Narrow Distribution Research Articles

Ca2+/CaM dependent protein kinase II (CaMKII)α and CaMKIIβ hub domains adopt distinct oligomeric states and stabilities.

Ca2+ /calmodulin-dependent protein kinase II (CaMKII) is a multidomain serine/threonine kinase that plays important roles in the brain, heart, muscle tissue, and eggs/sperm. The N-terminal kinase and regulatory domain is connected by a flexible linker to the C-terminal hub domain. The hub domain drives the oligomeric organization of CaMKII, assembling the kinase domains into high local concentration. Previous structural studies have shown multiple stoichiometries of the holoenzyme as well as the hub domain alone. Here, we report a comprehensive study of the hub domain stoichiometry and stability in solution. We solved two crystal structures of the CaMKIIβ hub domain that show 14-mer (3.1 Å) and 16-mer (3.4 Å) assemblies. Both crystal structures were determined from crystals grown in the same drop, which suggests that CaMKII oligomers with different stoichiometries likely coexist. To further interrogate hub stability, we employed mass photometry and temperature denaturation studies of CaMKIIβ and CaMKIIα hubs, which highlight major differences between these highly similar domains. We created a dimeric CaMKIIβ hub unit using rational mutagenesis, which is significantly less stable than the oligomer. Both hub domains populate an intermediate during unfolding. We found that multiple CaMKIIβ hub stoichiometries are present in solution and that larger oligomers are more stable. CaMKIIα had a narrower distribution of molecular weight and was distinctly more stable than CaMKIIβ.

Synergistic structural and electronic influences of Pt bead catalysts on dehydrogenation activity for liquid organic hydrogen carriers

Alumina-supported Pt bead catalysts with uniform (PtU/θ-Al2O3) or egg-shell (PtE/θ-Al2O3) structure and their corresponding potassium-doped counterparts (K-PtU/θ-Al2O3, K-PtE/θ-Al2O3) were synthesized to elucidate the influence of structure-induced active metal distribution and promotor on the dehydrogenation of liquid organic hydrogen carriers (LOHCs). Characterizations of the catalysts confirmed that different synthetic methods led to distinct Pt distributions on the Al2O3 surface. PtE/θ-Al2O3 and K-PtE/θ-Al2O3 had an average size of 1 nm with narrow Pt distributions while PtU/θ-Al2O3 and K-PtU/θ-Al2O3 exhibited bimodal distributions in Pt particle size (<0.2 nm and <0.8 nm), which also influenced the oxidation states. Introducing the promotor (K) facilitated electron transfer into Pt, which resulted in a more metallic state. When applied to the dehydrogenation of two different LOHCs, including methylcyclohexane and perhydro-monobenzyltoluene, K-PtE/θ-Al2O3 exhibited superior catalytic activity and durability compared to other catalysts. The improved activity of K-PtE/θ-Al2O3 was primarily attributed to the combined electronic influences of the catalyst bulk structure and promotor.

Flexural properties and fatigue limit of 3D-printed and milled resin-based materials.

The purpose of this study was to evaluate the flexural strength (FS), flexural modulus (FM), and fatigue limit (FL) of 3D-printed resin-based polymers and composites and compare them to 3D-printed composites. A bar-shaped specimen (25×2×2mm) was CAD designed according to ISO 4049:2019, and 60 duplicates of the 3D model were nested at a 45-degree angle with the printing platform and 3D-printed with three materials: denture teeth resin (Denture Teeth, Formlabs), temporary crown and bridge resin (Temporary CB, Formlabs), and composite (Flexcera Smile Ultra+, Desktop Health). The 3D model was also imported into a dental CAM software, duplicated 60 times, nested, and milled from a 3D-milled composite puck (Ivotion Denture Teeth, Ivoclar). All specimens were post-processed following the manufacturer's recommendation. The specimens were then subjected to a three-point bending test until failure using a Universal Testing Machine at a crosshead speed of 0.75mm/min, and FS and FM were calculated. The remaining thirty specimens were tested for Fatigue Limit using the staircase approach starting at 50% FS maximum up to 1.2M cycles at 10Hz. The data were analyzed using one-way ANOVA and the Weibull distribution (α = 0.05). The results showed that Ivotion and Flexcera had higher FS (110.3 ± 7.1MPa and 107.6 ± 6.4MPa, respectively) and FM (3.3 ± 0.1GPa and 3.0 ± 0.2GPa, respectively) compared to the 3D-printed Denture Teeth (FS = 66.4 ± 18.5MPa and FM = 1.8 ± 0.1GPa) and Temporary CB (FS = 79.6 ± 12.1MPa and FM = 2.7 ± 0.4GPa). Weibull analysis showed that the Ivotion and Flexcera had a more uniform and narrower spatial distribution of defects (m: 27.98 and 29.19) than the printed materials, which had m values of 8.17 and 4.11 for Temporary CB and Denture Teeth, respectively. Although no differences were found in the static properties (FS and FM) between Ivotion and Flexcera, Ivotion presented a higher endurance limit than Flexcera (51.43 vs. 40.95MPa). The Temporary CB presented 21.08MPa and Denture Teeth presented 17.80MPa of endurance limit. 3D-milled (Ivotion Denture Teeth) and 3D-printed (Flexcera Smile Ultra+) composites outperformed 3D-printed resins (Formlabs Denture Teeth and Temporary Crown & Bridge) in terms of flexural properties and fatigue resistance. 3D-milled (Ivotion) and 3D-printed (Flexcera) composites exhibited similar flexural properties, but 3D-milled composites showed a 25% higher fatigue endurance limit, suggesting improved clinical longevity.

