Phosphate Groups Research Articles

Enhancing the uranium (VI) adsorption performance of phosphoric acid functionalized porous silica by controlled introduction of phosphoric acid group

The post-grafting of porous silica with organic group is a common method for the synthesis of organo-functionalized silica adsorbent. However, this method usually produces adsorbents with limited adsorption performances due to the pore blocking caused by the irregular introduction of organic group. In this work, we report the controllable synthesis of phosphoric acid functionalized porous silica adsorbent based on the co-condensation method for uranium (VI) adsorptive removal with enhanced adsorption performance. Characterizations of the obtained silica verify its porous structure and confirm the homogeneous distribution of phosphoric acid groups inside the silica. This silica is able to efficiently remove 98 % of uranium from a 100 mg/L uranium (VI) solution within 10 min at a dosage of 0.6 g/L and the maximum uranium (VI) adsorption amount reaches 509 mg/g. Both adsorption capacity and adsorption rate of this silica are superior than that of the silica synthesized based on conventional post-grafting method. Moreover, this silica can be reused for five times with uranium (VI) removal efficiency above 95 % and it is well applied in adsorption column for dynamically adsorptive removal of uranium (VI) from real nuclear wastewater. Mechanism-related investigations reveal that uranium (VI) adsorption on this silica proceeds by effective ion exchange of uranium (VI) ion with either phosphoric acid or silanol group and the formation of uranyl phosphonate or uranyl silicate complex. This work provides a feasible strategy to synthesize functionalized porous silica without significant pore blocking, and demonstrates the enhancement effect of regulating surface adsorption groups on the adsorption performances of porous silica. Besides, this work offers a promising adsorbent for efficient treatment of uranium-containing nuclear wastewater and reveals the mechanism of uranium adsorption on those silica adsorbent containing phosphoric acid, thiol or thioether group.

NP-Collabs: Investigating Counterion-Mediated Bridges in the Multiply Phosphorylated Tau-R2 Repeat.

Tau is an intrinsically disordered (IDP) microtubule-associated protein (MAP) that plays a key part in microtubule assembly and organization. The function of tau can be regulated by multiple phosphorylation sites. These post-translational modifications are known to decrease the binding affinity of tau for microtubules, and abnormal tau phosphorylation patterns are involved in Alzheimer's disease. Using all-atom molecular dynamics simulations, we compared the conformational landscapes explored by the tau R2 repeat domain (which comprises a strong tubulin binding site) in its native state and with multiple phosphorylations on the S285, S289, and S293 residues, with four different standard force field (FF)/water model combinations. We find that the different parameters used for the phosphate groups (which can be more or less flexible) in these FFs and the specific interactions between bulk cations and water lead to the formation of a specific type of counterion bridge, termed nP-collab (for nphosphate collaboration, with n being an integer), where counterions form stable structures binding with two or three phosphate groups simultaneously. The resulting effect of nP-collabs on the tau-R2 conformational space differs when using sodium or potassium cations and is likely to impact the peptide overall dynamics and how this MAP interacts with tubulins. We also investigated the effect of phosphoresidue spacing and ionic concentration by modeling polyalanine peptides containing two phosphoserines located one-six residues apart. Three new metrics specifically tailored for IDPs (proteic Menger curvature, local curvature, and local flexibility) were introduced, which allow us to fully characterize the impact of nP-collabs on the dynamics of disordered peptides at the residue level.

Alkaline Phosphatase-Instructed Peptide Assemblies for Imaging and Therapeutic Applications.

Self-assembly, a powerful strategy for constructing highly stable and well-ordered supramolecular structures, widely exists in nature and in living systems. Peptides are frequently used as building blocks in the self-assembly process due to their advantageous characteristics, such as ease of synthesis, tunable mechanical stability, good biosafety, and biodegradability. Among the initiators for peptide self-assembly, enzymes are excellent candidates for guiding this process under mild reaction conditions. As a crucial and commonly used biomarker, alkaline phosphatase (ALP) cleaves phosphate groups, triggering a hydrophilicity-to-hydrophobicity transformation that induces peptide self-assembly. In recent years, ALP-instructed peptide self-assembly has made breakthroughs in biological imaging and therapy, inspiring the development of self-assembly biomaterials for diagnosis and therapeutics. In this review, we highlight the most recent advancements in ALP-instructed peptide assemblies and provide perspectives on their potential impact. Finally, we briefly discuss the ongoing challenges for future research in this field.

