bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of Hypothyroidism on Women
Authors: Shinde Aditi , Paunikar Vaishali
Published: January 2022

Background: To determine the impact of treating clinical hypothyroidism during gestation on maternal depressive symptoms.

Methods: Females with singleton pregnancies identified clinical hypothyroidism were randomised to prenatal thyroxine medication or sample in an auxiliary study to a multicenter trial. At the end of the pregnancy, the treatment was stopped. Females with overt thyroid disorder, diabetes, autoimmune disorder, or depression were excluded from the study. Before taking the survey medicine (between 3-4 months of pregnancy), between 32 and 38 weeks of pregnancy, and at one year post-delivery, contestants were examined for forbidding symptoms with the help of the Center for Epidemiological Studies-Anxiety zone(CES-D). The primary result was a score on the CES-D for mother depressive symptoms.

Results: In individuals with schizophrenia spectrum disorders, imbalanced thyroid hormonal state in general, as well as hypothyroidism and hyperthyroidism, were found in 29.3, 25.17, and 4.08 percent, respectively. These figures were similar to those seen in patients with mental abnormalities (23.24, 21.62 and 1.62 percent, respectively). Anti TPO positivity was found in 11 of the 18 patients with schizophrenia scale illness. There were no distinctions based on gender.

Conclusions: Patients with schizophrenia-spectrum disease and mood swings both had thyroid abnormalities. Patients with schizophrenia-spectrum abnormalities were more probably to have autoimmune thyroid disease than those with mood swings. The results highlight the importance of evaluating individuals with schizophrenia-scale abnormalities for thyroid hormone abnormalities and how it affects hypothyroidism.
Role of Diet, Exercise for Improvement of Immunity
Authors: Mawale Rushikesh , Dhok Archana
Published: January 2022

Background: Survival needs a healthy immune system. The immune gadget ought to be continuously on the lookout for indicators of invasion or hazard. Immune cells have to be able to differentiate between self and non-self-molecules and between probably dangerous non-self-molecules (which include those produced by using infections) and non-destructive non-self-molecules (e.g., from meals). The hyperlink between nutrients and vitamins and immune function is explored in this Special Issue of Nutrients.

Summary: We summarise the immune system's essential sports and how they interact with nutrition during existence on this prologue, highlighting the topics on this Special Issue. Macronutrients, micronutrients, and the microbiota within the gut all have a position in immune response modulation. Nutritional immune system law can help wholesome folks keep away from or postpone the emergence of immunological-mediated persistent diseases.

Conclusion: Continued looking at this discipline will subsequently result in a greater understanding of the position of meals and vitamins in immune features, making individualized vitamins a more viable alternative for enhancing human health.
Early Mobilization is the Key towards Early Functional Independence in a Patient Undergone Aortic Valve Replacement: A Case Study
Authors: Ingale Gunjan , Yadav Vaishnavi Dilip , Jain Moli Jai , Vardhan Vishnu
Published: January 2022

Heart disease due to valvular anomaly has increased prevalence along with increasing age. Rheumatic heart disease is a condition in which the heart valves have been permanently damaged post rheumatic fever. We report a patient with Aortic valve replacement using TTK CH 25 prosthetic valve who underwent post-operative physiotherapy which comprises 2 weeks of phase I cardiac rehabilitation, a home exercise program after discharge, and follow-up after 2 weeks. During follow up patient has a high level of independence, improvement in quality of life, lung function, and symptoms. This case report aims to highlight the significance of prompt diagnosis; treatment and most importantly rehabilitation incorporating early mobilization to get the patient back to his functional state. A scheduled exercise program benefits the patient and also minimizes complications after surgery.
Thymus vulgaris L. Essential Oil: Effect on Fatty Acids and Proteins Oxidation of Little Tuna (Euthynnus alletteratus) Minced during Refrigerated Storage
Authors: Hajlaoui Hafedh , Arraouadi Soumaya , Noumi Emira , Aouadi Kaïss , Snoussi Mejdi , Kadri Adel
Published: January 2022

People are uncomfortable having their food chemically treated to boost its shelf life. Thus, Tunisian Thymus vulgaris Essential Oil (TVEO) were investigated in parallel with its capacity to limit fatty acids and proteins oxidation in tuna (Euthynnus alletteratus) minced during refrigeration storage (4°C). Our results revealed that for tuna preservation, the measured concentrations of PV, TBARS and TVB-N during different storage periods showed a good efficiency of this Essential Oil (EO) (3%) in limiting lipids and proteins oxidation of tuna flesh. Moreover, we observed increase in all batches which was significantly different (P< 0.05) with lots treated with TVEO were the most conserved comparing to the BHT. Overall outcomes suggest that TVEO use for tuna conservation could represent a promising strategy to improve the qualitative characteristics as well as the safety of seafood.
Brief Review on Shatavari (Asparagus racemosus) and Its Medicinal Uses
Authors: Kurdukar Adish , Jogdand Sangita
Published: January 2022

Asparagus racemosus is another name for shatavari. It belongs to the family asparagaceae. It is an adaptable plant as well. The adaptation of human body to mental and physical stress is said to be achieved by the help of adaptogenic herbs like these.

Shatavari is an ayurvedic medicine staple that is made available in the form of analeptic for the wellbeing and vitality of person.

It is popular among all therapeutic plants due to various active biochemicals present in it such as steroidal glycosides, saponins (Shatavarins I, II, III, and IV), flavonoids, polyphenols, vitamins and alkaloids (racemosol). Shatavari extracts from its different parts like roots, flowers, leaves and stems are effective in treating female organs which are involved in reproduction.