Effect of short-chain branches in high-molecular-weight component on tensile properties of polyethylene solids

The effects of short-chain branches (SCBs) in the high-molecular-weight (MW) chains on the solid-state tensile properties of polyethylene (PE) have been investigated using blend samples of linear PE with a polydisperse MW distribution and PE with very narrow MW distribution and SCBs with four carbons. The introduction of SCBs in the high-MW chains had almost no effect on the crystalline structure, but relaxation of the interlamellar amorphous chains was only activated by blending the high-MW chains with a large fraction of SCBs (2.0 wt%). The blends of PE with 0.4 wt% SCBs resulted in significant increases in the strain-hardening modulus and strength without greatly decreasing the strain at break. The improvement in the strain-hardening modulus and strength by adding a small amount of SCBs (0.4 wt%) was significant compared with the improvement by adding linear PE or branched PE with a large amount of SCBs (2.0 wt%). For a small amount of SCBs, the SCBs will be incorporated into the crystalline structure, which enhances the fragmentation and subsequent orientation of the crystalline structure under yielding deformation. Consequently, blending the branched PE with a small amount of SCBs in the high-MW chains leads to significant improvement of the tensile properties.

Interannual Variation of Half-Hourly Extreme Precipitation in Africa: The Assessment of the Warmest Decade (2011–2020) Since the Beginning of Observations

AbstractAfrica is experiencing widespread extreme precipitation. However, the continent remains understudied regarding extreme precipitation variation, particularly at high temporal resolution. This study assessed the changes in spatial distribution, frequency, and intensity of half-hourly violent precipitation (≥ 50 mm/h) in Africa during 2011–2020. The data were sourced from the Integrated MultisatellitE Retrievals for Global Precipitation Measurement (IMERG) program. The results reflect that the 50–60 mm/h precipitation category was the most densely spatially distributed with less-discernable interannual changes. There was a strong interannual variation in the spatial distribution of the 60–70 mm/h and ≥ 70 mm/h precipitation categories. There was a general decrease in the frequency of occurrence of violent precipitation in all regions, except in North Africa (NA). Among the study regions, NA had the broadest precipitation intensity distribution extended to high values and consequently, on average, the most intense violent precipitation, followed by Southern Africa (SA) and Southwest Indian Ocean (SWIO). The regions in the tropics, i.e., West Africa (WA), Central Africa (CA), and East Africa (EA), had a relatively narrow intense violent precipitation distribution. The results further illustrate that the strength of climate variability modes has a strong influence in the distribution, frequency, and intensity of violent precipitation over the continent particularly the ≥ 70 mm/h precipitation category. This study underscores a need for a strengthened capacity in forecasting climate variability modes impacting on Africa, augmentation of continental precipitation observation network, and improved extreme precipitation adaptation infrastructure.

