Size Modification Research Articles

Vitamin D, acute respiratory infections, and Covid-19: The curse of small-size randomised trials. A critical review with meta-analysis of randomised trials.

Randomised trials conducted from 2006 to 2021 indicated that vitamin D supplementation (VDS) was able to prevent severe COVID-19 and acute respiratory infections (ARI). However, larger randomised trials published in 2022 did not confirm the health benefits of VDS in COVID-19 patients. To examine through a systematic review with meta-analysis the characteristics of randomised trials on VDS to COVID-19 patients and admission to intensive care unit (ICU), and of randomised trials on VDS for the prevention of ARI. A systematic search retrieved randomised trials on VDS to COVID-19 patients and admission to ICU. Data on VDS and ARI were extracted from the meta-analysis of Jolliffe et al. 2021. Groups were formed including trials with total numbers of patients below or above the median size of all trials. The associations between VDS vs no VDS, and admission to ICU were evaluated using random-effects models from which summary odds ratios (SOR) and 95% confidence intervals (CI) were obtained. Meta-analyses were done for all trials and for each group of trials, which allowed testing a possible effect modification of trial size. Publication bias was assessed using the Louis-Furuya-Kanaruori (LFK) index (no bias if index between -1 and +1) and the trim and fill method. Nine trials on VDS for preventing admission to ICU were identified, including 50 to 548 patients. The summary odds ratio (SOR) was 0.61 (95% CI: 0.39-0.95) for all trials, 0.34 (0.13-0.93) for trials including 50 to <106 patients and 0.88 (0.62-1.24) for trials including 106 to 548 patients (interaction p = 0.04). The LFK index was -3.79, and after trim and fill, the SOR was 0.80 (0.40-1.61). The SOR for the 37 trials on VDS for ARI prevention included 25 to 16,000 patients. The SOR was 0.92 (0.86-0.99) for all trials, 0.69 (0.57-0.83) for trials including 25 to <248 patients and 0.98 (0.94-1.03) for trials including 248 to 16,000 patients (interaction p = 0.0001). The LFK index was -3.11, and after trim and fill, the SOR was 0.96 (0.88-1.05). Strong publication bias affected small randomised trials on VDS for the prevention of severe COVID-19 and of ARI. Systematic reviews should beware of small-size randomised trials that generally exaggerate health benefits.

Platinum nanoparticles in cancer therapy: chemotherapeutic enhancement and ROS generation.

Platinum nanoparticles (PtNPs) offer significant promise in cancer therapy by enhancing the therapeutic effects of platinum-based chemotherapies like cisplatin. These nanoparticles improve tumor targeting, reduce off-target effects, and help overcome drug resistance. PtNPs exert their anti-cancer effects primarily through the generation of reactive oxygen species (ROS), which induce oxidative stress and apoptosis in cancer cells. Additionally, PtNPs interact with cellular signaling pathways such as PI3K/AKT and MAPK, sensitizing cancer cells to chemotherapy. Advances in PtNP synthesis focus on optimizing size, shape, and surface modifications to enhance biocompatibility and targeting. Functionalization with biomolecules allows selective tumor delivery, while smart release systems enable controlled drug release. In vivo studies have shown that PtNPs significantly inhibit tumor growth and metastasis. Ongoing clinical trials are evaluating their safety and efficacy. This review explores PtNPs' mechanisms of action, nanotechnology advancements, and challenges in biocompatibility, with a focus on their potential integration into cancer treatments.

Denovo variants in POGZ and YY1 genes: The novel mega players for neurodevelopmental syndromes in two unrelated consanguineous families.