For centuries, ayurvedic medicine has employed shatavari. However, there haven't been enough human trials to recommend it for any medical problem. It is, however, safe to consume it in modest doses, and doing so will allow you to benefit from its antioxidant and immune-boosting properties.

Except for being an indigenous medicinal plant which known to be important for its sapogenin content which is the precursor of many active pharmacological steroids, it also has many medicinal uses like antioxytoxic (shatavarin four),spasmodic to uterus, hypertensive as well as hypoglycemic activity, anticoagulant activity, antiviral activity, anticancer and antidysentric activity. In ayurvedic medicine asparagus racemosus is considered as tonic specific to females .Despite of being a herb which is rejuvenating it is used in infertility cases of females, increases libido , enhances ovulation as well as folliculogenesis, also increases lactation.
Role of Primary Care Physician in Management of Generalized Anxiety Disorder
Authors: Algaows Faisal Suliman , Alnajdi Hajar Saleh , Alsuqayh Khalifah Sulaiman , Alqahtani Basel Ali S. , Yahya Arishi, M. Khaled , Nawaf Farag N. Alomrani, , Abdulghani Sarh Sami , ALShammari Farah Najeh , Alsaykhan Khalid Ali , Ali Hozan Mohammed , Al Kuwaiti Sakinah Jawad , Bager S. Alsanna, Haytham , Ibrahim E. Alhazmi, Essa , Najmi Abdulelah Abdulrhman , Darwish Yassir Mohammed
Published: January 2022

Individual survival would be impossible without anxiety, which is a natural and important emotion. Anxiety is considered a disease that requires treatment when it occurs in the absence of a threat, or in a disproportionate proportion to a threat, as well as when it prevents the affected individual from leading a normal life. Generalized Anxiety Disorder (GAD) is a widespread mental disorder characterized by excessive and difficult-to-control anxiety and concerns. as well as a variety of psychological and physical symptoms. Patients with GAD frequently visit primary care, and it is widely acknowledged that the majority of patients should be treated in this environment. Clinical practice guidelines advocate pharmacological (e.g., SSRIs and venlafaxine) or cognitive behavior therapy as first-line therapies for GAD. There are several proposed etiological explanations for GAD, including Freud's psychoanalytic theory, Stack's interpersonal theory, and the Stress Diathesis Model. The exact pathophysiological process of the disease is not fully understood. Patients with GAD frequently visit primary care, and it is widely acknowledged that the majority of patients should be treated in this environment. Clinical practice guidelines advocate pharmacological (e.g., SSRIs and venlafaxine) or cognitive behavior therapy as first-line therapies for GAD. In this article, we’ll be discussing GAD epidemiology, etiology, evaluation, and treatment.
Fizicheski sostoyatelnie metriki c nezavisimimi parametrami vmesto standartnih metric s nefizicheskimi sledstviyami. 1. Zaryaghennie istochniki
Authors:   Centre for Theoretical Physics and Astrophysics, Zakir Zahid
Published: January 2022

Метрика вне шара с зарядом на поверхности, полученная из уравнений Эйнштейна-Максвелла, имеет три независимых параметра – заряд, радиус поверхности и гравитационный радиус шара, равный гравитационному радиусу вещества. Энергия электрического поля шара есть лишь вне шара и вносит вклад в метрику с тем же знаком, что и вещество. Поэтому рост заряда усиливает эффекты гравитации, увеличивая радиусы орбит и теней, красные смещения, углы отклонения. При коллапсе, в системе покоя центра, поверхность застывает над гравитационным радиусом шара, а внутренние слои застывают над гравитационным радиусом вещества внутри них, т.е. сколлапсировавший шар становится не чёрной дырой, а фрозаром, объектом с гравитационно-застывшей структурой. Метрика фрозара следует из метрики шара при стремлении поверхности его к гравитационному радиусу, а значит содержит два параметра вместо трёх. Заряд фрозара находится над гравитационным радиусом и полная масса, как и у шара, конечна. Наблюдаемые следствия метрики фрозара такие же, как и у шара. Напротив, в теории чёрных дыр в метрику Рейснера-Нордстрёма содержит полную массу на бесконечности, которая зависит от заряда и расходится, так как включает расходящуюся для точечного заряда энергию электрического поля. Игнорируя эту расходимость, полная масса перенормировалась заменой её на «наблюдаемую» массу. Потом, уже по ошибке, была упущена зависимость полной массы от заряда. Результатом такого двойного игнорирования был ряд нефизических следствий, обратных случаю шара. Утверждалось, что имеются два горизонта и рост заряда ослабляет гравитацию чёрной дыры, уменьшая гравитационный радиус и эффекты гравитации, такие как красные смещения, радиусы орбит и теней, т.е. всерьёз утверждалось, что положительная энергия электрического поля антигравитирует, что является физически абсурдным.
Seeking New Layered Oxyselenides with Promising Thermoelectric Performance
Authors: Yang Yueyang , Han Jian , Zhou Zhifang , Zou Mingchu , Xu Yushuai , Zheng Yunpeng , Nan Ce‐Wen , Lin Yuan‐Hua
Published: January 2022