Eggshell derived scaffold of hydroxyapatite-ammonium bicarbonate nano-composite: Bioactivity and cytotoxicity studies

This work investigated the facile synthesis of porous scaffold eggshell derived hydroxylapatite (ESHAp) as a composite with ammonium bicarbonate (AMB) for potential biomaterial in tissue engineering application. The phase purity, composition, size, functional groups and morphology of the apatite were elucidated using high resolution transmission electron microscopy (HTEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and scanning electron microscopy (SEM). The results showed that hydroxylapatite (HAp) nanoparticles have round morphologies with average diameters between 20 nm and 80 nm, FT-IR analysis confirmed significant hydroxylapatite functional groups like carbonate, phosphate, and hydroxyl groups, while XRD analysis revealed a well crystalline monophasic HAp powder. The scaffold samples containing 10, 20, 25 and 30 % of AMB withstood a compressive stress up to 5, 20, 30 and 42 N/mm2 respectively which indicates that the compressive stress increased with the AMB content introduced as the pore forming agent. MTT assay performed using MG63 osteosarcoma cell lines showed that on comparing the sample of ESTHAp which contained 0 % AMB with other samples in the range of 0.01–1 mM, viability of above 85 % MG63 cells was achieved except for ESTHAp with 40 % AMB, which showed some level of toxicity. The cell adhesion studies of sintered ESTHAp porous scaffold with different weight percent of the pore forming agents using inverted microscopic images of MG 63 cells incubated with ESTHAp samples and treated with heat at 1000 °C appeared to be unstable in the media used with particle leaching observed, and no cells observed near to the samples.

Efficient and Stable Perovskite Solar Cells via Multi-Functional Guanylurea Phosphate Zwitterionic Bridging Strategy

Buried interface defects and residual stresses significantly impede further improvements in the efficiency and stability of perovskite solar cells (PSCs). Herein, a flame retardant guanylurea phosphate (GUP) with multisite anchors serves as the zwitterionic bridge between SnO2 and perovskite. The phosphate groups within GUP facilitate bridging between SnO2 and perovskite while concomitantly passivating bifacial defects, thereby significantly inhibiting non-radiative recombination at the buried interface. Simultaneously, the planar configuration of the amidinourea unit strengthens the binding of amino (–NH2) and carbonyl (C=O) groups with [PbI6]4−, which enhances perovskite structure stability and relieves residual stresses. Contributing to the zwitterionic bridging strategy of multi-functional flame retardant, the power conversion efficiency (PCE) of GUP-treated PSCs significantly increased from 21.23 % to 24.03 %, with an open-circuit voltage (VOC) of up to 1.172 V, and exhibited outstanding stability. Unencapsulated PSCs treated with GUP maintained about 93.86 % and 80.53 % of their original efficiency after 1200 h of aging in the air at 25 °C with 25 ± 5 % relative humidity (RH) and after 600 h of aging in the air at 85 °C and 10 ± 5 % RH, respectively.

Modeling 2,4-dichlorophenoxyacetic acid adsorption on candle bush pod-derived activated carbon: Insights from advanced statistical physics models

The widespread usage of 2,4-Dichlorophenoxyacetic acid (2,4-D) as an herbicide has led to alarming levels of environmental pollution, presenting severe risks to ecosystems and human health. This study aimed to synthesize a new adsorbent, activated carbon from candle bush pods (CBAC) via low-temperature phosphoric acid activation and investigate its ability for adsorptive elimination of 2,4-D. The setup of a new adsorption system requires the experimental determination of adsorption isotherms and their thorough modeling, which is achieved through advanced statistical physics models (ASPMs). The characterization of CBAC revealed a porous morphology with a remarkable specific surface area (415.31 m2/g). XRD revealed graphitic carbon structures, while XPS detected phosphate groups, graphitic structures, and oxygen-containing functional groups. Double layer with single energy (DLSE) model – one of the ASPMs revealed both non-parallel and parallel orientation of 2,4-D molecules on CBAC, with saturation adsorption capacity values increasing with temperature (up to 252.35 mg/g) at pH 2. The adsorption was physisorption (ΔE = 12.62–16.26 kJ/mol) and spontaneous and endothermic. Hence, the findings herein demonstrate the potential of CBAC as a sustainable and effective adsorbent for mitigating environmental pollution caused by 2,4-D.