Novel denovo variants of exome sequences are major cause of pathogenic neurodevelopmental disorders with a dominant genetic mechanism that emphasize their heterogeneity and complex phenotypes. White Sutton syndrome and Gabriele-de-Vries syndrome are congenital neuro-impairments with overlap of severe intellectual disability, microcephaly, convulsions, seizures, delayed development, dysmorphism of faces, retinal diseases, movement disorders and autistic traits. POGZ gene codes for pogo transposable element-derived zinc-finger protein and YY1 gene regulates transcription, chromatin, and RNA-binding proteins that have been associated with White Sutton and Gabriele-de-Vries syndromes, in recent data. We present probands of two unrelated consanguineous families with complicated, unexplained neurocognitive syndromic characteristics clinically undiagnosed. Objectives of the study were to identify altered genetics and protein characteristics underlying molecular pathological pathways in both the patients. Whole exome sequencing identifies novel, denovo missense variant NM_015100.4: c.776 C>T (p. Pro259Leu) in exons 19 of POGZ gene and non-frameshift variant NM_003403.5: c.141_143delGGA (p. Glu47del) in exon 1 of YY1 gene for White Sutton syndrome in eight years five-month-old girl and Gabriele-de-Vries syndrome in seven years eight months old boy residing in Rawalpindi and Chakwal districts of Punjab, Pakistan respectively. Protein modelling for identified variants predicts size and conformation modifications in mutated amino acid residues that lead to damaging effects in the conserved domains expressed as neurological pathophysiology. The present study widens the diversely ethnic and highly inbred gene pool of Punjab, Pakistan population for spontaneously originated deleterious mutations and contributes to the continuously expanding phenotypic canvas. Molecular genetic identification and personalized diagnosis for the patients suffering from complicated neurodevelopmental phenotypes, for better care, management of day-to-day activities and prolonged life span are the utmost hopes.

Bimetallic doped carbon dot nanozymes for enhanced sonodynamic and nanocatalytic therapy.

Conventional inorganic semiconductors are not suitable for acting as nanozymes or sonosensitizers for in vivo therapeutic nanomedicine owing to the lack of excellent biocompatibility. Biocompatible carbon dots (CDs) exhibit a variety of biological activities due to their adjustable size and surface chemical modification; however, the simultaneous sonodynamic activity and multiple enzyme-mimicking catalytic activity of a single CD have not been reported. Herein, we report the development of bimetallic doped CDs as a high-efficiency nanozyme and sonosensitizer for enhanced sonodynamic therapy (SDT) and nanocatalytic therapy (NCT). By selecting metal-organic complexes like EDTA-FeNa as the carbon source, we ensure that the coordination environments of metal atoms are preserved throughout the low-temperature calcination process. Compared with the single metal doped CDs including Fe-CDs or Ni-CDs, the obtained Fe and Ni co-doped CDs (Fe-Ni-CDs) not only exhibit enhanced sonodynamic activity owing to the decreased bandgap, but also possess augmented dual enzyme-mimicking catalytic activities due to the synergistic effect of bimetallic ions. The Fe-Ni-CD-mediated cascade amplification of ROS generation could lead to the production of 1O2 and O2˙- through SDT, the generation of ˙OH through POD-mimicking catalytic activity, and the provision of more O2 for SDT through CAT-mimicking catalytic activity. Through the integrated multifunctionality of Fe-Ni-CDs, we successfully enhanced the effectiveness of antitumor treatment with a single drug injection and a single US irradiation for enhanced SDT and NCT. This work provides a distinct paradigm of endowing CDs with sonodynamic and multiple enzyme-mimicking catalytic activities for enhanced SDT and NCT through bimetallic ion doping.

Quantifying the growth mechanism of solid-state nanopores under high-voltage conditioning.

Solid-state nanopores exhibit dynamically variable sizes influenced by buffer conditions and applied electric field. While dynamical pore behavior can complicate biomolecular sensing, it also offers opportunities for controlled, in situ modification of pore size post-fabrication. In order to optimally harness solid-state pore dynamics for controlled growth, there is a need to systematically quantify pore growth dynamics and ideally develop quantitative models to describe pore growth. Using high-voltage pulse conditioning, we investigate the expansion of nanopores and track their growth over time. Our findings reveal that pore growth follows a two-regime model: an initial transient regime characterized by an exponential rise, followed by a steady-state regime with linear growth. The pore growth rate increases with voltage, while the duration of the transition regime decreases with voltage. We propose a simple electrochemical etching model based on hydrolysis and solute removal to quantify time-dynamics of growing pores and rationalize the mechanism of electric-field driven pore growth, with numerical solutions aligning closely with experimental data. These insights enhance the understanding of nanopore conditioning, providing a theoretical framework for controlled pore size modification.