Layered oxyselenides have been widely investigated as promising thermoelectric materials due to their unique merits such as super‐lattice structural features and intrinsic complexity, which contributes to low thermal conductivity and easily controllable electrical properties. Newly developed Bi2LnO4Cu2Se2 (Ln stands for lanthanide) oxyselenides are found to be potential thermoelectric systems since they have excellent electrical conductivity over 103 S cm−1. In this work, unique energy and time‐saving method combined self‐propagating high‐temperature synthesis (SHS) with spark plasma sintering (SPS) is adopted to successfully prepare a highly pure Bi2LnO4Cu2Se2 instead of a traditional solid‐state reaction. To explore the most suitable lanthanide for Bi2LnO4Cu2Se2, thermoelectric performance in a wide temperature range (300 to 923 K) of Bi2LnO4Cu2Se2 (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er) is deeply evaluated and studied. Ultimately, with a relatively high electrical conductivity, moderate Seebeck coefficient, and extremely low thermal conductivity, a maximum ZT value of ≈0.27 at 923K is achieved in Bi2DyO4Cu2Se2, which is 4 times larger than that of the ever‐reported Bi2YO4Cu2Se2 and proves a potential thermoelectric system for further investigation. This work may provide some enlightenment and broaden the horizon in finding new thermoelectric materials, especially for complex layered compounds.
Ultrafast Shaped Laser Induced Synthesis of MXene Quantum Dots/Graphene for Transparent Supercapacitors
Authors: Yuan Yongjiu , Jiang Lan , Li Xin , Zuo Pei , Zhang Xueqiang , Lian Yiling , Ma Yunlong , Liang Misheng , Zhao Yang , Qu Liangti
Published: January 2022

Ultratransparent electrodes have attracted considerable attention in optoelectronics and energy technology. However, balancing energy storage capability and transparency remains challenging. Herein, an in situ strategy employing a temporally and spatially shaped femtosecond laser is reported for photochemically synthesizing of MXene quantum dots (MQDs) uniformly attached to laser reduced graphene oxide (LRGO) with exceptional electrochemical capacitance and ultrahigh transparency. The mechanism and plasma dynamics of the synthesis process are analyzed and observed at the same time. The unique MQDs loaded on LRGO greatly improve the specific surface area of the electrode due to the nanoscale size and additional edge states. The MQD/LRGO supercapacitor has high flexibility and durability, ultrahigh energy density (2.04 × 10−3 mWh cm−2), long cycle life (97.6% after 12 000 cycles), and excellent capacitance (10.42 mF cm−2) with both high transparency (transmittance over 90%) and high performance. Furthermore, this method provides a means of preparing nanostructured composite electrode materials and exploiting quantum capacitance effects for energy storage.
A Gradient Model for the Spatial Patterns of Cities
Authors: Chang Jie , Yang Guofu , Liu Shun , Jin Hanhui , Wu Zhaoping , Xu Ronghua , Min Yong , Zheng Kaiwen , Xu Bin , Luo Weidong , Mao Feng , Ge Ying , Cheong Kang Hao
Published: January 2022

The dynamics of a city's structures are determined by the coupling of functional components (such as restaurants) and human population. Yet, there lacks mechanism models to quantify the forces on the spatial distribution of the components. Here, a gradient model is explored to simulate the individual density curves of multiple types of city functional components based on the equilibria of gravitational and repulsive forces along with the urban–rural gradient. The model is concise by relying on four key variables, the attributes of components include net ecosystem service (m) and environmental index (γ); and the attributes of cities include land rent exponent (σ) and population attenuation coefficient (β). The model has been used to simulate the distribution curves of 22 types of components on the urban–rural gradients in 13 cities in two periods. The model reveals a bottom‐up mechanism that the patterns of the components in a city are determined by the economic, ecological, and social attributes of both cities and components. Strongly backed by empirical data, the model can predict the distribution curves of many types of components along with the development of cities. This model provides a general tool for analyzing the distribution of multiple objects on the gradients.
Lithium‐Ion Battery State of Charge Estimation Using a New Extended Nonlinear State Observer
Authors: Sakile Rajakumar , Sinha Umesh Kumar
Published: January 2022

In this paper, an extended nonlinear state observer (ENSO) is proposed to estimate lithium‐ion batteries’ accurate state of charge (SOC). The two RC equivalent circuit model is used to describe the dynamic behavior of the lithium‐ion battery. Based on the circuit state equations, the proposed ENSO is designed to estimate SOC. The ninth‐order polynomial fitting curve shows a nonlinear relationship between open‐circuit voltage and SOC. Furthermore, the proposed ENSO's stability and convergence rate are guaranteed by Lyapunov's stability analysis. The performance of the proposed observer is compared to that of conventional techniques such as the unscented Kalman filter and sliding mode observer. The proposed method has given better dynamic performance with accurate SOC, reducing computational cost and enhancing the convergence capability compared to conventional methods. The proposed model's effectiveness is validated through the MATLAB/Simulink platform.
Rational‐Designed Principles for Electrochemical and Photoelectrochemical Upgrading of CO2 to Value‐Added Chemicals
Authors: Zhang Wenjun , Jin Zhong , Chen Zupeng
Published: January 2022

The chemical transformation of carbon dioxide (CO2) has been considered as a promising strategy to utilize and further upgrade it to value‐added chemicals, aiming at alleviating global warming. In this regard, sustainable driving forces (i.e., electricity and sunlight) have been introduced to convert CO2 into various chemical feedstocks. Electrocatalytic CO2 reduction reaction (CO2RR) can generate carbonaceous molecules (e.g., formate, CO, hydrocarbons, and alcohols) via multiple‐electron transfer. With the assistance of extra light energy, photoelectrocatalysis effectively improve the kinetics of CO2 conversion, which not only decreases the overpotentials for CO2RR but also enhances the lifespan of photo‐induced carriers for the consecutive catalytic process. Recently, rational‐designed catalysts and advanced characterization techniques have emerged in these fields, which make CO2‐to‐chemicals conversion in a clean and highly‐efficient manner. Herein, this review timely and thoroughly discusses the recent advancements in the practical conversion of CO2 through electro‐ and photoelectrocatalytic technologies in the past 5 years. Furthermore, the recent studies of operando analysis and theoretical calculations are highlighted to gain systematic insights into CO2RR. Finally, the challenges and perspectives in the fields of CO2 (photo)electrocatalysis are outlined for their further development.
Bioinspired Fatty Acid Amide‐Based Slippery Oleogels for Shear‐Stable Lubrication
Authors: Lee Jaehyeon , Kim Boram , Lee Ji Woong , Hong Chan Young , Kim Gwang Hoon , Lee Sang Joon
Published: January 2022