Promoting microalgal biofilm formation by crushed oyster shell-hydroxyapatite layer on micropatterned aluminum coating for heavy metal ions removal

Microalgal biomass has shown inspiring potential for the heavy metal removal from wastewater, and forming microalgal biofilm is one of the sustainable methods for the microalgal biomass production. Here we report the formation of microalgal biofilm by accelerated colonization of typical algae Chlorella on thermal sprayed aluminum (Al) coatings with biologically modified surfaces. Micro-patterning surface treatment of the Al coatings promotes the attachment of Chlorella from 6.31 % to 17.51 %. Further enhanced algae attachment is achieved through liquid flame spraying a bioactive crushed oyster shell-hydroxyapatite (CaCO3-HA) composite top layer on the micropatterned coating, reaching 46.03–49.62 % of Chlorella attachment ratio after soaking in Chlorella suspension for 5 days. The rapidly formed microalgal biofilm shows an adsorption ratio of 95.43 % and 85.23 % for low concentration Zn2+ and Cu2+ in artificial seawater respectively within 3 days. Quick interaction has been realized between heavy metal ions and the negatively-charged extracellular polymeric substances (EPS) matrix existing in the biofilm. Fourier transform infrared spectroscopy (FTIR) results indicate that both carboxyl and phosphoryl groups of biofilms are crucial in the adsorption of Cu2+ and the adsorption of Zn2+ is due to the hydroxyl and phosphate groups. Meanwhile, the biofilm could act as a barrier to protect Chlorella against the attack of the heavy metal ions with relatively low concentrations in aqueous solution. The route of quick cultivating microalgal biofilm on marine structures through constructing biological layer on their surfaces would give insight into developing new techniques for removing low concentration heavy metal ions from water for environmental bioremediation.

Fabrication of highly conductive VXC-72R carbon nanoparticles decorated Zr (IV)-based metal-organic framework for highly sensitive detection of methyl parathion

A simple and efficient ultrasonic-assisted strategy was used to prepare the nanocomposite of Vulcan XC-72R carbon (VXC-72R) nanoparticles and Zr(IV)-based metal-organic framework (UIO-66) nanoparticles. For the multifunctional VXC-72R@UIO-66 nanocomposite, VXC-72R nanoparticles possessed good conductivity property and good dispersion, which were conductive to form the interconnected carbon conductive channels; UIO-66 nanoparticles could improve the accumulation ability of methyl parathion (MP) because of the high affinity of Zr-O groups with phosphoric groups. Moreover, the introduction of VXC-72R nanoparticles could effectively make up the conductivity property of UIO-66 nanoparticles. The VXC-72R@UIO-66/GCE sensor presented good MP detection performance with limit of detection (LOD) of 1.35 nM (Linear MP concentration range: 0.01–10 μM). When used for the detection of MP in juice samples, the VXC-72R@UIO-66/GCE sensor showed acceptable recoveries of 96.00–104.67 %.