Review on molecular designing of polymeric carriers use in gene therapy for diabetes

Gene therapy holds promise for treating diabetes by addressing its root causes at the molecular level. A key factor in its success is the development of effective delivery systems, with polymeric carriers emerging as versatile vehicles. This review highlights the molecular design of polymeric carriers for diabetes gene therapy, focusing on critical parameters like polymer structure, size, charge, and surface modification that influence gene encapsulation and release. Biodegradable polymers such as PLGA, chitosan, and PEI are emphasized for their ability to protect therapeutic genes and enable controlled release. In diabetes, these carriers aim to deliver genes that modulate insulin production, enhance β-cell regeneration, or prevent immune-mediated destruction. The review also explores stimulus-responsive polymers that offer on-demand release based on glucose levels. Recent preclinical and clinical studies are discussed, addressing challenges and strategies for optimizing polymeric carriers. These molecular design insights could pave the way for safer, more efficient gene delivery systems in diabetes treatment. This abstract emphasizes the design principles, challenges, and emerging strategies in polymeric carrier systems for gene therapy in diabetes.

The Furan-Thiol-Amine Reaction Facilitates DNA-Compatible Thiopyrrole-Grafted Macrocyclization and Late-Stage Amine Transformation.

We here report an efficient DNA-compatible furan-thiol-amine reaction for macrocyclization and late-stage amine transformation. This reaction, conducted under mild conditions, enables the facile cyclization of DNA-conjugated linear peptides into thiopyrrole-grafted macrocycles regardless of ring size or side-chain modification with good to excellent conversion yields. Additionally, this strategy was employed for the late-stage transformation of terminal amines, serving as critical intermediates in the construction of DNA-encoded peptide libraries. Diverse amines were successfully converted into their corresponding thiopyrrole scaffolds, thereby expanding the structural diversity that can be achieved within DNA-encoded libraries.

A review of acolorimetric biosensor based on Fe3O4 nanozymes for food safety detection.

The issue of food safety poses a significant threat to human health. The colorimetric sensing method offers ahighly sensitive response, visualization, and easy operation, making it highly promising for applications in the field of bioanalysis. Fe3O4 nanomaterials not only possess the advantages of astraightforward preparation method, customizable functionalities, and facile surface modification, but also exhibit excellent peroxidase activity. The colorimetric biosensor based on aFe3O4 nanozyme is highly sensitive and has a low detection limit, making it widely recognized in the field of food safety detection. The review provides a summary of synthesis methods for Fe3O4 nanozymes and discusses the effects of different synthesis methods on their structures. Additionally, the catalytic mechanism of theFe3O4 nanozyme and the influence of particle size, structure, pH, metal doping, and surface modifications on the peroxide activity are analyzed. Finally, we introduce the application of colorimetric sensors based on Fe3O4 nanozymes in detecting antioxidants, heavy metal ions, pesticides, antibiotics, foodborne pathogen toxins, and other food additives and contaminants. This review is expected to provide reference and inspiration for future research on food safety detection through colorimetric sensors based on Fe3O4 nanozymes.

IMPLEMENTED RECONFIGURABLE CACHE MEMORY ARCHITECTURE BASED ON 32-BITS MIPS PROCESSOR

This work presents the design of a reconfigurable cache memory utilizing a 32-bit MIPS processor, implemented through the utilization of VHDL (Very high-speed IC Hardware Description Language). A comprehensive implementation of a 32-bit, single-cycle MIPS processor is presented in VHDL. This processor is capable of supporting 50 instructions, comprising 25-R-type, 16-I-type, and 9-J-type instructions. The processor incorporates a three-dimensional reconfigurable cache memory architecture, enabling the modification of cache memory size, cache organization (in terms of associativity), and cache block size. The reconfigurable cache memory concept proposes the use of multi-cache controller units to execute reconfiguration operations and ensure that all permitted cache memory sets can be utilized with varying levels of associativity. The design is built on an FPGA using the Xilinx ISE design suite, which is based on the hardware description language. To ensure that assess functionality of the proposed reconfigurable cache memory design for various reconfiguration scenarios, numerous assembly language programs have been developed and performed on the MIPS processor. The results validated the efficacy of the suggested reconfigurable cache memory concept and demonstrated its simulation using the Xilinx ISim simulator.