Liquid‐repellent technology is an efficient means of energy‐saving and biofouling avoidance. However, liquid‐repellent surfaces suffer from inefficient lubricant retention under shear flow and fouling problem in marine environment. Here, the authors demonstrate a fatty acid amide (FAA)‐based oleogel for stable and sustainable lubrication in marine environment. The lubrication management of marine creatures is emulated in synthetic oleogels by incorporating solid (FAA) and liquid lubricants into the molecular meshes of polymeric networks, with the nature‐derived solid lubricant providing multifunctional synergistic effects with liquid oil molecules for slippery property and remarkable anti‐biofouling. The lubricant‐confining gel achieves shear‐stable lubricity with efficient oil management. The oleogel provides continued lubrication without biofouling for approximately 4 months in marine field tests. The gel design provides a new paradigm for sustainable and shear‐stable lubrication in marine environment.
Cobalt‐Doping Stabilized Active and Durable Sub‐2 nm Pt Nanoclusters for Low‐Pt‐Loading PEMFC Cathode
Authors: Duan Xiao , Cao Feng , Ding Rui , Li Xiaoke , Li Qingbing , Aisha Ruziguli , Zhang Shiqiao , Hua Kang , Rui Zhiyan , Wu Yongkang , Li Jia , Li Aidong , Liu Jianguo
Published: January 2022

Proton exchange membrane fuel cells (PEMFCs) suffer severe performance loss in the high current density (HCD) region as Pt‐loading decreases. A smaller electrocatalyst size inducing a higher electrochemically active surface area (ECSA) is critical for solving this issue. However, the poor electrocatalytic activity and stability of sub‐2 nm nanoclusters limit the potential to reduce their size. In this study, 1.69 nm Co‐doped Pt nanoclusters with a large ECSA (116.19 m2 gPt–1) are synthesized. The mass activity (MA) (0.579 A mgPt–1) and stability (9% MA loss after 30k potential cycling) refresh the record of sub‐2 nm nanoclusters. The structural characterization and theoretical calculations reveal that doping reduces the total energy required to stabilize the nanoclusters. Dopant tailoring of the d‐band center and vacancy formation energy account for the activity and stability enhancement, respectively. Due to the larger ECSA and MA induced by doping, HCD voltage loss due to lower Pt‐loading is significantly reduced compared with commercial Pt/C. The peak power density of low‐Pt‐loading PEMFCs (0.075 mgPt cmMEA–2) with a doped nanocluster cathode is 0.811 W cm–2 (H2–air condition), which far exceeds commercial Pt/C (0.5 W cm–2) and that of most reported electrocatalysts.
Environmental patterns of adaptation after range expansion in Leontodon longirostris: The effect of phenological events on fitness‐related traits
Authors: de Pedro Manuel , Mayol Maria , González‐Martínez Santiago C. , Regalado Ingrid , Riba Miquel
Published: January 2022

Premise

Because of expected range shifts associated with climate change, there is a renewed interest in the evolutionary factors constraining adaptation, among which are genetic bottlenecks, drift, and increased mutational load after range expansion.

Here we study adaptation in the short‐lived species Leontodon longirostris showing reduced genetic diversity and increased genetic load along an expansion route.

Methods

We assessed the phenological patterns of variation, and their effect on fitness‐related traits, on 42 L. longirostris populations and six populations of the sister taxa L. saxatilis in a common garden located within the current range of both species. The comparison among L. longirostris populations allowed us to test for genetic clines consistent with local adaptation, whereas the comparison between taxa provided evidence for common adaptive features at the species level.

Results

We found significant within‐species variability for most traits, as well as differences with its close relative L. saxatilis. In general, seeds from drier, warmer, and unpredictable habitats showed overall lower and more restricted conditions for germination, seedlings emerged later and plants flowered earlier. Consequently, genotypes from arid and unpredictable environments attained smaller reproductive sizes and allocated more biomass to reproduction. Flowering time had the strongest direct effect on total plant size, but seedling emergence also showed an important indirect effect.

Conclusions

Our results show the crucial role of phenological patterns in shaping adaptive clines for major life‐history stage transitions. Furthermore, the genetic load observed in L. longirostris does not seem to preclude adaptation to the climatic variability encountered along the expansion route.
A 29‐gene signature associated with NOX2 discriminates acute myeloid leukemia prognosis and survival
Authors: Ijurko Carla , González‐García Nerea , Galindo‐Villardón Purificación , Hernández‐Hernández Ángel
Published: January 2022

