latter models still lack a complete statistical characterization in terms of prediction uncertainty, which is an advantage of the parametric counterparts. In the field of analytical calibration, developments regarding the estimation of prediction errors would derive in the calculation of other analytical figures of merit (AFOMs), such as sensitivity, analytical sensitivity, and limits of detection and quantitation. In this work, equations to estimate the sensitivity in MLP-based calibrations were deduced and are here reported for the first time. The reliability of the derived sensitivity parameter was assessed through a set of simulated and experimental data. The results were also applied to a previously reported MLP fluorescence calibration methodology for the biopharmaceutical industry, yielding a value of sensitivity ca. 30 times larger than for the univariate reference method.As interests increase in oligonucleotide therapeutics, there has been a greater need for analytical techniques to properly analyze and quantitate these biomolecules. This article looks into some of the existing chromatographic approaches for oligonucleotide analysis, including anion exchange, hydrophilic interaction liquid chromatography, and ion pair chromatography. Some of the key advantages and challenges of these chromatographic techniques are discussed. Colloid formation in mobile phases of alkylamines and fluorinated alcohols, a recently discovered analytical challenge, is discussed. Mass spectrometry is the method of choice to directly obtain structural information about oligonucleotide therapeutics. Mass spectrometry sensitivity challenges are reviewed, including comparison to other oligonucleotide techniques, salt adduction, and the multiple charge state envelope. Ionization of oligonucleotides through the charge residue model, ion evaporation model, and chain ejection model are analyzed. Therapeutic oligonucleotides have to undergo approval from major regulatory agencies, and the impurities and degradation products must be well-characterized to be approved. Current accepted thresholds for oligonucleotide impurities are reported. Aspects of the impurities and degradation products from these types of molecules are discussed as well as optimal analytical strategies to determine oligonucleotide related substances. Finally, ideas are proposed on how the field of oligonucleotide therapeutics may improve to aid in future analysis.The increasing and simultaneous pollution of plastic debris and antibiotic resistance in aquatic environments makes plastisphere a great health concern. However, the development process of antibiotic resistome in the plastisphere is largely unknown, impeding risk assessment associated with plastics. Here, we profiled the temporal dynamics of antibiotic resistance genes (ARGs), mobile genetic elements (MGEs), and microbial composition in the plastisphere from initial microbial colonization to biofilm formation in urban water. A total of 82 ARGs, 12 MGEs, and 63 bacterial pathogens were detected in the plastisphere and categorized as the pioneering, intermediate, and persistent ones. The high number of five MGEs and six ARGs persistently detected in the whole microbial colonization process was regarded as a major concern because of their potential role in disseminating antibiotic resistance. In addition to genomic analysis, D2O-labeled single-cell Raman spectroscopy was employed to interrogate the ecophysiology of plastisphere in a culture-independent way and demonstrated that the plastisphere was inherently more tolerant to antibiotics than bacterioplankton. Finally, by combining persistent MGEs, intensified colonization of pathogenic bacteria, increased tolerance to antibiotic, and potential trophic transfer into a holistic risk analysis, the plastisphere was indicated to constitute a hot spot to acquire and spread antibiotic resistance and impose a long-term risk to ecosystems and human health. These findings provide important insights into the antibiotic resistome and ecological risk of the plastisphere and highlight the necessity for comprehensive surveillance of plastisphere.Enzymatic reactions and noncovalent (i.e., supramolecular) interactions are two fundamental nongenetic attributes of life. Enzymatic noncovalent synthesis (ENS) refers to a process where enzymatic reactions control intermolecular noncovalent interactions for spatial organization of higher-order molecular assemblies that exhibit emergent properties and functions. Like enzymatic covalent synthesis (ECS), in which an enzyme catalyzes the formation of covalent bonds to generate individual molecules, ENS is a unifying theme for understanding the functions, morphologies, and locations of molecular ensembles in cellular environments. This review intends to provide a summary of the works of ENS within the past decade and emphasize ENS for functions. After comparing ECS and ENS, we describe a few representative examples where nature uses ENS, as a rule of life, to create the ensembles of biomacromolecules for emergent properties/functions in a myriad of cellular processes. Then, we focus on ENS of man-made (synthetic) molecules in cell-free conditions, classified by the types of enzymes. After that, we introduce the exploration of ENS of man-made molecules in the context of cells by discussing intercellular, peri/intracellular, and subcellular ENS for cell morphogenesis, molecular imaging, cancer therapy, and other applications. Finally, we provide a perspective on the promises of ENS for developing molecular assemblies/processes for functions. This review aims to