Golden era of radiosensitizers.

The past 30 years have brought undeniable progress in medicine, biology, physics, and research. Knowledge of the nature of the human body, diseases, and disorders has been constantly improving, and the same is true regarding their treatment and diagnosis. One of the greatest advances in recent years has been the introduction of nanoparticles (NPs) into medicine. NPs refer to a material at a nanometer scale (0.1-100 nm) with features (specific physical, chemical, and biological properties) that are broadly and increasingly used in the medical field. Their applications in cancer treatment and radiotherapy seem particularly attractive. In this field, inorganic/metal NPs with high atomic number Z have been employed mainly due to their ability to enhance ionizing radiation's photoelectric and Compton effects and thereby increase conventional radiation therapy's efficacy. The improvement NPs enable relates to their enhanced permeation ability and longer retention effect in tumor cells, capacity to reduce toxicity of commercially available cancer drugs through advanced NPs drug delivery systems, radiation sensitizers of tumors, or enhancers of radiation doses to tumors. Advanced options according to size, core, and surface modification allow even such multimodal approaches in therapy as nanotheranostics or combined treatments. The current state of knowledge emphasizes the role of gold nanoparticles (AuNPs) in sensitizing tumors to radiation. We have reviewed AuNPs and their radiosensitizing power during radiation treatment. Our results are divided into groups based on AuNPs' surface modification and/or core structure design. This study provides a complete summary of the in vivo sensitizing effect of AuNPs, surface-modified AuNPs, and AuNPs combined with different elements, providing evidence for further successful veterinarian and clinical implementation.

Genetic Heterogeneity in Four Probands Reveals HGSNAT, KDM6B, LMNA and WFS1 Related Neurodevelopmental Disorders.

Background: Neurodevelopmental disorders of genetic etiology are a highly diverse set of congenital recurrent complications triggered by irregularities in the basic tenets of brain development. Methods: We present whole exome sequencing analysis and expression characteristics of the probands from four unrelated Pakistani consanguineous families with facial dysmorphism, neurodevelopmental, ophthalmic, auditory, verbal, psychiatric, behavioral, dental, and skeletal manifestations otherwise unexplained by clinical spectrum. Results: Whole exome sequencing identifies a novel, bi-allelic, missense variant in the HGSNAT gene [NM_152419.3: c.1411G > A (p. Glu471Lys) exon 14] for proband family E-1 and a rare, bi-allelic, non-frameshift variant in the KDM6B gene [NM_001348716.2: c.786_791dupACCACC (p. Pro263_Pro264dup) exon 10] for proband family E-2, and a novel, mono-allelic, missense variant in the LMNA gene [NM_170707.4: c. 1328 A > G (p. Glu443Gly) exon 8] for proband family E-3 and an ultra-rare, mono-allelic, missense variant in the WFS1 gene [NM_006005.3: c.2131G > A (p. Asp711Asn) exon 8] for proband family E-4. Protein modelling shows conformation and size modifications in mutated residues causing damage to the conserved domains expressed as neurocognitive pathology. Conclusions: The current study broadens the distinctly cultural and genetically inbred pool of the Pakistani population for harmful mutations, contributing to the ever-expanding phenotypic palette. The greatest aspirations are molecular genetic profiling and personalized treatment for individuals with complex neurological symptoms to improve their life activities.

The Impact of Corneal Oedema on UV Light Transmission: An Experimental Study in Porcine Eyes.

