Highly active and regioselective hydroaminomethylation of olefins catalyzed by Rh/sulfoxantphos with ZSM-5.

Rh-catalyzed hydroaminomethylation has been developed with acid sulfoxantphos and ZSM-5. Linear amines were obtained in good yields (71-95%) with high l/b ratios (up to 132.4) and excellent TON values (up to 23 760). The ZSM-5 and SO3H group of ligands improved the performances of hydroformylation and reductive amination.

Enhanced identification and localization of metabolites in Scutellariae Radix using ion mobility enabled MALDI-Q-TOF/MS imaging.

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Fluorescent Noncovalent Organic Framework for Supporting Gold Nanoparticles as Heterogeneous Catalyst with Merits of Easy Detection and Recycle.

A porous noncovalent organic framework with AIE effect is designed and synthesized as the support for gold nanoparticles (AuNPs). The framework is fabricated through the electrostatic complexation between carboxymethyl cellulose and tetraphenylethene-containing ammonium surfactant, which can complex AuNPs via the noncovalent interactions to offer a heterogeneous catalyst. Compared to the covalent modification on cellulose, this noncovalent framework gains superiorities in the catalyst synthesis and the size control of AuNPs. The AIE property and water-insolubility allow such heterogeneous catalysts to be easily detected, separated, and recycled, opening a new pathway for the reduction of nitrobenzene compounds and some dye compounds in aqueous conditions, which present the features of green chemistry. The use of cellulose for developing new heterogeneous metal catalysts, especially in a noncovalent way, would promote the value-added utilization of cellulose. This work provides a design strategy for gaining heterogeneous metal catalysts by taking advantage of natural bioresources.

Semantic Relation Priming Is Not Constituent-Specific-Evidence from Electrophysiology.

Compound words in psycholinguistics pose a significant challenge for researchers as their meaning involves more than the sum of their parts. The role of semantic relations in this process is crucial, and studies have reported a phenomenon known as relation priming. It suggests that previously encountered relations enhance the processing of subsequent words with the same relation. Notably, this priming effect is limited to cases where there is morpheme repetition between the priming and target words. In the present study, 33 samples from the target group were selected, and the within-subject design of 3 morphemes (modifier-shared, head-shared, non-repeated) × 2 relations (relation-same, relation-different) was adopted to explore whether the relation priming effect would occur without morpheme repetition and its time course. Significant relation priming effects were found in both behavioral and electrophysiological experimental results. These findings indicating relation priming can occur independently of morpheme repetition, and it has been activated at a very early stage (about 200 ms). As the word processing progresses, this activation gradually strengthens, indicating that the relation role is slowly increasing in the process of compound word recognition. It may first be used as context information to help determine the constituent morphemes' meaning. After the meaning access of the constituent morphemes, they begin to play a role in the semantic composition process. This study uses electrophysiological technology to precisely describe the representation of relation and its time course for the first time, which gives us a deeper understanding of the relation priming process, and at the same time, sheds light on the meaning construction process of compounds.

Preparation of bifunctional monomer molecularly imprinted polymer filled solid-phase extraction for sensitivity improvement of quantitative analysis of sulfonamide in milk.

To solve the problems of unstable adsorption performance and high organic solvent consumption of traditional molecular imprinting materials, we developed a water-resistant and highly adsorptive molecularly imprinted sulfamethazine polymer (MIP) through a novel synthetic strategy consisting of the application of mixed functional monomers combined with hydrophobic crosslinkers. The results showed that the imprinting factor of the prepared MIP was increased from 0.93 to 4.38, and that the relative selection coefficient k' was 5.59. With the application of the material to be developed as a solid-phase extraction (SPE) filler for sulfonamides (SAs) in milk combined with UPLC-MS/MS, the validated method showed a sensitive quantification limit (0.89 µg/kg), a steady recovery (95.55%-97.97%) and an excellent precision (0.08%-2.92% RSD). Moreover, after 5 times usage, the recovery rate of MIP-SPE was still above 90%. Therefore, the prepared materials showed high performance of molecular adsorption and were water-resistant, which was also considered an excellent filler of SPE for SAs extraction in food or other fields.

Co-catalysis of rhodium/phosphoramidite catalyst and ZSM-35(10) for the tandem hydroformylation-acetalization of olefins.