be an updated introduction for researchers who are interested in exploring noncovalent synthesis for developing molecular science and technologies to address societal needs.The use of liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) has steadily increased in many application fields ranging from metabolomics to environmental science. HRMS data are frequently used for nontarget screening (NTS), i.e., the search for compounds that are not previously known and where no reference substances are available. However, the large quantity of data produced by NTS analytical workflows makes data interpretation and time-dependent monitoring of samples very sophisticated and necessitates exploiting chemometric data processing techniques. Consequently, in this study, a prioritization method to handle time series in nontarget data was established. As proof of concept, industrial wastewater was investigated. As routine industrial wastewater analyses monitor the occurrence of a limited number of targeted water contaminants, NTS provides the opportunity to detect also unknown trace organic compounds (TrOCs) that are not in the focus of routine target analysis. The deveed over time to reveal hidden factors accounting for the structure of the data. The detected features were reduced to 130 relevant time trends related to TrOCs for identification. Exemplarily, as proof of concept, one nontarget pollutant was identified as N-methylpyrrolidone. The developed chemometric strategies of this study are not only suitable for industrial wastewater but also could be efficiently employed for time trend exploration in other scientific fields.The reductive amination, the reaction of an aldehyde or a ketone with ammonia or an amine in the presence of a reducing agent and often a catalyst, is an important amine synthesis and has been intensively investigated in academia and industry for a century. Besides aldehydes, ketones, or amines, starting materials have been used that can be converted into an aldehyde or ketone (for instance, carboxylic acids or organic carbonate or nitriles) or into an amine (for instance, a nitro compound) in the presence of the same reducing agent and catalyst. Mechanistically, the reaction starts with a condensation step during which the carbonyl compound reacts with ammonia or an amine, forming the corresponding imine followed by the reduction of the imine to the alkyl amine product. Many of these reduction steps require the presence of a catalyst to activate the reducing agent. The reductive amination is impressive with regard to the product scope since primary, secondary, and tertiary alkyl amines are accessible and hydrogen is the most attractive reducing agent, especially if large-scale product formation is an issue, since hydrogen is inexpensive and abundantly available. Alkyl amines are intensively produced and use fine and bulk chemicals. They are key functional groups in many pharmaceuticals, agro chemicals, or materials. In this review, we summarize the work published on reductive amination employing hydrogen as the reducing agent. No comprehensive review focusing on this subject has been published since 1948, albeit many interesting summaries dealing with one or the other aspect of reductive amination have appeared. Impressive progress in using catalysts based on earth-abundant metals, especially nanostructured heterogeneous catalysts, has been made during the early development of the field and in recent years.We investigated the influence of various factors (including solvent mixtures) on chiral recognition of chiral carboxylates, using the titration method under 1H NMR control. We found that strong binding carboxylates (geometrical matching) is not enough for the satisfactory differentiation of enantiomers. Moreover, solvent mixture studies indicate a significant influence of environment on the formation of diastereomeric complexes and variations among them. Our findings offer insights into the complementarity of chiral recognition processes.Classical hydroformylation catalysts use mononuclear rhodium(I) complexes as precursors; however, very few examples of bimetallic systems have been reported. Herein, we report fully substituted dirhodium(II,II) complexes (C1-C6) containing acetate and diphenylformamidinate bridging ligands (L1-L4). The structure and geometry around these paddlewheel-type, bimetallic cores were confirmed by single-crystal X-ray diffraction. The complexes C3-C6 show electrochemical redox reactions, with the expected reduction (Rh24+/3+) and two oxidation (Rh24+/5+ and Rh25+/6+) electron transfer processes. Furthermore, the bimetallic complexes were evaluated as catalyst precursors for the hydroformylation of 1-octene, with the acetate-containing complexes (C1 and C2) showing near quantitative conversion (>99%) of 1-octene, excellent activity and chemoselectivity toward aldehydes (>98%), with moderate regioselectivity toward linear products. Replacement of the acetate with diphenylformamidinate ligands (complexes C3-C6) yielded moderate-to-good chemoselectivity and regioselectivity, favoring linear aldehydes.As one of the most effective surface-enhanced infrared absorption (SEIRA) techniques, metal-insulator-metal structured metamaterial perfect absorbers possess an ultrahigh sensitivity and selectivity in molecular infrared fingerprint detection. However, most of the localized electromagnetic fields (i.e., hotspots) are confined in the dielectric layer, hindering the interaction between analytes and hotspots. By replacing the dielectric layer with the nanofluidic channel, we develop a sapphire (Al2O3)-based