Background/Objectives: Corneal oedema is known for changing the cornea's optical properties, particularly its ability to transmit ultraviolet (UV) light, which is crucial for visual clarity and eye health. This study explores how changes in corneal thickness in oedematous states affect UV light transmission. Methods: This study included 107 porcine eyes with artificially induced corneal oedema. Corneal thickness (CCT) was measured histologically, UV transmittance was assessed using a UV/VIS spectrometer, and endothelial cell parameters were evaluated with specular microscopy. Statistical analyses included the Kruskal-Wallis test, Mann-Whitney U test, and Spearman's correlation. Results: The findings indicated a significant increase in CCT in oedematous corneas at 24 and 48 h post extraction compared to controls, with median CCT values of 816.59 ± 139.71 μm for controls, 1022.40 ± 234.48 μm at 24 h, and 1074.21 ± 220.83 μm at 48 h (p < 0.001). UV transmittance (395-280 nm) decreased substantially, dropping from 50.79 ± 7.65% in controls to 43.24 ± 5.35% at 24 h and 39.66 ± 6.51% at 48 h (p < 0.001). There was a significant negative correlation between CCT and UV transmittance (ρ = -0.346, p < 0.001). Endothelial parameters showed notable changes: maximum cell area (AreaMAX) decreased at 24 and 48 h, while endothelial cell density (ECD) increased at 24 h. Conclusions: Our study found a substantial inverse link between CCT and UV light transmission in oedematous corneas, highlighting the importance of UV protection, especially in individuals who are prone to recurrent oedema. Changes in CCT and endothelial measures, such as AreaMAX and ECD, are useful signs of corneal integrity. However, the study's small sample size and potential tissue modifications during processing need more research with bigger, in vivo samples to corroborate these findings and improve therapeutic use.

Sustainable alloy design: Fe-enhanced Ti alloys for superior mechanical performance in additive manufacturing

The use of titanium (Ti) in the additive manufacturing (AM) industry has been steadily increasing. However, iron (Fe), a significant impurity originating from the sponge production process, is difficult to remove due to high energy requirements. Consequently, fully eliminating Fe from Ti is challenging and expensive. Understanding the role of Fe in Ti alloys and determining a maximum allowable threshold for AM is therefore critical. This knowledge could potentially relax current industry standards and enable the development of more sustainable Ti alloys. This study investigated the effect of Fe on the microstructure development and mechanical properties of Ti-Fe alloys, with a focus on their suitability for additive manufacturing. Through an in-situ alloying approach, Fe content was systematically increased from 0 to 3 wt%, leading to significant grain size reduction, from over 100 μm to less than 5 μm. These modifications in grain size and morphology, achieved by adjusting the Fe content in laser-based powder bed fusion (LPBF) fabricated Ti alloys, are directly related to substantial enhancements in the mechanical properties. The hardness increased from 171 to 366 HV, and the tensile strength effectively doubled from 426 to 1026 MPa while maintaining ductility. XRD analysis revealed the presence of a full α phase when the Fe content was ≤ 0.75 wt%. However, at higher Fe concentrations, small β peaks were observed. To identify the strengthening mechanisms, theoretical frameworks such as the Hall-Petch relationship and Labusch model were employed. Two significant inflection points were identified at Fe concentrations of 0.1 % and 1 wt%, indicating three important compositional ranges: Region #1 (Fe ≤ 0.1 wt%), Region #2 (0.1–1 wt% Fe), and Region #3 (1–3 wt% Fe). The strengthening mechanism in each region is discussed in detail.

MoS2 Nanosheets at Low Doses Induced Cardiotoxicity in Developing Zebrafish via Ferroptosis: Influence of Lateral Size and Surface Modification.

The widespread applications of molybdenum disulfide (MoS2) nanosheets inevitably result in their release into aquatic environments, necessitating an exploration of their potential toxic effects on aquatic organisms. This study analyzes the cardiac responses of zebrafish larvae exposed to MoS2, with a focus on the influence of size and surface modifications. At higher concentrations (1 and 5 mg/L), MoS2 nanosheets hampered larval growth without influencing cardiomyogenesis. At lower doses (0.5-100 μg/L), small-sized MoS2 (ssMoS2, 187.2 nm) significantly impaired cardiac development, as proved by morphology abnormality, decreased heartbeat, stroke volume, and cardiac output, whereas these undesirable changes were not observed in the cysteine-modified form. Large-sized nanosheets (1.638 μm) did not localize to the heart, barely showing a cardiac disorder. Transcriptomics, biochemical analysis, and computational simulation validated that ssMoS2 aggravated Fe2+ overload through excessive ferritinophagy and ferroportin-1 inhibition, accompanied by down-regulation of glutathione peroxidase 4 and activation of PUFAs esterification, leading to ferroptosis. Significant associations between ferroptosis signals and cardiac indices, along with the ferrostatin-1 inhibition test, confirmed the ferroptosis-mediated cardiotoxicity of ssMoS2. Our study provides a key understanding of molecular events underlying MoS2-induced cardiotoxicity and highlights the importance of size and surface characteristics, which are significant for risk assessment and the safe design of nanoproducts.