The molecular complexity displayed in acute myeloid leukemia (AML) hinders patient stratification and treatment decisions. Previous studies support the utility of using specific gene panels for this purpose. Focusing on two salient features of AML, the production of reactive oxygen species (ROS) by NADPH oxidases (NOX) and metabolism, we aimed to identify a gene panel that could improve patient stratification. A pairwise comparison of AML versus healthy gene expression revealed the downregulation of four members of the NOX2 complex including CYBB (coding for NOX2) in AML patients. We analyzed the expression of 941 genes related to metabolism and found 28 genes with expression correlated to CYBB. This panel of 29 genes (29G) effectively divides AML samples according to their prognostic group. The robustness of 29G was confirmed by 6 AML cohort datasets with a total of 1821 patients (overall accuracies of 85%, 78%, 80%, 75%, 59% and 83%). An expression index (EI) was developed according to the expression of the selected discriminatory genes. Overall Survival (OS) was higher for low 29G expression index patients than for the high 29G expression index group, which was confirmed in three different datasets with a total of 1069 patients. Moreover, 29G can dissect intermediate‐prognosis patients in four clusters with different OS, which could improve the current AML stratification scheme. In summary, we have found a gene signature (29G) that can be used for AML classification and for OS prediction. Our results confirm NOX and metabolism as suitable therapeutic targets in AML.
Outcome of Progressive Multifocal Leukoencephalopathy Treated by Interleukin‐7
Authors: Lajaunie Rébecca , Mainardi Ilaria , Gasnault Jacques , Rousseau Vanessa , Tarantino Andrea G. , Sommet Agnès , Cinque Paola , Martin‐Blondel Guillaume ,   PML study group
Published: January 2022

Objective

Restoring anti‐JC virus (JCV) immunity is the only treatment of progressive multifocal leukoencephalopathy (PML). Interleukin‐7 is a cytokine that increases number and function of T cells. We analyzed a population of PML patients who received recombinant human IL‐7 (rhIL‐7) to estimate survival and its determinants.

Methods

After exclusion of patients with missing data or receiving other immunotherapies, findings from 64 patients with proven PML who received rhIL‐7 between 2007 and 2020 were retrospectively analyzed. Logistic regression was used to analyze variables associated with one‐year survival.

Results

Underlying conditions were HIV/AIDS (n = 27, 42%), hematological malignancies (n = 16, 25%), primary immunodeficiencies (n = 13, 20%), solid organ transplantation (n = 4, 6%) and chronic inflammatory diseases (n = 4, 6%). One‐year survival was 54.7% and did not differ by underlying condition. Survival was not associated with baseline characteristics, but with a >50% increase in blood lymphocytes (OR 4.1, 95%CI 1.2–14.9) and CD4+ T cells (OR 5.9, 95%CI 1.7–23.3), and a > 1 log copies/mL decrease in cerebrospinal fluid JCV DNA (OR 7.6, 95%CI 1.6–56.1) during the first month after rhIL‐7 initiation. Side effects were mainly local and flu‐like symptoms (n = 8, 12.5%) and PML‐immune reconstitution inflammatory syndrome (IRIS) (n = 5, 8%).

Interpretation

In this non‐controlled retrospective study, survival did not differ from that expected in HIV/AIDS patients, but might have been improved in those with hematological malignancies, primary immunodeficiencies and transplant recipients. RhIL‐7 might have contributed to the increase in blood lymphocytes and decrease in CSF JCV replication that were associated with better survival. ANN NEUROL 2022;91:496–505
Mechanismus der bifunktionellen Multiprodukt‐Sesterterpensynthase AcAS aus Aspergillus calidoustus
Authors: Quan Zhiyang , Hou Anwei , Goldfuss Bernd , Dickschat Jeroen S.
Published: January 2022

Die chimäre Multiprodukt‐Sesterterpensynthase AcAS aus Aspergillus calidoustus lieferte neben fünf bekannten Sesterterpenen das spirocyclische Calidousten, welches ein neues Gerüst aufweist. Der komplexe Cyclisierungsmechanismus zu allen sechs Verbindungen wurde durch Isotopenmarkierungsexperimente in Kombination mit DFT‐Rechnungen untersucht. Chemisch synthetisiertes 8‐Hydroxyfarnesyldiphosphat wurde mit Isopentenyldiphosphat und AcAS in vier oxygenierte Sesterterpenoide umgewandelt, die strukturell den Cytochrom‐P450‐Oxidationsprodukten der Sesterterpen‐Kohlenwasserstoffe ähneln. Das Proteinengineering von AcAS erweiterte dessen Substratspektrum und führte zu signifikant verbesserten Enzymausbeuten.
Unmasking the Critical Role of the Ordering Degree of Bimetallic Nanocatalysts on Oxygen Reduction Reaction by In Situ Raman Spectroscopy
Authors: Chen Heng‐Quan , Ze Huajie , Yue Mu‐Fei , Wei Di‐Ye , A Yao‐Lin , Wu Yuan‐Fei , Dong Jin‐Chao , Zhang Yue‐Jiao , Zhang Hua , Tian Zhong‐Qun , Li Jian‐Feng
Published: January 2022

Precise control and accurate understanding of the ordering degree of bimetallic nanocatalysts (BNs) are challenging yet crucial to acquire advanced materials for the oxygen reduction reaction (ORR). AuCu BNs with various ordering degrees were synthesized to evaluate the influence of ordering degree on the ORR at a molecular level using in situ Raman spectroscopy. The activity of AuCu BNs was improved by over 2 times after a disorder‐to‐order transition, making the performance of highly ordered AuCu BNs exceed that of benchmark Pt/C. Direct Raman spectroscopic evidence of key intermediate (*OH) demonstrates that the active site is the combination site of Au and Cu. Moreover, two distinct *OH species are observed on the ordered and disordered structure, and the ordered site is more beneficial for ORR due to its lower affinity to *OH. This work deepens the understanding on the important role of ordering degree on BNs and enables the design of improved catalysts.
The synthesis of a copper metal‐organic framework Cu3TDPAT and its application in a Morita‐Baylis‐Hillman (MBH) reaction
Authors: Yang Yanan , Shang Hailing , Li Xiujuan , Zhu Kaicheng , Luan Yi
Published: January 2022