A novel electrochemiluminescence aptasensor for ultrasensitive lincomycin detection using Ti3C2–TiO2–Ru probe

The presence of lincomycin (LIN) residues in food poses significant health risks to humans, necessitating a highly sensitive and specific detection method for LIN. This study used a self-enhancing Ti3C2–TiO2–Ru probe to develop an electrochemiluminescence aptasensor to detect LIN. The Ti3C2–TiO2 was synthesized in situ by harnessing the unique reducibility of Ti3C2, with TiO2 serving as a co-reaction accelerator. Moreover, Ti3C2–TiO2 served as a carrier with an excellent negative charge, allowing for the immobilization of a substantial amount of Ru(bpy)32+ through electrostatic adsorption, thus forming a self-enhancing Ti3C2–TiO2–Ru probe. Furthermore, the specific affinity of LIN toward the aptamer and the chelating interaction between the Ti and phosphate groups ensured highly precise LIN detection. This sensor demonstrated excellent performance, with a detection limit of 0.025 ng mL−1 and a detection range of 1.0 × 10−1–1.0 × 104 ng mL−1. The LIN detection in milk showed commendable recovery rates, ranging from 94.4% to 106.0%.

Responses of Dunaliella sp. AL-1 to chromium and copper: Biochemical and physiological studies

Microalgae have gained recognition as versatile candidates for the remediation of heavy metals (HMs). This study investigated the biosorption potential of Dunaliella sp. AL1 for copper (Cu(II)) and hexavalent chromium (Cr(VI)) in aqueous solutions. The marine microalga Dunaliella sp. AL1 was exposed to half-sublethal concentrations of both metals in single and bimetallic systems, and responses in algal growth, oxidative stress, photosynthetic pigment production, and photosynthetic performance were evaluated. Cu and/or Cr exposure increased the generation of reactive oxygen species (ROS) in microalgae cells but did not impact algal growth. In terms of photosynthesis, there was a decrease in chlorophylls and carotenoids production in the microalgae culture treated with Cr, either alone or in combination with Cu. The study recorded promising metal removal efficiencies: 26.67%–20.11% for Cu and 94.99%–95.51% for Cr, in single and bimetallic systems, respectively. FTIR analysis revealed an affinity of Cu and Cr ions towards aliphatic/aldehyde C–H, N–H bending, and phosphate groups, suggesting the formation of complex bonds. Biochemical analysis of microalgae biomass collected after the removal of Cr alone or in combination with Cu showed a significant decrease in total carbohydrate content and soluble protein levels. Meanwhile, higher lipid accumulation was recorded and evidenced by BODIPY 505/515 staining. Fatty acid composition analysis by GC revealed a modulation in lipid composition, with a decrease in the ratio of unsaturated fatty acids (UFA) to saturated fatty acids (SFA), in response to Cu, Cr, and Cu–Cr exposure, indicating the suitability of the biomass for sustainable biofuel production.

NucleoFind: a deep-learning network for interpreting nucleic acid electron density.

Nucleic acid electron density interpretation after phasing by molecular replacement or other methods remains a difficult problem for computer programs to deal with. Programs tend to rely on time-consuming and computationally exhaustive searches to recognise characteristic features. We present NucleoFind, a deep-learning-based approach to interpreting and segmenting electron density. Using an electron density map from X-ray crystallography obtained after molecular replacement, the positions of the phosphate group, sugar ring and nitrogenous base group can be predicted with high accuracy. On average, 78% of phosphate atoms, 85% of sugar atoms and 83% of base atoms are positioned in predicted density after giving NucleoFind maps produced following successful molecular replacement. NucleoFind can use the wealth of context these predicted maps provide to build more accurate and complete nucleic acid models automatically.

Programmable Framework Nucleic Acid-Modified Nanomagnetic Beads for Efficient Isolation of Exosomes and Exosomal Proteomics Analysis.

