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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2021 · IF 4.098

Sensitive and reliable identification of fentanyl citrate in urine and serum using chloride ion-treated paper-based SERS substrate

Siqingaowa Han,Chen Zhang,Shuang Lin,Xuanyu Sha,Wuliji Hasi

Recently, the phenomenon of fentanyls overdose leading to death is emerging in an endless stream. There is an urgent requirement to quickly identify fentanyl content in body fluids for medical and judicial purposes. With this in mind, we present a paper-based SERS substrate decorated with uniform gold nanospheres treated by chloride ion for the detection of fentanyl citrate in urine and serum. In particular, the paper-based SERS sensor was prepared by liquid/liquid self-assembly technique and chloride ion was introduced to clean and modify the substrate surface, which improved the sensitivity of the solid substrate with an enhancement factor (EF) as high as 1.64 × 10 5 . Moreover, the uniformity of each paper-based substrate and the repeatability on different batches of substrate were excellent, and there was no obvious change in the intensity response of Raman spectra within a month. As a result, the quantitative analysis of fentanyl citrate in artificial urine and rat serum were performed based on the modified paper-based substrate with the limit of detection as low as 0.59 μg/mL and 2.78 μg/mL, respectively. Both the concentrations of the two biological samples with the Raman signal intensity were linearly plotted and the recovery of the spiked samples with different concentrations was collected to verify the accuracy of the quantitative curves. All the results suggest that this work makes SERS method available for the rapid identification and quantitative analysis of illicit drug in the real biological samples.

CAS / MDL: 7647-14-5 16903-35-8
研究领域: 分析化学 · 法医学 · 药物检测
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CONSTRUCTION AND BUILDING MATERIALS · 2024 · IF 7.4

Sustainable enhancement of fly ash/steel slag composite cement: The role of TriDiethanolamine Citrate in promoting hydration and microstructure

Bin Zeng,Shaojie Jia,Wenjin Han,Xumin Zhuang,Liwu Mo,Toshiharu Kishi

The development of sustainable cementitious materials is critical for reducing the environmental impact of the cement industry. This study examined the feasibility of using the new amide-alcohol organic hydration promoter, TriDiethanolamine Citrate (TriDECA), in fly ash or steel slag (FA/SS) composite cement. The effects of TriDECA on the hydration process, hydration products, microstructure and compressive strength of FA/SS composite cement, as well as its impact on the dissolution of FA and SS, were systematically investigated. Results demonstrated that TriDECA significantly accelerated the dissolution of FA and SS, promoted the formation of hydration products (C-S-H, AFm), and refined the pore structure. Additionally, TriDECA increased the concentration of critical ions in the pore solution, promoted hydration and enhanced overall performance. At 28 days, FA-TriDECA and SS-TriDECA showed 8.1 % and 14.2 % higher strength than FA-TEA and FA-Ref, respectively. For SS-TriDECA, the increase was 13.2 % and 11.2 % compared to SS-TEA and SS-Ref, respectively. These findings suggest that TriDECA is a promising additive for enhancing the sustainability and performance of FA/SS composite cements, offering advantages in hydration promotion and microstructure improvement over traditional alkanolamines.

CAS / MDL: 102-71-6
研究领域: 建筑材料学 · 可持续材料科学
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CRYSTENGCOMM · 2021 ·Vol. 23 ·期 48 ·8588-8600 · IF 3.545

Modulation of the calcium oxalate dihydrate to calcium oxalate monohydrate phase transition with citrate and zinc ions