The pancancer overexpressed NFYCAntisense 1 controls cell cycle mitotic progression through in cis and in trans modes of action

Antisense RNAs (asRNAs) represent an underappreciated yet crucial layer of gene expression regulation. Generally thought to modulate their sense genes in cis through sequence complementarity or their act of transcription, asRNAs can also regulate different molecular targets in trans, in the nucleus or in the cytoplasm. Here, we performed an in-depth molecular characterization of NFYCAntisense1 (NFYC-AS1), the asRNA transcribed head-to-head to NFYC subunit of the proliferation-associated NF-Y transcription factor. Our results show that NFYC-AS1 is a prevalently nuclear asRNA peaking early in the cell cycle. Comparative genomics suggests a narrow phylogenetic distribution, with a probable origin in the common ancestor of mammalian lineages. NFYC-AS1 is overexpressed pancancer, preferentially in association with RB1 mutations. Knockdown of NFYC-AS1 by antisense oligonucleotides impairs cell growth in lung squamous cell carcinoma and small cell lung cancer cells, a phenotype recapitulated by CRISPR/Cas9-deletion of its transcription start site. Surprisingly, expression of the sense gene is affected only when endogenous transcription of NFYC-AS1 is manipulated. This suggests that regulation of cell proliferation is at least in part independent of the in cis transcription-mediated effect on NFYC and is possibly exerted by RNA-dependent in trans effects converging on the regulation of G2/M cell cycle phase genes. Accordingly, NFYC-AS1-depleted cells are stuck in mitosis, indicating defects in mitotic progression. Overall, NFYC-AS1 emerged as a cell cycle-regulating asRNA with dual action, holding therapeutic potential in different cancer types, including the very aggressive RB1-mutated tumors.

Hybrid anionic block copolymerization: From organocatalysis‐streamlined crossover to internally microphase‐separated aggregates

AbstractPolyolefin‐b‐poly(ethylene oxide) (PEO) represents the most widely investigated amphiphilic block copolymers. So far, one‐pot continuous synthesis of such hybrid block copolymers has only been fulfilled by anionic polymerization through sequential addition of vinyl monomers and ethylene oxide (EO). It still remains challenging to achieve altogether high block efficiency, high polymerization efficiency, and high molar mass for PEO. Here, we report a one‐pot hybrid block copolymerization approach to polyisoprene/polystyrene(PI/PS)‐b‐PEO, in which PI/PS are formed by sBuLi‐initiated anionic vinyl‐addition polymerization, then in situ employed as macroinitiators for the anionic ring‐opening polymerization (ROP) of EO aided by an organic Lewis pair. The cooperative (dual‐ion‐complexing) catalytic effect of organobase and triethylborane is proven, for the first time, effective for lithium alkoxide initiator system, allowing to achieve at room temperature high ROP activity (complete EO conversion and PEO of 3–64 kg/mol reached in 1–6 h), narrow molar mass distribution, controlled block lengths and composition. Density functional theory calculation shows that phosphazene bases are particularly effective, compared with N‐heterocyclic bases, for complexing with Li+ and enhancing the nucleophilicity of oxyanion. The rate of ROP is also affected by Li+‐induced aggregation of the chain‐end ion pairs, which though can be offset by adequate catalyst loadings. The versatility of this approach is further demonstrated in the one‐pot synthesis of tri‐/tetrablock ter‐/quaterpolymers constituted by PI, PS, PEO, and poly(propylene oxide). Of great interest, PS‐b‐PI‐b‐PEO triblock terpolymer with a specific composition is found to form internally microphase‐separated micellar aggregates when dispersed in water.

Magneto-thermal limitations in superconducting cavities at high radio-frequency fields

The performance of superconducting radio-frequency Nb cavities at high radio-frequency (rf) fields in the absence of field emission can be limited by either a sharp decrease of the quality factor Q0(Bp) above peak surface magnetic fields Bp ∼100 mT or by a quench. We have measured Q0(Bp) at 2 K of several 1.3 GHz single-cell Nb cavities with different grain sizes, and with different ambient magnetic fields and cooldown rates below the critical temperature. Temperature mapping and a novel magnetic field mapping systems were used to find the location of “hot-spots” and regions of trapped magnetic flux. The use of a variable input coupler allowed further exploring the dissipative state. The results showed a remarkable thermal stability in some cavities with up to 200 W of rf power dissipation at 2 K, whereas other cavities quenched at much lower rf power. We observed a narrow distributions of the onset fields of hot-spots which were not affected by thermal cycling or by conditions which favor the formation of Nb hydrides. Furthermore, a poor correlation was found between the location of hot-spots and trapped vortices. We suggest that the totality of our experimental data can be explained by a sharp increase of the residual surface resistance above 120–140 mT due to the field-induced breakdown of a proximity-coupled metallic suboxide layer at the surface.