A highly effective Morita‐Baylis‐Hillman (MBH) reaction was developed employing Cu (II) derived Cu3TDPAT as the dual‐functional metal‐organic frameworks (MOFs) catalyst. Four kinds of copper salts were employed as precursors to synthesize Cu3TDPAT. The resultant Cu3TDPAT MOFs were used as catalysts for the MBH model reaction of 4‐fluorobenzaldehyde and 2‐cyclopentene‐1‐one under various reaction conditions. The results showed that Cu3TDPAT‐c derived from copper nitrate was the optimal catalyst to achieve a high yield (up to 99%). With the presence of aromatic aldehydes and basic triazine groups in Cu3TDPAT, the Lewis acid and base sites in Cu3TDPAT MOF played a significant role during the reaction to effect the formation of CC single bond between 4‐fluorobenzaldehyde and 2‐cyclopentene‐1‐one to generate benzyl methyl acrylonitrile products. In addition, after optimization, this catalyst showed good catalytic performance for the MBH reaction with high thermal stability, reliability, and recyclability. This optimal catalytic performance shows great potential for further development.
Switchable activity of a Ru catalyst bearing an annulated mesoionic carbene ligand for oxidation of primary amines
Authors: Yadav Suman , Pal Saikat , Pal Nilay Kumar , Din Reshi Noor U , Pal Sourav , Bera Jitendra K.
Published: January 2022

The catalytic activity of a Ru complex 1, bearing a fused π‐conjugated imidazo[1,2–a][1,8]naphthyridine‐based mesoionic carbene (MIC) ligand, is examined for the oxidation of primary amines. Complex 1 affords nitrile or imine depending on the nature of the terminal oxidants and solvents used in the reactions. Primary amines are converted to nitriles using NaIO4 in EtOAc/H2O mixture, whereas imines are obtained under O2 balloon pressure in toluene. A variety of nitriles and imines are accessed with high yields and selectivity. A set of control experiments, reaction profiles, and kinetic studies are undertaken to disclose the mechanistic details for nitrile and imine formation. The catalytic reactions illustrate a subtle dependency on the choice of oxidants and solvents in the oxidation of primary amines.
Diluted High‐Concentration Electrolyte Based on Phosphate for High‐Performance Lithium‐Metal Batteries
Authors: Liu Mengchuang , Li Xing , Zhai Baoyu , Zeng Ziqi , Hu Wei , Lei Sheng , Zhang Han , Cheng Shijie , Xie Jia
Published: January 2022

Lithium (Li) metal is an ultra‐high specific capacity and low potential ‘‘holy grail’’ anode for developing high energy density rechargeable Li metal batteries (LMBs), but its practical application suffers from the low Coulombic efficiency (CE) and dendritic lithium growth due to its thermodynamic instability to organic solvents. Here, we report a new diluted high concentration electrolyte (DHCE) containing lithium bis(fluorosulfonyl)imide, triethyl phosphate and fluorobenzene cosolvent, which not only guarantees lithium metal anode (LMA) with an 98.4 % high average CE over 250 cycles but greatly improves Li||NMC622 cells property (70 % capacity retention after 200 cycles at C/3 current density). Therefore, this new electrolyte can provide more possibilities for developing high‐energy‐density LMBs.
Hot electrons generated from Mn‐doped quantum dots via upconversion for photocatalysis applications
Authors: Wang Chih‐Wei , Orrison Connor , Son Dong Hee
Published: January 2022

There is a growing interest in the application of photogenerated hot electrons in semiconductor or metallic nanostructures such as in photocatalysis and photovoltaics taking advantage of their large excess kinetic energy and long‐range transfer capability. Among various nanostructures that can generate hot electrons, Mn‐doped semiconductors quantum dots (QDs) have shown their unique ability to produce highly energetic hot electrons via upconversion process. Compared to the plasmonic hot electrons, upconverted hot electrons in Mn‐doped QDs possess several eV larger energy and can even produce photoelectron emission above the vacuum level from a subpopulation of hot electrons under weak visible excitation equivalent to the concentrated solar radiation. The present account reviews recent progresses made in the research on hot electron generation via upconversion and their application in photocatalytic reactions that highlights the benefits of long‐range transfer of energetic hot electrons.
Preparation of Porous Zn0.76Co0.24S Yolk‐Shell Microspheres with Enhanced Electrochemical Performance for Sodium Ion Batteries
Authors: Li Zuze , Zheng Yang , Li Qun , Gu Tingting , Shen Xueran , Ma Tiantian , Jiao Qingze , Zhao Yun , Li Hanshen , Feng Caihong
Published: January 2022

Transition metal sulfides, due to excellent redox reversibility and considerable electronic conductivity, have been proposed as an available alternative material for rechargeable batteries. In this work, porous Zn0.76Co0.24S (ZCS) yolk‐shell microspheres are favorably obtained through a facile solvothermal manner, followed by a vulcanization process. The effects of vulcanization temperature on the morphology, structure, and electrochemical performance of the products are also explored. Owing to the unique buffering space and generous active sites of yolk‐shell structure, the electrode material exhibits excellent cycle and rate performance. Comparatively, Zn0.76Co0.24S vulcanized at 140 °C (ZCS‐140) retains a capacity of 671 mAh g−1 at 100 mA g−1 after 100 cycles and delivered a reversible capacity of 389 mAh g−1 at 1 A g−1 after 1000 cycles with a decay of only 0.029 % per cycle, which is better than that of ZCS‐120 and ZCS‐160, indicating its potential to be a promising next‐generation anode for SIBs.
Electrochemical Kinetics of Layered Manganese Phosphate via Interfacial Polypyrrole Chemical Binding
Authors: Du Jia‐Lin , Bao Xu , Zhang Wei‐Bin , Zhang Lun , Guo Yao‐Wen , Zhou Xia , Zhang Xian‐Li , Chai Shan‐Shan , Guo Shao‐Bo , Han Xiong‐Wei , Long Jianping
Published: January 2022