The Rh/BINAPa and ZSM-35(10) co-catalyzed tandem hydroformylation-acetalization of olefins has been developed. A series of olefins with various alcohols performed well in the process, affording the corresponding acetals with high regioselectivities (l/b ≥ 30.5) and excellent catalytic activities (TON of the Rh catalyst up to 4.3 × 104). Control experiments and DFT calculations indicated that the Rh/L11-catalyzed hydroformylation occurred in the solvent outside the molecular sieve, while the acetalization of intermediate aldehydes with alcohols takes place mainly in the interior of the molecular sieve.

Influencing factors of employee brand equity from the perspective of FinTech.

Recent years have seen a heated discussion on what influences employees' recognition of enterprise brand equity among the psychological community. Some empirical evidence suggests that the brand equity of consumers and brand equity of sales are two categories that should be studied. However, more recent discussions have focused more on the former. In contrast, this study discusses the factors influencing brand equity based on the employee level. Moreover, this paper examines whether FinTech can help companies get out of financing difficulties and thus improve employees' brand equity recognition. This research illustrates how FinTech has become an essential driver of brand equity value. Based on micro panel data on enterprises from 2011 to 2019, we analyze the transmission mechanism between the two factors and the mediating role of financing constraints. FinTech's development promotes employees' recognition of corporate brand equity, and financing constraints are an essential transmission path between the two factors. Furthermore, the impact of financing constraints on employee brand equity identity is characterized by cross-regional economic heterogeneity. In contrast, the development of FinTech characterizes the cross-enterprise heterogeneity in employees' recognition of brand equity value. Altogether, this study demonstrates the promising application of FinTech in influencing the mechanisms of employee brand equity.

Case report: Combined therapy of bilateral subthalamic nucleus deep brain stimulation and spinal cord stimulation significantly improves motor function in a patient with multiple system atrophy with predominant parkinsonism.

Multiple system atrophy with predominant parkinsonism (MSA-P) is a highly incapacitating disease with a short life expectancy and symptomatic therapy is still limited. In this report, we presented the case of a 65-year-old woman with a 3-year history of severe rigidity, bradykinesia, and gait dysfunction alongside severe freezing of gait diagnosed with MSA-P. She underwent combined therapy of bilateral subthalamic nucleus deep brain stimulation (DBS) and low-thoracic spinal cord stimulation (SCS). The double-blind evaluation of the Movement Disorder Society Sponsored Revision of the Unified Parkinson's Disease Rating Scale part III and 7-m Timed Up and Go at follow-ups showed her cardinal parkinsonian symptoms benefit significantly from DBS stimulation, while the improvement of SCS was mainly embodied in lower-limb symptoms. The combined stimulation achieved a better improvement of motor function than either DBS or SCS stimulation alone. Most notably, the improvement of lower-limb symptoms was significantly enhanced by the combined stimulation.

Cathode enabled high faradaic efficiency: reduction of imines to amines with H2O as a H-source.

Benefiting from a high overpotential of the competitive hydrogen evolution reaction with a carbon paper cathode, the desired electrochemical reduction of imines was achieved with high faradaic efficiency by using H2O as a H-source. With this sustainable atom-economic strategy, a series of potentially versatile amines were obtained in medium-to-high yields (49-86%).

Desorption Electrospray Ionization Mass Spectrometry Imaging Illustrates the Quality Characters of Isatidis Radix.

For a long history, herbal medicines have made significant contributions to human health all around the world. However, the exploration of an effective approach to illustrate their inner quality remains a challenge. So, it is imperative to develop new methods and technologies to characterize and identify quality markers of herbal medicines. Taking Isatidis Radix, the dried root of Isatis indigotica as an example, desorption electrospray ionization (DESI), in combination with quadrupole-time-of-flight mass spectrometry (Q-TOF/MS), was applied in this work for the first time to reveal the comprehensive spatial distribution of metabolites and, further, to illustrate quality characters of this herbal medicine. After simple pretreatment, 102 metabolites including alkaloids, sulfur-containing compounds, phenylpropanoids, nucleosides, amino acids, organic acids, flavonoids, phenols, terpenes, saccharides, peptides, and sphingolipids were characterized, some of which were successfully localized and visualized in the transverse section of the root. Based on the ion images, samples with different quality characters were distinguished unambiguously by the pattern recognition method of orthogonal partial least squares discrimination analysis (OPLS-DA). Simultaneously, 11 major influencing components exerting higher ion intensities in superior samples were identified as the potential quality markers of Isatidis Radix. Desorption electrospray ionization (DESI) mass spectrometry imaging (MSI), together with chemometric analysis could not only improve the understanding of the plant biology of herbal medicines but also be beneficial in the identification of quality markers, so as to carry out better quality control of herbal medicines.