Exosomes are increasingly being regarded as emerging and promising biomarkers for cancer screening, diagnosis, and therapy. The downstream molecular analyses of exosomes were greatly affected by the isolation efficiency from biosamples. Among the current exosome isolation strategies, affinity nanomaterials performed comparably better with selectivity and specificity. However, these techniques did not take the structure and size of exosomes into account, which may lead to a loss of isolation efficiency. In this article, a framework nucleic acid was employed to prepare a well-designed nanosized bead Fe3O4@pGMA@DNA TET@Ti4+ for enrichment of exosomes. The abundant phosphate groups in the framework nucleic acid provide binding sites to immobilize Ti4+, and its rigid three-dimensional skeleton makes them act as roadblocks to barricade exosomes and provide affinity interactions on a three-dimensional scale, resulting in the improvement of isolation efficiency. The model exosomes can be effectively isolated with 92% recovery in 5 min. From 100 μL of HeLa cell culture supernatant, 34 proteins out of the top 100 commonly identified exosomal proteins were identified from the isolated exosomes by the novel beads, which is obviously more than that by TiO2 (19 proteins), indicating higher isolation efficiency and exosome purity by Fe3O4@pGMA@DNA TET@Ti4+ beads. The nanobeads were finally applied for comparing exosomal proteomics analysis from real clinical serum samples. Twenty-five upregulated and 10 downregulated proteins were identified in the lung cancer patients group compared to the health donors group, indicating that the novel nanobeads have great potential in isolation of exosomes for exosomal proteomics analysis in cancer screening and diagnosis.

Benzohydroxamate and nitrobenzohydroxamate affect membrane order: Correlations between spectroscopic and molecular dynamics to approach tuberculosis

This work correlates the effects of benzohydroxamate (BH) and nitrobenzohydroxamate (NBH) anions in two membrane models which may be used for anti-tuberculosis (anti-TB) spectroscopic studies and/or computational studies. Firstly, the BH and NBH influence in the physico-chemical properties of soy asolectin (ASO)-based large multilamellar vesicles (MLVs) were evaluated by spectroscopic and calorimetric studies. In parallel, the BH and NBH interaction with a Mycobacterium tuberculosis (Mtb) inner membrane model, composed of phosphatidyl-myo-inositol-dimannoside (PIM2), was investigated by molecular dynamics (MD) simulations. Spectroscopic data showed a localization of BH close to the lipid phosphate group, while NBH was found close to the choline region. The BH ordered the ASO choline, phosphate and carbonyl regions and disrupted the acyl methylenes, reducing the membrane packing of the lipid hydrophobic region. On the other hand, NBH showed an ordering effect in all the lipid groups (polar, interface and hydrophobic ones). By MD studies, it was found that NBH enhanced the stability of the PIM2 membrane more than BH, while also being positioned closer to its mannosyl oxygens. As in ASO MLVs, BH was localized close to the PIM2 phosphate group and disrupted its acyl chains. However, higher values of lateral diffusion were observed for NBH than BH. Despite this, BH and NBH increased the membrane thickness by 35 %, which suggests a global ordering effect of both drugs. Findings of this work reinforce the accordance and complementarity between MLVs based on ASO and the PIM2 MD model results to study the drug effects in Mtb membrane properties.

Assembly of protein-directed fluorescent gold nanoclusters for high-sensitivity detection of uranyl ions

Uranium is a key element in the nuclear industry, whose accidental release causes health and environmental problems. In this paper, a protein-directed fluorescent sensor with aggregation-induced emission characteristics (gold nanoclusters@ovalbumin, AuNCs@OVA) was synthesized for the detection of UO22+ with high sensitivity and selectivity. The sensor exhibited good fluorescence stability, and its fluorescence intensity could be selectively enhanced by UO22+. Based on FT-IR and XPS analyses, the increase in fluorescence intensity of AuNCs@OVA after the addition of UO22+ was attributed to aggregation induced by the complexation between UO22+ and the amino, carboxyl, hydroxyl, and phosphate groups of ovalbumin. The detection limit was determined to be 34.4 nM, and the sensor showed excellent ion selectivity for UO22+. In combination with a smartphone program, the sensor could realize the real-time detection of UO22+ in a quantitative and portable way.

Phosphoryl group wires stabilize pathological tau fibrils as revealed by multiple quantum spin counting NMR.