mid-infrared (MIR) hybrid nanofluidic-SEIRA (HN-SEIRA) platform for liquid sensors with the aid of a low-temperature interfacial heterogeneous sapphire wafer direct bonding technique. The robust atomic bonding interface is confirmed by transmission electron microscope observation. We also establish a design methodology for the HN-SEIRA sensor using coupled-mode theory to carry out the loss engineering and experimentally validate its feasibility through the accurate nanogap control. Thanks to the capillary for, demonstrating a way toward quantitative molecule identification and dynamic analysis for the chemical and biological reaction processes.The heterobimetallic metallacrown (MC), (TMA)2Mn(OAc)2[12-MCMn(III)Cu(II)N(shi)-4](CH3OH)·2.90CH3OH, 1, where TMA+ is tetramethylammonium, -OAc is acetate, and shi3- is salicylhydroximate, consists of a MnII ion captured in the central cavity and alternating unambiguous and ordered manganese(III) and copper(II) sites about the MC ring, a first for the archetypal MC structure design. DC-magnetometry characterization and subsequent simulation with the Spin Hamiltonian H = -J1( s 1 + s 3)· s 5 - J2( s 2 + s 4)· s 5 - J3Σi=14 s i · s i+1 + d( s z,12 + s z,32) + μBΣj=15g j s j · B indicates an S = 5/2 ground state and a sizable axial zero-field splitting on MnIII. AC-susceptibility measurements reveal that 1 displays slow magnetization relaxation akin to single-molecule magnet (SMM) behavior.Although sodium vanadium fluorophosphate, Na3(VO1-xPO4)2F1+2x (0 ≤ x ≤ 1), is a highly promising cathode candidate for sodium-ion batteries because of its stable structure and high working voltage, the low charge diffusion dynamics and the inactive materials used in traditional coating electrodes reduce the energy density of a sodium-ion full battery. Hence, Na3V2O2(PO4)2F/graphene aerogels (NVPF/GAs) with a three-dimensional continuous porous network are first prepared by coassembly and freeze-drying. The three-dimensional porous network helps to obtain a high NVPF content of 81 wt %, relieve the volume change for improving the cyclability, and enhance the wettability of the electrode with the electrolyte for accelerating the diffusion dynamics of sodium ions and electrons. As a directly used freestanding cathode without the use of any binder/collector, an optimized freestanding NVPF/GA electrode exhibits excellent cycling and rate performances compared to traditional coating electrodes. The average capacities at current densities of 0.2, 0.5, 1.0, 2.0, and 5.0 C are 135.4, 128.0, 125.1, 121.9, and 115.1 mA h g-1, respectively. Especially, it maintains a capacity retention of 100% after 1000 cycles at an ultrahigh current of 40 C. A sodium-ion full battery with the NVPF/GA cathode and the Sb/graphene/carbon anode attains a of 82.1 mA h g-1 without an obvious decline after 100 cycles.The safety issue caused by thermal runaway poses a huge threat toward the lifespan and application of high-density electrochemical energy storage devices, especially in the field of micro-energy, such as microsupercapacitors (MSCs). The heat accumulation is difficult to be eliminated, considering the narrow space inside integrated electronic devices attached to the MSC group. Active thermal management is of paramount importance to ensure the normal operation of electronic devices. However, existing one-time thermal protection strategies cannot fully meet current requirements. Herein, we report a promising thermoreversible temperature-responsive electrolyte system, which can shut down the current flow before thermal runaway occurs, thanks to the sol-gel transition of Pluronic [poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide)]-based graft copolymer solution. As the temperature rises to 80 °C, the self-protective electrolyte will change from the sol state to gel state. Meanwhile, the ilosed herein is expected to provide new insights into the new-generation smart MSCs for their wide applications in diverse fields such as microelectronics and wearable devices.Fourier transform mass spectrometers routinely provide high mass resolution, mass measurement accuracy, and mass spectral dynamic range. In this work, we utilize 21 T Fourier transform ion cyclotron resonance (FT-ICR) to analyze product ions derived from the application of multiple dissociation techniques and/or multiple precursor ions within a single transient acquisition. This ion loading technique, which we call, "chimeric ion loading", saves valuable acquisition time, decreases sample consumption, and improves top-down protein sequence coverage. In the analysis of MCF7 cell lysate, we show collision-induced dissociation (CID) and electron-transfer dissociation (ETD) on each precursor on a liquid chromatography-mass spectrometry (LC-MS) timescale and improve mean sequence coverage dramatically (CID-only 15% vs chimeric 33%), even during discovery-based acquisition. This approach can also be utilized to multiplex the acquisition of product ion spectra of multiple charge states from a single protein precursor or multiple ETD/proton-transfer reactions (PTR) reaction periods. The analytical utility of chimeric ion loading is demonstrated for top-down proteomics, but it is also likely to be impactful for tandem mass spectrometry applications in other areas.Pursuing high-performance cathode materials for sodium-ion batteries (SIBs) has great significance in the modern green energy world. The P2-type sodium-based layered oxide Na0.67[Mn0.67Ni0.33]O2 with high operating potential upon 4.3 V and high theoretical capacity has emerged as the most promising cathode. However, the