In Situ Alkyl Radical Recycling-Driven Decoupled Electrophotochemical Deamination.

Molecular electrophotocatalysis has emerged as a powerful strategy for the development of sustainable synthetic protocols. With the proof-of-concept, we exploited a versatile electrophotocatalytic deaminative alkylation approach. Mechanistic investigation indicated that in situ recycling of the alkyl radicals was the key point. Notably, ligand modification and late-stage functionalization of pharmaceuticals were also established, highlighting its feasibility in practical utilization.

The application of mass spectrometry imaging in traditional Chinese medicine: a review.

Mass spectrometry imaging is a frontier technique which connects classical mass spectrometry with ion imaging. Various types of chemicals could be visualized in their native tissues using mass spectrometry imaging. Up to now, the most commonly applied mass spectrometry imaging techniques are matrix assisted laser desorption ionization mass spectrometry imaging, desorption electrospray ionization mass spectrometry imaging and secondary ion mass spectrometry imaging. This review gives an introduction to the principles, development and applications of commonly applied mass spectrometry imaging techniques, and then illustrates the application of mass spectrometry imaging in the investigation of traditional Chinese medicine. Recently, mass spectrometry imaging has been adopted to explore the spatial distribution of endogenous metabolites in traditional Chinese medicine. Data collected from mass spectrometry imaging can be further utilized to search for marker components of traditional Chinese medicine, discover new compounds from traditional herbs, and differentiate between medicinal plants that are similar in botanical features. Moreover, mass spectrometry imaging also plays a role in revealing the pharmacological and toxicological mechanisms of traditional Chinese medicine.

Highly sensitive detection of three protein toxins via SERS-lateral flow immunoassay based on SiO2@Au nanoparticles.

We developed surface-enhanced Raman scattering-lateral flow immunoassay (SERS-LFIA) biosensor strips based on SiO2@Au nanoparticles (NPs) for the specific and highly sensitive detection of ricin, staphylococcal enterotoxin B (SEB), and botulinum neurotoxin type A (BoNT/A). SiO2@Au NPs were used to prepare SERS tags with useful properties, such as light weight, uniform particle size, good dispersion, and high SERS performance. The detection limit of the SERS-LFIA strips developed herein for ricin, SEB, and BoNT/A was 0.1, 0.05, and 0.1 ng/mL. Their sensitivity was 100-fold higher than that of colloidal gold-LFIA strips, and the same batch of strips had good repeatability. Moreover, the test was completed within 15 min, indicating that the strips are suitable for the rapid and on-site detection of the said toxins. The SERS-LFIA strips based on SiO2@Au NPs developed herein for the detection of toxins are important to the prevention of bioterrorism attacks.

Distribution visualization of the chlorinated disinfection byproduct of diazepam in zebrafish with desorption electrospray ionization mass spectrometry imaging.

Diazepam (DZP) was routinely prescribed to a large population troubled with anxiety disorders. However, due to the overuse and misuse, DZP and its chlorination disinfection byproduct 2-methylamino-5-chlorobenzophenone (MACB) caused environmental pollution and can be detected ubiquitously in drinking water in Beijing, China. However, little information is known about the metabolic dynamics of MACB. Here, we established desorption electrospray ionization mass spectrometry (DESI-MS) imaging method to visually and quantitatively assess the distribution and metabolism of MACB in zebrafish. The results showed that MACB specifically accumulated in spinal cord particularly in female zebrafish. Meanwhile, the accumulation of MACB could pass through the blood-brain barrier (BBB) and induced microglial phagocytosis of neurons. Therefore, the intervention strategies should be explored to restrict the release of such substances, eliminating the potential risks for both human beings and the eco-environment.

A Systematic Review and Meta-analysis on the Effectiveness of Transcranial Direct Current Stimulation on Swallowing Function of Poststroke Patients.