In Vivo Screening of Barcoded Gold Nanoparticles Elucidates the Influence of Shapes for Tumor Targeting

AbstractGold nanoparticles (NPs) are promising for cancer therapy due to their versatile shapes, optical properties, adjustable sizes, and facile functionalization. However, their diverse physicochemical properties, complex in vivo environments, and cellular heterogeneity lead to markedly different interactions with cells, impacting reproducibility and application selection. To address this, we implemented a DNA barcoding system to label gold NPs with varying shapes, sizes, and surface modifications for tumor delivery optimization. Six NP species, comprising three shapes (sphere, rod, triangle) and two sizes (40 nm, 80 nm), were tagged with unique DNA barcodes. Barcodes demonstrated minimal detachment, no interference with cell interactions, and resistance to DNase digestion. Next‐generation sequencing revealed that sphere NPs exhibited poor in vitro uptake but superior in vivo tumor targeting, likely due to enhanced endothelial interactions and reduced macrophage clearance. Additionally, 80 nm nanotriangles displayed excellent tumor targeting both in vitro and in vivo. Supporting experiments validated these findings. To demonstrate practical utility, the NPs were applied in siRNA delivery and photothermal therapy in a breast tumor model. This study pioneers the integration of DNA barcoding with gold NPs to systematically explore shape, size, and surface modifications for in vivo delivery.

Annular cement sheath characterization and hydraulic aperture assessment through single- and two-phase seepage tests

The integrity of well barriers is critical throughout the life cycle of oil and gas wells, with annular cement as a key component in maintaining the structural integrity of the barrier system. In this study, an annular cemented section with a well-defined microannulus was systematically constructed and characterized, and both single- and two-phase seepage tests were conducted to gain a deeper understanding of how relative permeability impacts the estimation of hydraulic aperture in potential leakage pathways. The test cell design allows modification of the microannulus gap size by changing the pressure applied inside the inner casing. This enables studying different microannulus sizes throughout the conducted tests. The single-phase seepage tests showed consistent measurements of hydraulic aperture for both gas and water, despite variations in fluid type and applied pressure, with surface roughness likely affecting the non-linear behavior of the hydraulic aperture under stress. The two-phase seepage tests demonstrated a clear relationship between breakthrough pressure and microannulus size, with the van Genuchten model providing a better fit for relative permeability and capillary pressure data. Breakthrough time experiments revealed that initial permeability estimations were significantly lower than those obtained from single-phase tests; however, once relative permeability at breakthrough was accounted for, the estimated absolute permeability values aligned closely with the single-phase experimental data. These findings offer valuable insights into the complex interactions between cement sheath integrity and gas migration, potentially contributing to developing new well integrity assessment technologies, including tracer gas below the well barrier element, as well as insights relevant for both gas migration and sustained casing pressure analysis.