Hyperphosphorylation of the protein tau is one of the biomarkers of neurodegenerative diseases in the category of tauopathies. However, the molecular level, mechanistic, role of this common post-translational modification (PTM) in enhancing or reducing the aggregation propensity of tau is unclear, especially considering that combinatorial phosphorylation of multiple sites can have complex, non-additive, effects on tau protein aggregation. Since tau proteins stack in register and parallel to elongate into pathological fibrils, phosphoryl groups from adjacent tau strands with 4.8 Å separation must find an energetically favorable spatial arrangement. At first glance, this appears to be an unfavorable configuration due to the proximity of negative charges between phosphate groups from adjacent neighboring tau fibrils. However, this study tests a counterhypothesis that phosphoryl groups within the fibril core-forming segments favorably assemble into highly ordered, hydrogen-bonded, one-dimensionally extended wires under biologically relevant conditions. We selected two phosphorylation sites associated with neurodegeneration, serine 305 (S305p) and tyrosine 310 (Y310p), on a model tau peptide jR2R3-P301L (tau295-313) spanning the R2/R3 splice junction of tau, that readily aggregate into a fibril with characteristics of a seed-competent mini prion. Using multiple quantum spin counting (MQ-SC) by 31P solid-state NMR of phosphorylated jR2R3-P301L tau peptide fibrils, enhanced by dynamic nuclear polarization, we find that at least six phosphorous spins must neatly arrange in 1D within fibrils or in 2D within a protofibril to yield the experimentally observed MQ-coherence orders of four. We found that S305p stabilizes the tau fibrils and leads to more seeding-competent fibrils compared to jR2R3 P301L or Y310p. This study introduces a new concept that phosphorylation of residues within a core forming tau segment can mechanically facilitate fibril registry and stability due a hitherto unrecognized role of phosphoryl groups to form highly ordered, extended, 1D wires that stabilize pathological tau fibrils.

A Multimodal System for Lipid A Structural Analysis from a Single Colony.

Structural elucidation of Gram-negative bacterial lipid A traditionally requires chemical extraction followed by tandem MS data in the negative ion mode. Previously, we reported FLAT and FLATn as methods to rapidly determine the structure of lipid A without chromatographic techniques. In this work, we extend the capability and effectiveness of these techniques to elucidate the chemical structure in a de novo manner by including the use of positive ion mode (FLAT+ and FLATn+) spectral approaches. Advantages of positive mode analysis of lipid A include the generation of more interpretable and informative fragmentation patterns that include the identification of diagnostic fragments, including selective dissociation of a glycosidic bond between two glucosamine units and the selective dissociation at the secondary acyl chain in 2'-N, allowing for the determination of the composition of fatty acids. As a proof of principle, we present here two previously uncharacterized structures of lipid A from Roseomonas mucosa (R. mucosa) and Moraxella canis (M. canis). In R. mucosa, we determined the lipid A structure with a nonconventional backbone of-β-1,6 linked 2,3-dideoxy-2,3-diamno-d-glucopyranose further modified with galacturonic acid in the place of typical 1-phosphate, and in M. canis, we assigned a single discrete structure using the specific fragmentation patterns of terminal phosphate groups present in lipid A. Therefore, FLATn+, in combination with FLAT and FLATn, provides a multimodal structural platform for rapid structure characterization of unusual and complex lipid A structures from a single colony.

Kinetic Properties of Combustion and Pyrolysis of Masson Pine with Synergistic Flame Retardancy by GUP-APP-silica Sol

ABSTRACT In order to investigate the effect of guanylurea phosphate-ammonium polyphosphate-silica sol on the combustion and pyrolysis characteristics of Masson Pine, UL-94 horizontal and vertical burner, LOI tester, cone calorimeter, and thermogravimetric analysis were used to study the flame retardant wood, and Coats-Redfern model was used to analyze its pyrolysis kinetics. The results showed that the combined use of guanylurea phosphate-ammonium polyphosphate-silica sol had a significant synergic flame retardant effect on Masson pine. When the mass ratio of guanylurea phosphate, ammonium polyphosphate, and silica sol was 2:1:1, the heat release rate and total heat release of flame retardant pine were decreased by 54.7% and 44.7% compared with pure Masson pine, and the LOI was increased by 77.8% compared with the control group. In addition, the addition of silica sol in the flame retardant reduces the effect of flame retardant on the mechanical properties of wood. Raman analysis of carbon layer showed that the R-value of char residue decreased by 5% and 13% when the mass fraction ratio of guanylurea phosphate, ammonium polyphosphate, and silica sol was 5:1:2 and 2:1:1, respectively, indicating that the compound flame retardant effectively promoted the conversion of amorphous carbon into graphite structure. The TG results of the 5:1:2 and 2:1:1 ratios of guanylurea phosphate, ammonium polyphosphate, and silica sol groups showed that the pyrolysis temperature of flame-retardant pine advanced by about 100°C at the heating rate of 15 ℃/min, and the final char residue rate and apparent activation energy were 15.22%, 18.61%, 24.35 kJ/mol, and 23.76 kJ/mol, respectively. These results indicated that the synergistic flame retardant system of guanylurea phosphate-ammonium polyphosphate-silica sol reduced the apparent activation energy of pine pyrolysis, effectively inhibited the pyrolysis of Masson Pine, and enhanced the thermal stability, char forming ability, and flame retardant property.