OBJECTIVE: The purpose of this study was to investigate the therapeutic effects of transcranial direct current stimulation on swallowing function in poststroke patients. DESIGN: We searched for potentially eligible randomized controlled trials from electronic databases, including the PubMed, Embase, Web of Science, Cochrane Library, China National Knowledge Infrastructure, Wanfang, and Chinese Science and Technology Periodical (VIP) databases, from their inception to January 15, 2021. All statistical analyses were performed using RevMan 5.4, and the standardized mean difference with 95% confidence intervals was estimated for the swallowing function outcomes and to understand the mean effect size. RESULTS: Ten studies involving 343 participants were included in this meta-analysis. The overall analyses demonstrated a significant effect size for swallowing function. Subgroup analyses suggested that both acute and chronic stroke patients showed significant effects on swallowing function after transcranial direct current stimulation. Furthermore, compared with sham stimulation, transcranial direct current stimulation anodal to the affected, unaffected, and bilateral hemispheres can produce a significant effect size for swallowing function in stroke patients. CONCLUSIONS: This meta-analysis showed that transcranial direct current stimulation is likely to be effective for the recovery of dysphagia in poststroke patients, in the acute or chronic phase, and that the effect of anodal transcranial direct current stimulation to unaffected hemispheres is larger.

Prevention and Treatment of Hardware-Related Infections in Deep Brain Stimulation Surgeries: A Retrospective and Historical Controlled Study.

BACKGROUND: Hardware-related infection in deep brain stimulation (DBS) is one of the most commonly reported complications frequently resulting in the removal of implantable pulse generator (IPG). OBJECTIVE: The aim of this study was to establish a useful strategy to better prevent and treat those infections and to improve the preservation rates of IPG. METHODS: We conducted a retrospective and historical controlled study of all adult patients (≥18 years old) who had undergone initial DBS implantation at a single center. All participants were enrolled in the control group (between June 2005 and June 2014) or intervention group (between July 2014 and May 2019) based on their surgery dates. We used the intraoperative irrigation with hydrogen dioxide solution in the intervention group. Based on the dates of diagnosis, patients with hardware-related infection after DBS were enrolled in group A (between June 2005 and June 2014) or group B (between July 2014 and May 2019). IPG-sparing algorithm (Isa) was applied for group B. The early-onset IPG infections of the control and intervention groups were evaluated. The IPG preservation rates in both groups A and B were statistically analyzed. RESULTS: Six cases of early IPG infection and subsequent IPG removal occurred in the control group, while none occurred after intraoperative usage of the hydrogen dioxide in the intervention group. IPG preservation rate of infected cases in group B was significantly higher than that in group A (70% vs.16%, p = 0.004). CONCLUSION: The combined application of hydrogen dioxide solution and Isa seems to be an effective strategy to prevent IPG infection.

Automatic and sensitive detection of West Nile virus non-structural protein 1 with a portable SERS-LFIA detector.

A portable surface-enhanced Raman scattering (SERS)-lateral flow immunoassay (LFIA) detector has been developed for the automatic and highly sensitive detection of West Nile virus (WNV) non-structural protein 1 (NS1) and actual WNV samples. Au@Ag nanoparticles (Au@Ag NPs) labeled with double-layer Raman molecules were used as SERS tags to prepare WNV-specific SERS-LFIA strips. On this platform, the WNV-specific antigen NS1 protein was quantitatively and sensitively detected. The detection limit for the WNV NS1 protein was 0.1 ng/mL, which was 100-fold more sensitive than visual signals. The detection limit for inactivated WNV virions was 0.2 × 102 copies/µL. The sensitivity of the SERS-LFIA detector was comparable to that of the fluorescence quantitative reverse transcription-polymerase chain reaction assay. The prepared SERS-LFIA strips exhibited high sensitivity and good specificity for WNV. Thus, the strips developed herein have clinical application value. Moreover, the portable SERS-LFIA detector enabled automatic and rapid detection of the SERS-LFIA strips. The platform established herein is expected to make a substantial contribution to the diagnosis and control of outbreaks of emerging infectious diseases, including WNV.

Nigral Iron Deposition Is Associated With Levodopa-Induced Dyskinesia in Parkinson's Disease.