(Invited) A Study of Si-based Metallic Glass Anodes for Li-ion Batteries

Silicon has been considered a promising low-cost negative electrode material for high-energy lithium-ion batteries due to its high gravimetric (400 Wh kg–1) and volumetric energy density (> 800 Wh L–1), low operating voltage (~0.3 V) and abundance in the Earth crust. During the past decades, development of Si-based negative electrodes has been greatly accelerated by modification of morphology, size, composition, and surface engineering. Accordingly, the cycle life of Si-based cells has improved dramatically over the years and is now approaching performance targets showing > 300 Wh kg–1 even after 1,000 cycles. However, as Si is gradually adopted into commercial batteries, the calendar life of the Si-based cells with high silicon content (>40%) is identified to be insufficient (1-2 years) and thus represents a major roadblock to widespread deployment. Interfacial instability of silicon in organic carbonate carbonate electrolytes and continuous electrolyte decomposition lead to a gradual electroyte consumption and shift of active lithium inventory in the cell. A steady growth of the SEI layer accompanies is linked with active lithium loss, which causes severe cell capacity fade and impedance rise. To prevent such a Si negative electrode and cell degradation mechanism, it is essential to exercise better control over the kinetics of electrolyte reduction and SEI layer formation process.Among various approaches to improve the interfacial as well as mechanical stability of silicon, embedding metallic inactive phases into amorphous Si matrix was widely studied. Dahn et al. has demonstrated this idea through a series of studies of over 200 different Si-based amorphous alloys1-3. Amorphous Si-alloys suppress two-phase coexistence of the Li-rich and Li-poor phase which leads to lattice mismatch and crack propagation. Thus, amorphous alloy films showed better capacity retention with less swelling and particle collapse. Furthermore, the inactive metal matrix serves as a buffer for the large volume expansion of Si (~280%), thus improving cycle stability without a significant decrease in the volumetric energy density.In this study we report on the synthesis and evaluation of Silicon-Me amorphous alloys (Me: Ni, Cu, Mn, Ti, Fe) for applications as negative electrodes in high-energy density Li-ion batteries with improved calendar life. Numerous Si-Me metallic glass alloy model electrodes were synthesized, using ultra-fast laser and splat quenching techniques to screen, evaluate, and optimize their electrochemical performance with a focus on the long-term interfacial stability in Li-ion batteries. Si0.85Ni0.15 has emerged as the best performing metallic glass alloy composition and its fabrication was successfully scaled-up with melt spinning technique. The melt-spun Si0.85Ni0.15 thin ribbon was ball-milled into fine powder to be used in conventional composite electrode fabrication for Li-ion batteries. Metallic glass Si0.85Ni0.15 anode showed improved passivation behavior and outperformed a conventional nano-sized Si electrode in both cycle and calendar life tests.AcknowledgementsThis research was supported by the US Department of Energy (DOE)’s Vehicle Technologies Office under the Silicon Consortium Project directed by Brian Cunningham and managed by Anthony Burrell. The work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231. This research also used resources of the Advanced Light Source, a U.S. DOE Office of Science User Facility under contract no. DE-AC02-05CH11231; in particular, Beamline 2.4 was used. Melt-spinning production rates and metrics are provided from ECO FM Co. References Fleischauer, M. D.; Dahn, J. R., Combinatorial Investigations of the Si-Al-Mn System for Li-Ion Battery Applications. J. Electrochem. Soc. 2004, 151 (8), A1216.Hatchard, T. D.; Topple, J. M.; Fleischauer, M. D.; Dahn, J. R., Electrochemical Performance of SiAlSn Films Prepared by Combinatorial Sputtering. Electrochemical and Solid-State Letters 2003, 6 (7), A129.Fleischauer, M. D.; Topple, J. M.; Dahn, J. R., Combinatorial Investigations of Si-M (M = Cr + Ni, Fe, Mn) Thin Film Negative Electrode Materials. Electrochemical and Solid-State Letters 2005, 8 (2), A137.

(Invited) air/Liquid Interfacial Formation Process of Electrically Conductive Metal-Organic Framework Nanosheets