Effect of Terminal Phosphate Groups on Collisional Dissociation of RNA Oligonucleotide Anions.

The increasing need for mass spectrometric analysis of RNA molecules calls for a better understanding of their gas-phase fragmentation behaviors. In this study, we investigate the effect of terminal phosphate groups on the fragmentation spectra of RNA oligonucleotides (oligos) using high-resolution mass spectrometry (MS). Negative-ion mode collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) were carried out on RNA oligos containing a terminal phosphate group on either end, both ends, or neither end. We find that terminal phosphate groups affect the fragmentation behavior of RNA oligos in a way that is dependent on the precursor charge state and the oligo length. Specifically, for precursor ions of RNA oligos of the same sequence, those with 5'- or 3'-phosphate, or both, have a higher charge state distribution and lose the phosphate group(s) in the form of a neutral (H3PO4 or HPO3) or an anion ([H2PO4]- or [PO3]-) upon CID or HCD. Such a neutral or charged loss is most conspicuous for precursor ions of an intermediate charge state, e.g., 3- for 4-nt oligos or 4- and 5- for 8-nt oligos. This decreases the intensity of sequencing ions (a-, a-B, b-, c-, d-, w-, x-, y-, z-ions) and hence is unfavorable for sequencing by CID or HCD. Removal of terminal phosphate groups by calf intestinal alkaline phosphatase improved MS analysis of RNA oligos. Additionally, the intensity of a fragment ion at m/z 158.925, which we identified as a dehydrated pyrophosphate anion ([HP2O6]-), is markedly increased by the presence of a terminal phosphate group. These findings expand the knowledge base necessary for software development for MS analysis of RNA.

Effect of phytic acid/rust conversion layer on corrosion protection of rusty mild steel

In this study, a rust/phytic acid (rust/PA) conversion layer was prepared on rusty mild steel by dipping rusty steel panels into a phytic acid solution. After treating with phytic acid, the free phosphate group in the conversion layer chelated with Fe3+ and generated insoluble salt, which could form a new dense conversion layer. The dense rust/PA conversion layer effectively strengthened the interfacial bonding between the coatings and rusty metal substrate and exhibited good corrosion protection and defect healing abilities.

A Small-Molecule NIR-II Probe for the Diagnosis of Hemorrhagic Diseases.

Numerous hemorrhagic disorders, particularly those presenting deep hemorrhage, pose diagnostic challenges, often leading to delayed treatment and severe outcomes. Near-infrared (NIR)-II fluorescence imaging offers advantages such as deep tissue penetration, real-time visualization, and a high signal-to-background ratio, making it highly suitable for diagnosing hemorrhagic diseases. In this study, an NIR-II fluorescent probe LJ-2P carrying carboxylic and phosphoric acid groups is successfully applied for imaging hemorrhagic diseases. LJ-2P demonstrates a strong affinity for fibrinogen and fibrin clots both computationally and experimentally, thus exhibiting increased brightness upon coagulation. As compared to Indocyanine Green, LJ-2P provides a longer imaging window, higher imaging specificity, and signal-to-background ratio, as well as superior photobleaching resistance in three disease models: gastric, pulmonary, and cerebral hemorrhages. These results reveal that LJ-2P demonstrates enhanced imaging capabilities, enabling precise identification of hemorrhagic sites.