OBJECTIVE: To investigate iron deposition in the substantia nigra (SN) of Parkinson's disease (PD) patients associated with levodopa-induced dyskinesia (LID). METHODS: Seventeen PD patients with LID, 17 PD patients without LID, and 16 healthy controls were recruited for this study. The mean QSM values of the whole, left, and right SN were compared among the three groups. A multivariate logistic regression model was constructed to determine the factors associated with increased risk of LID. The receiver operating characteristic curve of the QSM value of SN in discriminating PD with and without LID was evaluated. RESULTS: The mean QSM values of the whole and right SN in the PD with LID were higher than those in the PD without LID (∗ P = 0.03, ∗ P = 0.03). Multivariate logistic regression analysis revealed that the QSM value of whole, left, or right SN was a predictor of the development of LID (∗ P = 0.03, ∗ P = 0.04, and ∗ P = 0.04). The predictive accuracy of LID in adding the QSM value of the whole, left, and right SN to LID-related clinical risk factors was 70.6, 64.7, and 67.6%, respectively. The QSM cutoff values between PD with and without LID of the whole, left, and right SN were 148.3, 165.4, and 152.7 ppb, respectively. CONCLUSION: This study provides the evidence of higher iron deposition in the SN of PD patients with LID than those without LID, suggesting that the QSM value of the SN may be a potential early diagnostic neuroimaging biomarker for LID.

Evaluation of the Direct Effect of Bilateral Deep Brain Stimulation of the Subthalamic Nucleus on Levodopa-Induced On-Dyskinesia in Parkinson's Disease.

Objective: This study aimed to evaluate the direct anti-dyskinesia effect of deep brain stimulation (DBS) of subthalamic nucleus (STN) on levodopa-induced on-dyskinesia in Parkinson's disease (PD) patients during the early period after surgery without reducing the levodopa dosage. Methods: We retrospectively reviewed PD patients who underwent STN-DBS from January 2017 to October 2019 and enrolled patients with levodopa-induced on-dyskinesia before surgery and without a history of thalamotomy or pallidotomy. The Unified Dyskinesia Rating Scale (UDysRS) parts I+III+IV and the Unified Parkinson's Disease Rating Scale part III (UPDRS-III) were monitored prior to surgery, and at the 3-month follow-up, the location of active contacts was calculated by postoperative CT-MRI image fusion to identify stimulation sites with good anti-dyskinesia effect. Results: There were 41 patients enrolled. The postoperative levodopa equivalent daily dose (LEDD) (823.1 ± 201.5 mg/day) was not significantly changed from baseline (844.6 ± 266.1 mg/day, P = 0.348), while the UDysRS on-dyskinesia subscores significantly decreased from 24 (10-58) to 0 (0-18) [median (range)] after STN stimulation (P < 0.0001). The levodopa-induced on-dyskinesia recurred in stimulation-off/medication-on state in all the 41 patients and disappeared in 39 patients when DBS stimulation was switched on at 3 months of follow-up. The active contacts which correspond to good effect for dyskinesia were located above the STN, and the mean coordinate was 13.05 ± 1.24 mm lateral, -0.13 ± 1.16 mm posterior, and 0.72 ± 0.78 mm superior to the midcommissural point. Conclusions: High-frequency electrical stimulation of the area above the STN can directly suppress levodopa-induced on-dyskinesia.

Real-time authentication of animal species origin of leather products using rapid evaporative ionization mass spectrometry and chemometric analysis.

Increasing accounts of fraud and persistent labeling problems have brought the authenticity of leather products into question. In this study, we developed an extremely simplified workflow for real-time, in situ, and unambiguous authentication of leather samples using rapid evaporative ionization mass spectrometry (REIMS) coupled with an electric soldering iron. Initially, authentic leather samples from cattle, sheep, pig, deer, ostrich, crocodile, and snake were used to create a chemometric model based on principal component analysis and linear discriminant analysis algorithms. The validated multivariate statistical model was then used to analyze and generate live classifications of commercial leather samples. In addition to REIMS analysis, the microstructures of leathers were characterized by scanning electron microscopy to provide complementary information. The current study is expected to provide a high-throughput tool with superior efficiency and accuracy for authenticating the identity of leathers and other consumer products of biogenic origin.