Synthesis of alternating copolymer PAspNa‐alt‐PAsp(Pr) for drug delivery system

AbstractAlternating copolymers (ACs) contain two distinct monomeric unit types dispersed in alternating order of hydrophilic block and hydrophobic block. ACs have extensive and versatile applications in both academia and industry, especially in drug delivery systems (DDS) due to their unique physical and chemical properties. In the present research, poly(β‐benzyl l‐aspartate) (PBLA) was prepared by ring‐opening polymerization of BLA‐NCA. The result obtained from GPC showed that PBLA was successfully synthesized with narrow weight distribution Mw/Mn = 1.055. The outcome of copolymer has the degree of polymerization (DP) of PBLA was 50 based on the 1H NMR spectroscopy. Further, alternating copolymer poly(aspartate‐sodium) alternating poly(aspartate‐R) (PAspNa‐alt‐PAsp(Pr)), which allows the installation of expected compounds into a polymer backbone of PBLA without unwanted side effects, was synthesized via 2 steps: (1) aminolysis by 0.5 fold primary amine to attach hydrophobic group and (2) hydrolysis slowly by NaOH solution to form the hydrophilic group on the side chain of the polymer. The novel alternating copolymer synthesized successfully in this study was expected to be a promising candidate for drug delivery devices.

Well-defined non-symmetric NHC-iron(III) catalyst for photoinduced atom-transfer radical polymerization of methyl methacrylate

Photoinduced atom transfer radical polymerization (photo-ATRP) has emerged as a prominent technique in contemporary polymer chemistry, offering a potent means to create precisely structured materials. Well-defined catalysts are essential for controlling the growth of polymers with reproducible results; however, most photo-ATRP catalytic systems involve mixing the metal salt with the ligand. Herein we present a well-defined iron(III) based photo-ATRP catalyst bearing bidentate NHC ligand, 3-Methyl-1-phenyl-1H-3,1-benzimidazol-3-ium iodide (Pmb). The [FeBr(Pmb)2] was successfully synthesized and fully characterized by FTIR, UV–Vis, and EPR spectroscopic studies, elemental analysis, MALDI-TOF mass spectrometry, and computational studies. [FeBr(Pmb)2] was employed as the catalyst for photo-ATRP of methyl methacrylate (MMA) under ultraviolet light irradiation (365 nm). The catalytic activity of [FeBr(Pmb)2] in the photo-ATRP of MMA was evaluated under different conditions using EBPA as the initiator. The polymerizations showed robust activity, yelding in polymers with controlled molecular weights and a narrow molecular weight distribution (MWD). Remarkably, this was achieved with low catalysts loading (102.6 ppm), mainly at the molar ratio [MMA]/[EBPA]/[Fe] = 200/1/0.04. Well-defined polyMMA was synthesized and temporal control over photo-ATRP was successfully demonstrated through “on/off” experiments. For example, photo-ATRP of MMA with a molar ratio of [200/1/0.04] after 12 h at T = 25 °C in bulk resulted in PMMA with a polydispersity (Ð) of 1.15 at 50 % monomer conversion.

Photon-Momentum-Enabled Electronic Raman Scattering in Silicon Glass.

The nature of enhanced photoemission in disordered and amorphous solids is an intriguing question. A point in case is light emission in porous and nanostructured silicon, a phenomenon that is still not fully understood. In this work, we study structural photoemission in heterogeneous cross-linked silicon glass, a material that represents an intermediate state between the amorphous and crystalline phases, characterized by a narrow distribution of structure sizes. This model system shows a clear dependence of photoemission on size and disorder across a broad range of energies. While phonon-assisted indirect optical transitions are insufficient to describe observable emissions, our experiments suggest these can be understood through electronic Raman scattering instead. This phenomenon, which is not commonly observed in crystalline semiconductors, is driven by structural disorder. We attribute photoemission in this disordered system to the presence of an excess electron density of states within the forbidden gap (Urbach bridge) where electrons occupy trapped states. Transitions from gap states to the conduction band are facilitated through electron-photon momentum matching, which resembles Compton scattering but is observed for visible light and driven by the enhanced momentum of a photon confined within the nanostructured domains. We interpret the light emission in structured silicon glass as resulting from electronic Raman scattering. These findings emphasize the role of photon momentum in the optical response of solids that display disorder on the nanoscale.