The major limitation of low‐cost and high‐safety aqueous manganese‐based materials for electrochemical energy storage is largely hampered by their poor cyclic stability, usually caused by the manganese dissolution and interfacial kinetics. Herein, we synthesized a manganese phosphate material via interfacial polypyrrole chemical binding, with unique structural properties for aqueous supercapacitor application. It exhibited higher specific capacitance, remarkable rate performance and better cycle stability compared to bare manganese phosphate. In contrast with interfacial polypyrrole coating on manganese phosphate nanosheets, the polypyrrole could form a Mn−N bond with the manganese phosphate, indicating stable chemical binding. Thus, the appropriate interfacial chemical binding is an efficient strategy to improve the nanostructure stability and electrochemical kinetics of manganese‐based materials for aqueous electrochemical energy storage.
Comparative enantioseparation of planar chiral ferrocenes on polysaccharide‐based chiral stationary phases
Authors: Dessì Alessandro , Sechi Barbara , Dallocchio Roberto , Chankvetadze Bezhan , Pérez‐Baeza Mireia , Cossu Sergio , Mamane Victor , Pale Patrick , Peluso Paola
Published: January 2022

Planar chiral ferrocenes are well‐known compounds that have attracted interest for application in synthesis, catalysis, material science, and medicinal chemistry for several decades. In spite of the fact that asymmetric synthesis procedures for obtaining enantiomerically enriched ferrocenes are available, sometimes, the accessible enantiomeric excess of the chiral products is unsatisfactory. In such cases and for resolution of racemic planar chiral ferrocenes, enantioselective high‐performance liquid chromatography (HPLC) on polysaccharide‐based chiral stationary phases (CSPs) has been used in quite a few literature articles. However, although moderate/high enantioselectivities have been obtained for planar chiral ferrocenes bearing polar substituents, the enantioseparation of derivatives containing halogens, or exclusively alkyl groups, remains rather challenging. In this study, the enantioseparation of ten planar chiral 1,2‐ and 1,3‐disubstituted ferrocenes was explored by using five polysaccharide‐based CSPs under multimodal elution conditions. Baseline enantioseparations were achieved for nine analytes with separation factors (α) ranging from 1.20 to 2.92. The presence of π‐extended systems in the analyte structure was shown to impact affinity of the most retained enantiomer toward amylose‐based selectors, observing retention times higher than 80 min with methanol‐containing mobile phases (MPs). Electrostatic potential (V) analysis and molecular dynamics (MD) simulations were used in order to study interaction modes at the molecular level.
Jürgen Caro zum 70.
Authors: Voigt Ingolf
Published: January 2022

No abstract.
Adaptive estimation for functional data: Using a framelet block‐thresholding method
Authors: Cheng Kun , Chen Di‐Rong
Published: January 2022

This article considers a framelet block‐thresholding method for estimating mean and covariance functions from discretely sampled noisy observations. Estimated convergence rates are established for all types of sampling schemes. In particular, the results reveal a phase transition phenomenon related to the number of observations on each curve. It is shown that the proposed procedures are adaptive in automatically adjusting the smoothness properties of the underlying mean and covariance functions. In contrast, theoretical results for other smoothing methods hold in the setting where smoothness parameters are assumed to be known, since the regularization parameters of estimators that depend on smoothness properties need to be chosen carefully. Simulation studies are provided to offer empirical support for the theoretical results. A comparison with other methods demonstrates that the proposed method outperforms in adaptivity. An application to a real dataset is also provided to illustrate the proposed estimation procedure.
Balancing Histone Deacetylase (HDAC) Inhibition and Drug‐likeness: Biological and Physicochemical Evaluation of Class I Selective HDAC Inhibitors
Authors: Schäker‐Hübner Linda , Haschemi Reza , Büch Thomas , Kraft Fabian B. , Brumme Birke , Schöler Andrea , Jenke Robert , Meiler Jens , Aigner Achim , Bendas Gerd , Hansen Finn K.
Published: January 2022

Herein we report the structure‐activity and structure‐physicochemical property relationships of a series of class I selectiveortho‐aminoanilides targeting the “foot‐pocket” in HDAC1&2. To balance the structural benefits and the physicochemical disadvantages of these substances, we started with a set of HDACi related to tacedinaline (CI‐994) and evaluated their solubility, lipophilicity (log D7.4) and inhibition of selected HDAC isoforms. Subsequently, we selected the most promising “capless” HDACi and transferred its ZBG to our previously published scaffold featuring a peptoid‐based cap group. The resulting hit compound10 c(LSH‐A54)showed favorable physicochemical properties and is a potent, selective HDAC1/2 inhibitor. The following evaluation of its slow binding properties revealed thatLSH‐A54binds tightly to HDAC1 in an induced‐fit mechanism. The potent HDAC1/2 inhibitory properties were reflected by attenuated cell migration in a modified wound healing assay and reduced cell viability in a clonogenic survival assay in selected breast cancer cell lines.
Structurally Reinforced Silicon/Graphene Composite for Lithium‐Ion Battery Anodes: Carbon Anchor as a Conductive Structural Support
Authors: Hoon Park Byung , Yang Hanmo , Gil Choi Yong , Kim Kwang‐Bum
Published: January 2022