material suffers from severe capacity decay during the electrochemical reaction process. Herein, the P2-Na0.67[Mn0.67Ni0.21Li0.06Zn0.06]O2 cathode is gained by moderately substituting lithium/zinc for the nickel sites. The inactive Li/Zn co-substitution is endowed with the ability to stabilize the crystal structure, resulting in enhanced electrochemical kinetics and remarkable long cyclic performance in liquid- and solid-state electrolytes. Thus, the Li/Zn co-substituted cathode presents a specific capacity of 154 mAh g-1 at the first discharge process, excellent rate capability with 77 mAh g-1 at a high current density of 5 C, and long cyclic stability in liquid-state batteries. Excitingly, it is also endowed with a high capacity retention of 85% after 500 cycles in solid-state batteries. Furthermore, ex situ XRD, TEM, and ex situ XPS are applied to reveal the structural evolution and charge compensation mechanism of P2-Na0.67[Mn0.67Ni0.21Li0.06Zn0.06]O2, allowing a deep insight into the great significance of structural stability.In the current information age, the realization of memory devices with energy efficient design, high storage density, nonvolatility, fast access, and low cost is still a great challenge. As a promising technology to meet these stringent requirements, nonvolatile multistates memory (NMSM) has attracted lots of attention over the past years. Owing to the capability to store data in more than a single bit (0 or 1), the storage density is dramatically enhanced without scaling down the memory cell, making memory devices more efficient and less expensive. Multistates in a single cell also provide an unconventional in-memory computing platform beyond the Von Neumann architecture and enable neuromorphic computing with low power consumption. In this review, an in-depth perspective is presented on the recent progress and challenges on the device architectures, material innovation, working mechanisms of various types of NMSMs, including flash, magnetic random-access memory (MRAM), resistive random-access memory (RRAM), ferroelectric random-access memory (FeRAM), and phase-change memory (PCM). The intriguing properties and performance of these NMSMs, which are the key to realizing highly integrated memory hierarchy, are discussed and compared.Multicore iron oxide nanoparticles, also known as colloidal nanocrystal clusters, are magnetic materials with diverse applications in biomedicine and photonics. Here, we examine how both of their characteristic dimensional features, the primary particle and sub-micron colloid diameters, influence their magnetic properties and performance in two different applications. The characterization of these basic size-dependent properties is enabled by a synthetic strategy that provides independent control over both the primary nanocrystal and cluster dimensions. Over a wide range of conditions, electron microscopy and X-ray diffraction reveal that the oriented attachment of smaller nanocrystals results in their crystallographic alignment throughout the entire superstructure. We apply a sulfonated polymer with high charge density to prevent cluster aggregation and conjugate molecular dyes to particle surfaces so as to visualize their collection using handheld magnets. These libraries of colloidal clusters, indexed both by primary nanocrystal dimension (dp) and overall cluster diameter (Dc), form magnetic photonic crystals with relatively weak size-dependent properties. In contrast, their performance as MRI T2 contrast agents is highly sensitive to cluster diameter, not primary particle size, and is optimized for materials of 50 nm diameter (r2 = 364 mM-1 s-1). These results exemplify the relevance of dimensional control in developing applications for these versatile materials.Graphitic carbon nitride (CN) suffers from rapid recombination of photoexcited charges due to the existing highly symmetrical tri-s-triazine ring and long charge diffusion path, resulting in moderate photocatalytic activity. The bridged phenyl embedded in the CN structure was used to reduce the symmetry of the tri-s-triazine ring. In addition, the CN material was constructed with a porous and hollow sphere structure to shorten the diffusion path of charge carriers. Herein, simple thermal polymerization of a trimesic acid-doped melamine-cyanuric acid (MCA) supramolecular was employed to construct phenyl-bridged graphitic carbon nitride (Ph-CN-MCA) with a hollow sphere structure composed of porous nanosheets for visible-light catalytic H2 evolution. The porous and hollow sphere-structured Ph-CN-MCA possessed increased degree of polymerization, more negative conduction band potential, enlarged Brunauer-Emmett-Teller (BET) surface area, and shortened charge diffusion path. In addition, bridged phenyl embedded in the Ph-CN-MCA structure not only accelerated the dissociation of photogenerated carriers but also narrowed the band gap and extended the visible-light absorption. Further, the separated highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of Ph-CN-MCA facilitated the spatial dissociation of photogenerated charges, which was also confirmed by theoretical calculations. As a consequence, compared with the reference CN-MA catalyst prepared from melamine, Ph-CN-MCA showed approximately 48.42 times the photocatalytic H2 evolution under visible-light irradiation. The developed synthetic method herein highlights that phenyl-bridged graphitic carbon nitride with a porous and hollow sphere structure could provide an efficient platform to boost the dissociation of photoexcited charge carriers and photocatalytic H2 evolution.