Schottky contacts on sulfurized silicon carbide (4H-SiC) surface

In this Letter, the effect of a sulfurization treatment carried out at 800 °C on silicon carbide (4H-SiC) surface was studied by detailed chemical, morphological, and electrical analyses. In particular, x-ray photoelectron spectroscopy confirmed sulfur (S) incorporation in the 4H-SiC surface at 800 °C, while atomic force microscopy showed that 4H-SiC surface topography is not affected by this process. Notably, an increase in the 4H-SiC electron affinity was revealed by Kelvin Probe Force Microscopy in the sulfurized sample with respect to the untreated surface. The electrical characterization of Ni/4H-SiC Schottky contacts fabricated on sulfurized 4H-SiC surfaces revealed a significant reduction (∼0.3 eV) and a narrower distribution of the average Schottky barrier height with respect to the reference untreated sample. This effect was explained in terms of a Fermi level pinning effect induced by surface S incorporation.

Rarities pattern of vascular plants in the high-altitude forests of Indian western Himalaya: Conservation implications

The assessment of plant rarity patterns and mapping of endemic species is a challenging task, however, this kind of assessment having great conservation significance. In the present study, a classification system of rarity, considering biogeographical, ecological and abundance of species was developed along with assessing the vegetation composition. Following systematic random approach of vegetation sampling, three altitude transects were sampled within each 100 m interval in three possible aspects (North-West, North-East and South-West) in the high-altitude forested zone (2000–3300 m asl) of Kedarnath Wildlife Sanctuary (KWS). The study identified a total of 295 plant species (191 genera and 70 families) in the studied region. Considering different attributes of rarity, 8- rarity groups were used for identification of rare and endemic plants. Altogether, most of the species exhibited wide geographical distribution an attribute of commonness, and few of these have narrow distributions due to habitat specificity. The lower altitudinal zone exhibited the maximum floristic diversity (184 spp.; 62.4 %), and minimum in the higher zone (134 spp.; 45.4 %). Tree species richness decreases, and its endemic subset increased along the altitudinal gradient due to remoteness, habitat heterogeneity, isolation of the areas and other environmental factors. A sharp decline was observed in the tree species richness from lower (33 spp.; 84.6 %) to higher altitude (8 spp.; 20.51 %). The species to genera ratio in the entire altitudinal range was 1.2 for trees and 1.6 for shrubs and herbs. Rarity analysis of these native and endemic species has highlighted conservation priorities at local and regional scale.

Mitogenomics reveals extremely low genetic diversity in the endangered Jilin clawed salamander: Implications for its conservation.

The Jilin clawed salamander (Onychodactylus zhangyapingi) is an endemic, endangered, and level-two protected amphibian species of China. In the context of serious threats to amphibians worldwide, conservation studies of this endangered species are urgently needed. In this study, mitogenomic conservation genetics and species distribution modeling analyses were performed for O. zhangyapingi. Sixty-three samples were collected from nine different locations, and the complete mitochondrial genome was sequenced. Population genetic analyses revealed that O. zhangyapingi exhibits only one genetic structure with extremely low nucleotide diversity. Late Pleistocene climate cooling may have led to a reduction in effective population size and extremely low mitogenomic nucleotide diversity in this salamander, and the subsequent temperature increase (~20 kya to present) provided the opportunity for rapid population growth. The continuous highly suitable region for O. zhangyapingi is only approximately 3000 km2 on the southeastern boundary of Jilin Province, China. Fortunately, there are three large forested national nature reserves within the distribution of O. zhangyapingi that can effectively protect endangered species. Our findings suggest that O. zhangyapingi is a vulnerable species with a narrow distribution and extremely low genetic diversity, and we should pay more attention to the conservation management of this species.