Jing Zhang,Wenjun Zhang,Christine V. Putnis,Lijun Wang

As one of the most ubiquitous biominerals, calcium oxalate (CaOx) exhibits different hydrate phases. Although the monohydrate (whewellite, COM) is the thermodynamically favorable phase at ambient temperatures, the metastable dihydrate (weddellite, COD) can still stably exist in pathological mineralization but the stabilization mechanisms remain unclear. Herein, the in situ phase transformation of nano-sized COD to COM in the presence of citrate (CA) and zinc ions (Zn2+) as stabilizers was observed by time-resolved atomic force microscopy (AFM) and Raman spectroscopy. By a combination of zeta potential measurement, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), we demonstrate that CA can form a protective layer on the surface of nano-sized COD crystals to inhibit aggregation and delay the phase transformation of COD to COM. Due to the stabilizing/destabilizing effect of CA on the specific faces of COD, atypical-shaped COD crystals form. In addition, Zn2+ can substitute Ca2+ sites within the COD unit cell, shrinking the COD structure by compressing the “zeolite-like” channels to reduce weakly-bonded interchannel H2O molecules. This generates relatively smaller and more stable COD crystals with a typical pyramid shape to further retard COM formation. The obtained results provide new insights into modulating the stability of the metastable CaOx phases for potential control over pathological mineralization.

CAS / MDL: 7646-85-7
研究领域: 生物矿化 · 病理学 · 材料科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

Citrate/Tb lanthanide coordination polymer nanoparticles: Preparation and sensing of guanosine-5-monophosphate

Baoxia Liu,Haoshuang Shen,Daosheng Liu,Yuanqiang Hao,Xu Zhu,Qi Shen,Peng Qu,Maotian Xu

Metal-organic coordination polymers have emerged as attractive functional materials due to their tunable structures and unique properties. In this work, by the self-assembly of citrate (Cit) and lanthanide ions, we developed lanthanide coordination polymer nanoparticles (LCPNPs), Cit/Tb, for fluorescence sensing of guanosine-5-monophosphate (GMP). The LCPNP-based Cit/Tb sensor alone displayed weak luminescence, however, the addition of GMP to Cit/Tb led to the formation of a ternary LCPNP, Cit/Tb-GMP, with a significantly enhanced luminescence (15-fold) owing to the intramolecular energy transfer from GMP to Cit/Tb and the hydrophobic environment in the polymer interior. This luminescence turn-on assay exhibited excellent selectivity and high sensitivity for GMP with detection limit of 100 nmol L −1 . Furthermore, the Cit/Tb LCPNP possesses a long luminescence lifetime of up to a millisecond, which is important for detecting GMP in complicated samples of infant formula and ham by time-resolved fluorimetry. We believe that the presented Cit-based nanosensor would inspire the development of various new LCPNP-based fluorescent assays by utilizing Cit or other water-soluble, non-toxic organic ligands for a variety of applications in fluorescence sensing, bio-imaging, drug delivery and so on.

研究领域: 化学 · 生物分析 · 材料科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Terahertz spectroscopy of citrate Salts: Effects of crystalline state and crystallization water

Yanchun Shen,Ximing Qiao,Ziyu Song,Shaobo Zhong,Dongshan Wei

Citrate salts are widely used as food additives and medicines for health and treatment. Accurate and fast detection of citrate salts is most important in food industry and medicine health. In this work, terahertz (THz) time-domain spectroscopy was used to detect and analyze different citrate salts and differentiate their crystalline hydrates. Effects of the crystalline state, the crystallization water and the metal cation on the THz spectra of citrate salts were investigated. Results indicate the crystalline states of the citrate salt samples strongly influence their THz featuring absorption peaks and citrate salts with crystallization water have larger absorption coefficients at the same frequency and higher possibility of existing featuring absorption peaks in comparison with citrate salts without crystallization water. Size of the metal cation also influences the THz absorption peak of the citrate salt and a small cation radius results in a large absorption peak frequency. This work illustrates the terahertz spectroscopy can be well used as a new technique to detect the citrate salts and differentiate their crystalline hydrates.

研究领域: 食品科学 · 药学 · 光谱学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Readily available, biocompatible sodium citrate catalyst for efficient glycerol carbonate production through transesterification of glycerol and ethylene carbonate

Haoru Tang,Cong Luo,Houfang Lu,Kejing Wu,Yingying Liu,Yingming Zhu,Binshen Wang,Bin Liang