Development of rational methods for creating ordered two-dimensional (2D) structures with nanometer scale precision is one of the central issues in the nanoscience and nanotechnology fields because of their intrinsic physical-chemical properties which are seen in those of their equivalent bulk state. Inclusion of highly regulated nanopores into the nanosheet structure will further open the possible applications such as nanosieves, molecular/ion storage and sensor devices as well as introducing guest molecules into the nanopores tune variedly the sheet properties (electric conduction, nanoheterojunction). Utilizing molecular building units are suitable for creating such porous nanosheets because of rich variety of design and facile modification of size and shape.Here, I present a facile bottom-up synthesis of molecular nanosheets with both positional and size regulated nanopores utilizing air/liquid interfaces[1-5]. By applying liquid interfaces, growth direction of the object can be well controlled with utilizing self-assembly feature of the molecules under mild conditions. We have succeeded to tune finely the nanosheet structures by rational modification of molecular building units . The highly crystalline structure remains after transferring a solid substrate from the liquid surface as well as without any supports. Notably, such highly oriented porous crystalline structure is obtained specifically by applying bottom up synthesis at air/liquid interfaces, not by other techniques.I also present detailed insights into the formation process of electrically conductive MOF nanosheets composed of 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and Ni(II) ions (HITP-Ni-NS) at the air/liquid interface [6-8]. The morphological and structural features of HITP-Ni-NS strongly depend on the standing time—the time without any external actions involved, but leaving the interface undisturbed after setting the ligand solution onto the metal-ion solution. We find that the fundamental features of HITP-Ni-NS are determined by the standing time with conductivity sensitively influenced by such pre-determined HITP-Ni-NS characteristics. These findings will lead towards the establishment of a rational strategy for creating MOF nanosheets at the air/liquid interface with desired properties, thereby accelerating their use in diverse potential applications.1. R. Makiura et al. Nature Mater. 9, 565 (2010).2. S. Motoyama, R. Makiura, O. Sakata, H. Kitagawa, J. Am. Chem. Soc. 133, 5640 (2011).3. R. Makiura, O. Konovalov, Sci. Rep. 3, 2506 (2013).4. R. Makiura et al. ACS Nano, 11, 10875–10882 (2017).5. R. Makiura et al, Coord. Chem. Rev. 469, 214650 (2022).6. R. Makiura et al, ACS Appl. Mater. Interfaces, 13, 54570 (2021).7. R. Makiura et al, J. Colloid Interface Sci. 651, 769 (2023).8. R. Makiura et al, Langmuir. 39, 8952 (2023). Figure 1

Early autonomous patterning of the anteroposterior axis in gastruloids.

Minimal in vitro systems composed of embryonic stem cells (ESCs) have been shown to recapitulate the establishment of the anteroposterior (AP) axis. In contrast to the native embryo, ESC aggregates - such as gastruloids - can break symmetry, which is demarcated by polarization of the mesodermal marker T, autonomously without any localized external cues. However, associated earliest patterning events, such as the spatial restriction of cell fates and concomitant transcriptional changes, remain poorly understood. Here, we dissect the dynamics of AP axis establishment in mouse gastruloids, particularly before external Wnt stimulation. Through single-cell RNA sequencing, we identify key cell state transitions and the molecular signatures of T+ and T- populations underpinning AP polarization. We also show that this process is robust to modifications of aggregate size. Finally, transcriptomic comparison with the mouse embryo indicates that gastruloids develop similar mesendodermal cell types, despite initial differences in their primed pluripotent populations, which adopt a more mesenchymal state in lieu of an epiblast-like transcriptome. Hence, our findings suggest the possibility of alternate ESC states in vivo and in vitro that can converge onto similar cell fates.

Cellulose nanocrystals (CNCs) with different degrees of amination to enhance tolerance to Fe (III) and enhance oil displacement performance

Cellulose nanocrystals (CNCs) have been widely concerned in enhanced oil recovery (EOR) due to their abundant resources, small size and easy modification. In crude oil extraction, Fe (III) is increasingly produced. However, CNCs are very sensitive to Fe (III) and easy to aggregate, which brings obstacles to the application of CNCs. In order to improve the tolerance of CNCs to Fe (III), the surface of CNCs was modified with Aminopropyltrimethoxysilane (APTMS), N-[3-Trimethoxysilyl)propyl]ethylenediamine (TMPED) and N-[3-(trimeth-oxysilyl)propyl]diethylenetriamine (TMPDET), respectively. The products were named CNC-APTMS, CNC-TMPED and CNC-TMPDET. The N content in CNC-APTMS, CNC-TMPED and CNC-TMPDET are 1.36 wt%, 2.03 wt% and 2.17 wt%, respectively. The adsorption amount of Fe (III) by CNCs, CNC-APTMS, CNC-TMPED and CNC-TMPDETDT are ∼155 mg/g, ∼ 13 mg/g, ∼ 29 mg/g and ∼ 18 mg/g, respectively. This indicates that compared to CNCs, the modified CNCs improve significantly the tolerance to Fe (III). Moreover, compared to CNCs, in the presence of Fe (III), there is less remaining oil in the glass model after modified CNCs dispersion flooding. The improvement of tolerance to Fe (III) and the excellent oil displacement performance of the modified CNCs in the presence of Fe (III) make them the potential green oil displacement agents.