Efficient copper plating on glass substrates through amine-functionalized nanocomposite-immobilized silver nanoparticles

Amine-functionalized silver nanocatalyst was synthesized using polyethyleneimine (PEI) and glutaraldehyde (GA) and applied to electroless copper on the glass substrate. The formation mechanism of the polyethyleneimine-glutaraldehyde (PEI-GA) was firstly analyzed, then the polyethyleneimine-glutaraldehyde-silver (PEI-GA-Ag) was measured, which showed that the silver nanoparticles (AgNPs) were spherical with an average size of about 5 nm and a narrow particle distribution, and PEI-GA-Ag was analyzed by UV-Vis to demonstrate the synthesized AgNPs were uniformly dispersed and stable without agglomeration for a period of 10 months. The application of PEI-GA-Ag nanocomposite in the glass metallization process resulted in the formation of a complete, uniform copper layer on grit-blasted glass, which passed adhesion tests successfully without flaking. After 10 mins of electroless copper plating, the thickness of the copper layer is approximately 1 µm, displaying a sheet resistance of 0.018 Ω/square, and the resistivity is 1.8×10−6 Ωcm, which is close to that of a bulk copper. This proposes that PEI-GA-Ag has excellent stability and catalytic efficiency and can be effectively used in electroless plating processes to replace conventional expensive palladium colloid catalysts.

Well-defined star (co)polypeptides via a fast, efficient, and metal-free strategy

Polypeptides, especially star polypeptides, as a unique kind of biological macromolecules have broad applications in biomedical fields such as drug release, gene delivery, tissue engineering, and regenerative medicines due to their close structural similarity to naturally occurring peptides and proteins, biocompatibility, and amino acid functionality. However, the synthesis of star polypeptide mainly relies on the conventional primary amine-initiated ring-opening polymerization (ROP) of N-carboxyanhydrides (NCA) and suffers from low polymerization activity and limited controllability. This study proposes a fast, efficient and metal-free strategy to access star (co)polypeptides by combining the Michael reaction between acrylates and secondary aminoalcohols with the hydrogen-bonding organocatalytic ROP of NCA. This approach enables the preparation of a library of star (co)polypeptides with predesigned molecular weights, narrow molecular weight distributions, tunable arm number, and arm compositions. Importantly, this method exhibits high activity and selectivity at room temperature, making it both practical and versatile in synthesis applications.

Improved synthesis of metformin hydrochloride-sodium alginate (MH-NaALG) microspheres using ultrasonic spray drying

Metformin Hydrochloride (MH), an orally administered antidiabetic drug from the biguanide family, encounters issues of wide particle size distribution, inefficient dissolution rates and short half-life leading to excess dosage which can result in lactic acidosis. Novel approaches that yield smaller particle size and uniform distribution at higher yields are significant to tackle problems associated with solubility and optimum dosage levels of the administered drugs. In the current research related to microsphere synthesis, a controlled process based on pressure and ultrasonic nozzles for the atomization of liquid, was applied with an objective of optimizing particle size of microspheres of MH in sodium alginate, a biopolymer excipient matrix. The study carried out in spray dryer elucidated parameter optimization using one variable at a time approach by varying important parameters as inlet temperature of air (120°C–150 °C), rate of flow of feed (1.5 mL/min-3 mL/min), aspirator rate (800 rpm–1400 rpm) and polymer content in feed solution (1 g–8 g) using ultrasonic and pressure nozzles for comparison with the target output parameter as particle size and yield. While the particle size at optimum conditions were <10 μm for both types of atomization, ultrasound assisted spray drying exhibited narrower distribution compared to the pressure atomization. Particle characterization performed using SEM, optical microscopy, FTIR, XRD and DSC revealed slight deformation with no chemical interaction and slight decrease in crystalline nature of pure drug. Overall, an improved process based on the use of ultrasound with optimized parameters has been demonstrated for synthesis of MH containing microspheres.

High effects of climate oscillations on population diversity and structure of endangered Myricaria laxiflora.