As a by-product in the biodiesel industry, surplus glycerol (Gly) has attracted considerable concern. The transesterification of Gly is one of the most promising reaction pathways to convert Gly to a value-added chemical such as glycerol carbonate (GC). Currently, development of catalysts for the transesterification with high activity is underway. Herein, a readily available biocompatible sodium citrate (Na 3 -citrate) catalyst was applied for efficient production of GC through transesterification of Gly and ethylene carbonate (EC). The effects of reaction parameters such as reaction time, EC to Gly molar ratio, reaction temperature, and catalyst loading on the reaction were investigated. Under optimal conditions, 0.01 wt% of Na 3 -citrate showed high catalytic activities with a Gly conversion of > 99 %, a GC yield of > 99 %, and a high turnover frequency of 16,925 g GC ⋅g −1 Cat ⋅h −1 . Furthermore, the reaction kinetic model for transesterification was established, and the activation energy of the Na 3 -citrate catalyzed transesterification was calculated as 51.3 kJ·mol −1 . In addition, density functional theory calculations were used to unveil mechanism of the Na 3 -citrate catalyzed transesterification. It revealed that citrate anion of Na 3 -citrate could activate hydroxy of Gly via strong hydrogen bond interaction, thereby efficiently promoting transesterification by reducing energy barrier of rate-determining step.

CAS / MDL: 56-40-6 6674-22-2
研究领域: 化学工程 · 催化科学 · 可再生资源转化
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FOOD HYDROCOLLOIDS · 2024 · IF 11

Phase separation and gelation of gelatin-glucose syrup mixtures and gummy confections: Effects of moisture content, sugars, citric acid, and citrates

Ruican Wang,Richard W. Hartel,Xinyu Zhai,Wenhui Fu,Yi Sun,Shuo Wang

Phase separation is a prevalent phenomenon in gummy confections, often arising from potential molecular incompatibility between gelatin and long-chain polysaccharides in glucose syrups (GS). This study focuses on analyzing the phase separation and gelling behaviors of gelatin-GS mixtures, elucidating the roles played by water content and small molecular weight (MW) additional ingredients. Mixtures with 6% gelatin, 40% GS, and varying portions of water, sucrose/allulose, citric acid (CA), and citrates (soluble/insoluble) were prepared. Phase separation behaviors were observed using inverted fluorescent microscopy, with the gel properties characterized using rheology, texture profile analysis (TPA), and water-holding capacity (WHC) analysis. The results highlight the significant impacts of these small MW components on biopolymer compatibility (cosolubility). In gelatin-GS-water mixtures, reducing the water ratio without the addition of sugars promoted phase separation towards the polysaccharide-rich morphologies, while enhancing the sol-gel transition and gel strength due to increased gelatin/water ratio. The incorporation of sucrose or allulose into gelatin-GS-water mixtures, without altering the gelatin/GS/water ratio, generally improved the protein-polysaccharide co-solubility during mixing but had an adverse overall effect on gel formation. Acidification with CA increased the surface charges of the proteins, enhancing the biopolymer miscibility and gelling performance. Soluble citrates, e.g., sodium citrate (SC) and potassium citrate (PC), promoted protein-polysaccharide miscibility and gelation at low concentrations (1–5%), but led to severe phase separation and weakened gelation at higher dosage levels (7.5–10%). In contrast, insoluble citrate, i.e., calcium citrate (CC), marginally enhanced the protein-polysaccharide miscibility while facilitating gummy gelation as an active filler.

研究领域: 食品科学 · 生物化学
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MATERIALS & DESIGN · 2024 · IF 7.6

Improved synergistic anticancer action of quercetin and tamoxifen citrate supported by an electrospun complex nanostructure

Jiaojiao Li,Qing Du,Jiangling Wan,Deng-Guang Yu,Fei Tan,Xiangliang Yang

A tri-fluid electrospinning process was successfully developed to prepare tri-chamber complex nanofibers. The core–shell and Janus structure were combined to form a delicate and complicated architecture for solving the problem of co-administration of quercetin and tamoxifen citrate, improving the oral bioavailability, and enhancing their synergistic anti-breast cancer actions. Scanning electron microscope, transmission electron microscope and confocal fluorescent microscopy images showed the complex structure of the designed nanofibers. Fourier transform infrared and X-ray diffraction analyses verified that the model drugs and the polymeric excipients had good compatibility and were presented in an amorphous state. The in vitro release study certified that the tri-chamber nanofibers facilitated the rapid release of quercetin compared with that of the crude drug (90% versus 38%) and the delayed and sustained release of tamoxifen citrate at the same time interval (decreased by 1.88 times). The in vivo pharmacokinetic and pharmacodynamic analysis verified that the tri-chamber nanofibers could result in increased oral bioavailability and enhanced synergistic anticancer action of quercetin and tamoxifen citrate. The findings proved that a new medicated drug delivery system with advanced dual-, time-, and target-specific drug release profiles was developed using the electrospun complex nanostructure.