Herein, a Si/reduced graphene oxide (rGO)/C microsphere composite is reported, wherein sucrose‐derived carbon binds Si nanoparticles (NPs) and rGO to act as a carbon anchor and links neighboring rGO sheets to reinforce the composite structure. In this structurally reinforced Si/rGO/C composite, the electron conduction pathways between rGO and Si NPs were maintained even under large volume changes during repeated charge–discharge processes. Consequently, the Si/rGO/C composite anode exhibited an initial discharge capacity of 1209 mAh g−1 and superior cyclability (92 % retention at 100 cycles), initial coulombic efficiency of 80.5 %, and high‐rate capability even at a high C rate (6 C). Furthermore, the change in anode thickness after repeated cycling was negligible, confirming the structural stability imparted by the sucrose‐derived carbon binder. A full cell assembled with a LiCoO2 cathode and the Si/rGO/C composite anode remained stable over 200 cycles.
Genome‐wide off‐target analyses of CRISPR/Cas9‐mediated T‐cell receptor engineering in primary human T cells
Authors: Kaeuferle Theresa , Stief Tanja A , Canzar Stefan , Kutlu Nayad N , Willier Semjon , Stenger Dana , Ferrada‐Ernst Paulina , Habjan Nicola , Peters Annika E , Busch Dirk H , Feuchtinger Tobias
Published: January 2022

Objectives

Exploiting the forces of human T cells for treatment has led to the current paradigm of emerging immunotherapy strategies. Genetic engineering of the T‐cell receptor (TCR) redirects specificity, ablates alloreactivity and brings significant progress and off‐the‐shelf options to emerging adoptive T‐cell transfer (ACT) approaches. Targeted CRISPR/Cas9‐mediated double‐strand breaks in the DNA enable knockout or knock‐in engineering.

Methods

Here, we perform CRISPR/Cas9‐mediated TCR knockout using a therapeutically relevant ribonucleoprotein (RNP) delivery method to assess the safety of genetically engineered T‐cell products. Whole‐genome sequencing was performed to analyse whether CRISPR/Cas9‐mediated DNA double‐strand break at the TCR locus is associated with off‐target events in human primary T cells.

Results

TCRα chain and TCRβ chain knockout leads to high on‐target InDel frequency and functional knockout. None of the predicted off‐target sites could be confirmed experimentally, whereas whole‐genome sequencing and manual Integrative Genomics Viewer (IGV) review revealed 9 potential low‐frequency off‐target events genome‐wide. Subsequent amplification and targeted deep sequencing in 7 of 7 evaluable loci did not confirm these low‐frequency InDels. Therefore, off‐target events are unlikely to be caused by the CRISPR/Cas9 engineering.

Conclusion

The combinatorial approach of whole‐genome sequencing and targeted deep sequencing confirmed highly specific genetic engineering using CRISPR/Cas9‐mediated TCR knockout without potentially harmful exonic off‐target effects.
LncRNA LINC00942 promotes chemoresistance in gastric cancer by suppressing MSI2 degradation to enhance c‐Myc mRNA stability
Authors: Zhu Yiran , Zhou Bingluo , Hu Xinyang , Ying Shilong , Zhou Qiyin , Xu Wenxia , Feng Lifeng , Hou Tianlun , Wang Xian , Zhu Liyuan , Jin Hongchuan
Published: January 2022

Background

Chemoresistance to cisplatin (DDP) remains a major challenge in advanced gastric cancer (GC) treatment. Although accumulating evidence suggests an association between dysregulation of long non‐coding RNAs (lncRNAs) and chemoresistance, the regulatory functions and complexities of lncRNAs in modulating DDP‐based chemotherapy in GC remain under‐investigated. This study was designed to explore the critical chemoresistance‐related lncRNAs in GC and identify novel therapeutic targets for patients with chemoresistant GC.

Methods

Chemoresistance‐related lncRNAs were identified through microarray and verified through a quantitative real‐time polymerase chain reaction (qRT‐PCR). Proteins bound by lncRNAs were identified through a human proteome array and validated through RNA immunoprecipitation (RIP) and RNA pull‐down assays. Co‐immunoprecipitation and ubiquitination assays were performed to explore the molecular mechanisms of the Musashi2 (MSI2) post‐modification. The effects of LINC00942 (LNC942) and MSI2 on DDP‐based chemotherapy were investigated through MTS, apoptosis assays and xenograft tumour formation in vivo.

Results

LNC942 was found to be up‐regulated in chemoresistant GC cells, and its high expression was positively correlated with the poor prognosis of patients with GC. Functional studies indicated that LNC942 confers chemoresistance to GC cells by impairing apoptosis and inducing stemness. Mechanically, LNC942 up‐regulated the MSI2 expression by preventing its interaction with SCFβ‐TRCP E3 ubiquitin ligase, eventually inhibiting ubiquitination. Then, LNC942 stabilized c‐Myc mRNA in an N6‐methyladenosine (m6A)‐dependent manner. As a potential m6A recognition protein, MSI2 stabilized c‐Myc mRNA with m6A modifications. Moreover, inhibition of the LNC942‐MSI2‐c‐Myc axis was found to restore chemosensitivity both in vitro and in vivo.

Conclusions

These results uncover a chemoresistant accelerating function of LNC942 in GC, and disrupting the LNC942‐MSI2‐c‐Myc axis could be a novel therapeutic strategy for GC patients undergoing chemoresistance.