Exploring the effects of climate oscillations on the population diversity and structure of endangered organisms in the Three Gorges Reservoir (TGR) area is essential for hydrological environment changes on endangered organism evolution. Myricaria laxiflora is an endemic and endangered shrub restricted to the TGR along the banks of Yangtze River, China. Recently, six natural populations of this species were newly found upstream and downstream of the TGR, whose habitats have been dramatically changed by the summer flooding regulated by large dams. To study the water level fluctuations and climatic shifts on the genetic diversity and genetic differentiation of the six natural populations, 303 individuals from six populations were analyzed based on one nuclear DNA (ITS) and four chloroplast fragments (trnL-F, psbA-trnH, rps16, and rpl16). The phylogenetic tree and significant genetic divergence identified in the cpDNA and ITS with genetic isolation and limited gene flow among regions suggested that the six populations separated well to two groups distributed upstream and downstream. The MaxEnt modeling results indicated that obvious unidirectional eastward migration via Yangtze River gorges watercourse mediated from Last Interglacial to Last Glacial Maximum were showed with the narrow scale distributions of six remnant populations and nine extirpated populations. The initial habitat fragmentation could be triggered by the accumulation of local habitat loss of the impoundment of the TGR during the Present period and might remain stable restoration with bidirectional diffusion in the Future. Divergences among M. laxiflora populations might have been induced by the drastic changes of the external environment and limited seed/pollen dispersal capacity, as the results of long-term ecological adaptability of summer flooding stress. The haplotypes of nuclear gene could be used for population's differentiation and germplasm protection. This identified gene flow and range dynamics have provided support for the gene-flow and geology hypothesis. It is also crucial for rescuing conservation to understand the impact of environmental dynamics on endangered organism evolution.

Mixed-mode size-exclusion silica resin for polishing human antibodies in flow-through mode

The polishing step in the downstream processing of therapeutic antibodies removes residual impurities from Protein A eluates. Among the various classes of impurities, antibody fragments are especially challenging to remove due to the broad biomolecular diversity generated by a multitude of fragmentation patterns. The current approach to fragment removal relies on ion exchange or mixed-mode adsorbents operated in bind-and-gradient-elution mode. However, fragments that bear strong similarity to the intact product or whose biophysical features deviate from the ensemble average can elude these adsorbents, and the lack of a chromatographic technology enabling robust antibody polishing is recognized as a major gap in downstream bioprocessing. Responding to this challenge, this study introduces size-exclusion mixed-mode (SEMM) silica resins as a novel chromatographic adsorbent for the capture of antibody fragments irrespective of their biomolecular features. The pore diameter of the silica beads features a narrow distribution and is selected to exclude monomeric antibodies, while allowing their fragments to access the pores where they are captured by the mixed-mode ligands. The static and dynamic binding capacity of the adsorbent ranged respectively between 30-45 and 25–33 gs of antibody fragments per liter of resin. Selected SEMM-silica resins also demonstrated the ability to capture antibody aggregates, which adsorb on the outer layer of the beads. Optimization of the SEMM-silica design and operation conditions – namely, pore size (10 nm) and ligand composition (quaternary amine and alkyl chain) as well as the linear velocity (100 cm/h), ionic strength (5.7 mS/cm), and pH (7) of the mobile phase – afforded a significant reduction of both fragments and aggregates, resulting into a final antibody yield up to 80% and monomeric purity above 97%.

Supported Platinum Nanoparticles Catalyzed Carbon-Carbon Bond Cleavage of Polyolefins: Role of the Oxide Support Acidity.

Supported platinum nanoparticle catalysts are known to convert polyolefins to high-quality liquid hydrocarbons using hydrogen under relatively mild conditions. To date, few studies using platinum grafted onto various metal oxide (MxOy) supports have been undertaken to understand the role of the acidity of the oxide support in the carbon-carbon bond cleavage of polyethylene under consistent catalytic conditions. Specifically, two Pt/MxOy catalysts (MxOy = SrTiO3 and SiO2-Al2O3; Al = 3.0 wt %, target Pt loading 2 wt % Pt ∼1.5 nm), under identical catalytic polyethylene hydrogenolysis conditions (T = 300 °C, P(H2) = 170 psi, t = 24 h; Mw = ∼3,800 g/mol, Mn = ∼1,100 g/mol, Đ = 3.45, Nbranch/100C = 1.0), yielded a narrow distribution of hydrocarbons with molecular weights in the range of lubricants (Mw = < 600 g/mol; Mn < 400 g/mol; Đ = 1.5). While Pt/SrTiO3 formed saturated hydrocarbons with negligible branching, Pt/SiO2-Al2O3 formed partially unsaturated hydrocarbons (<1 mol % alkenes and ∼4 mol % alkyl aromatics) with increased branch density (Nbranch/100C = 5.5). Further investigations suggest evidence for a competitive hydrocracking mechanism occurring alongside hydrogenolysis, stemming from the increased acidity of Pt/SiO2-Al2O3 compared to Pt/SrTiO3. Additionally, the products of these polymer deconstruction reactions were found to be independent of the polyethylene feedstock, allowing the potential to upcycle polyethylenes with various properties into a value-added product.