研究领域: 药剂学 · 肿瘤学 · 生物材料学
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Biomaterials Science · 2023 ·Vol. 11 ·期 10 ·3524-3546 · IF 6.6

Synergistic inhibition of calcium oxalate crystal formation and synergistic protection of HK-2 cells from crystal damage by sulfated Laminarin polysaccharide and potassium citrate

Jing-Hong Liu,Jian-Ming Ouyang

Objective: The first objective is to study the synergistic inhibition of calcium oxalate (CaOx) formation by Laminarin polysaccharides (DLP and SDLP, before and after sulfation) and potassium citrate (K3cit) and determine the synergistic protection of renal epithelial cells (HK-2 cells) caused by CaOx crystal damage. The second objective is to explore new ways to prevent and treat kidney stones. Methods: The CaOx crystals regulated by five additives (K3cit group, DLP group, SDLP group, DLP–K3cit synergistic group and SDLP–K3cit synergistic group) were characterized by FT-IR, XRD, SEM, zeta potential, ICP, and TGA. The protective effect of each additive group on HK-2 cells damaged by nano-calcium oxalate monohydrate (nano-COM) was compared by detecting cell viability, the cell reactive oxygen species level, the cell survival rate, and mitochondrial membrane potential. Results: When DLP or SDLP acted synergically with K3cit, the synergistic group induced the same amount of COD at a lower concentration or more COD formation at the same concentration, highlighting the synergistic enhancement effect of 1 + 1 > 2. At 0.3 g L−1, the COD contents induced by DLP, SDLP, K3cit, DLP–K3cit, and SDLP–K3cit synergistic groups were 20.3%, 75.8%, 75.4%, 87.3%, and 100%, respectively. The synergistic group increased the concentration of soluble Ca2+ ions in the supernatant, increased the absolute value of the zeta potential on the surface of CaOx crystals, and inhibited the aggregation among the crystals. TGA and DTG analyses established the adsorption of polysaccharides in the crystals. Cell experiments showed the ability of the synergistic group to significantly inhibit the damage of nano-COM crystals on HK-2 cells, reduce the level of reactive oxygen species and mortality, and improve cell viability and the mitochondrial membrane potential. Conclusions: The synergistic group can more effectively induce COD formation and cell protection than the standalone polysaccharide group or K3cit group. The synergistic groups, especially SDLP–K3cit, may be a potential drug for inhibiting the formation of CaOx kidney stones.

研究领域: 医学 · 生物化学
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ANALYTICAL CHEMISTRY · 2021 · IF 6.986

Use of Triangular Silver Nanoplates as Low Potential Redox Mediators for Electrochemical Sensing

Xuwen Gao,Shuangtian Dong,Li Fu,Bin Zhang,Hsien-Yi Hsu,Guizheng Zou

Redox mediators can facilitate the electrochemical communication between targets and electrodes for material characterization and investigation. To provide an alternative to the chemical-based redox mediators, herein, we present a nanoparticle-based redox mediator, i.e., the trisodium citrates (TSC)-capped triangular silver nanoplates (Tri-Ag-NPTSC), which demonstrates an efficient oxidative process at around 0.13 V (vs Ag/AgCl) with acceptable redox reversibility by exploiting the interaction between the carbonyl group of TSC and the Ag element of Tri-Ag-NPTSC. The TSC of Tri-Ag-NPs can be selectively replaced by thiols and enable the obtained Tri-Ag-NPTSC-thiol with changed electrochemical redox response, which could be utilized to determine various thiols at 0.13 V, a much lowered oxidative potential than traditional redox mediators, with a similar linear response range, response slope, and limit of detection (LOD). This work proposes a surface-engineering approach to design and develop electrochemical redox probes using Ag nanoparticles with particular morphology, indicating that the interaction between the carbonyl group and Ag nanoparticles might be extended to sensing application beyond the surface-enhanced Raman scattering.

研究领域: 材料科学 · 分析化学
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INORGANIC CHEMISTRY COMMUNICATIONS · 2025 · IF 5.4

Acid-citrate sequential engineered Hangjin2# clay for photo-fenton degradation of methyl orange: electron transfer mechanism analysis

Zhengjiang Liu,Yunting Zhang,Junjie Tang,Jiani Wu,Timur Borjigin,Lei Xing

Technological advancements and industrialization resulted in a significant increase in the discharge of hazardous waste into aquatic environments, highlighting the urgent need for environmentally friendly remediation strategies. In this context, the present study introduces Hangjin2 # clay as a novel, eco-friendly heterogeneous photo-Fenton-like catalyst for the degradation of methyl orange, a representative model pollutant in wastewater treatment. The skeletal structure and ionic coordination environment of Hangjin2 # clay were altered via acid and sodium citrate modification, which triggered structural and coordination rearrangements. This modification also immobilized Fe 2+ and generated both Lewis and Brønsted acid sites on the Hangjin2 # clay surface. The Lewis acid sites enhanced the adsorption of H 2 O 2 , while the Brønsted acid sites facilitated the formation of hydroxyl radicals through proton transfer processes. These effects collectively promoted efficient Fe 3+ /Fe 2+ redox cycling, thereby enhancing the photo-Fenton catalytic performance. XPS and FTIR analyses revealed that acid-activated iron ions, chelated by sodium citrate, underwent isomorphous substitution with tetrahedral Si 4+ in Hangjin2 # clay, as evidenced by characteristic Si-O-Fe vibrational features and binding energy shifts in the Fe 2p 3/2 orbitals. In photo-Fenton degradation experiments using hydrated systems, the catalyst achieved a 98.9 % degradation rate of 50 mg/L methyl orange under optimal conditions (25 mM H 2 O 2 , pH 3, and 1 g/L catalyst) after 90 min. Additionally, stability tests demonstrated a maintained removal efficiency of 98 % after three successive catalytic cycles.

研究领域: 环境化学 · 催化科学 · 水污染控制 · 材料科学与工程 · 表面化学
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TALANTA · 2017 · IF 4.162

Disperse magnetic solid phase microextraction and surface enhanced Raman scattering (Dis-MSPME-SERS) for the rapid detection of trace illegally chemicals

Shihua Yu,Zhigang Liu,Weixian Wang,Li Jin,Weiqing Xu,Yuqing Wu

The technique of solid phase micro-extraction (SPME) is an important method for sample pretreatment in analytical chemistry , especially for the analysis in micro-systems. Surface enhanced Raman scattering (SERS) is an ultra-sensitive and fast detection technique. Both are particularly important in qualitative analysis of trace amount of substance. In this study, combining the magnetic nanoparticles with magnetic SPME device, we develop a high efficient new pretreatment method named as disperse magnetic solid phase micro-extraction (Dis-MSPME). In comparison to the traditional SPME, the proposed Dis-MSPME realizes solid phase micro-extraction from dispersive system, which improved the extraction efficiency largely. Conjunction the advantages both of Dis-MSPME and SERS is proposed as Dis-MSPME-SERS as a new detection method, which realize enrichment, magnetic separation and detection all-in-one. Making it a simpler, more efficient and sensitive approach in identifying the illegal additives. Sildenafil citrate (SC) in 500   μL health wine as an example of illegal additive was successfully detected in a LOD of 1.0 × 10 −8   M. Moreover, comparative study on the extract efficient of Dis-MSPME-SERS with SPME-SERS shows it takes only 10   min to detect sildenafil citrate in the health wine, from enrichment to detection by Dis-MSPME-SERS.

研究领域: 分析化学 · 检测技术
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