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FOOD CHEMISTRY · 2024 · IF 8.5

Interaction of L-proline with water and ice: Implications for Litopenaeus Vannamei Cryoprotection during temperature fluctuation

Yejun Zhang,Yongzhen Wang,Hao Dong,Jiao Li,Jianan Sun,Xiangzhao Mao

Temperature fluctuations can negatively affect the quality of frozen shrimp. Research on novel cryoprotectants to replace traditional agents (phosphate, etc.) has become a hotspot. Our results indicated that L-Proline could reduce thawing losses, delay texture deterioration and improve the functional properties of myofibrillar proteins of shrimp. Thawing loss in the proline group (3.2 %) was significantly lower than that in the control (5.4 %) after 3 freeze-thaw cycles ( p  < 0.05). Compared to Na 4 P 2 O 7 , proline had better permeability and greater ability to inhibit ice crystal growth and volume expansion. Through molecular simulations, we found that proline might inhibit ice crystal formation by forming glassy states with water. Hydrogen bonding between proline and water/ice played a major role, and only a small amount of proline was required to significantly reduce the ice crystal growth rate from 0.16 m/s to 0.06 m/s. Briefly, proline exhibited potential as a cryoprotectant for shrimp in temperature fluctuations.

CAS / MDL: 147-85-3 7722-88-5
研究领域: 食品科学 · 分子生物学
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CHEMICAL ENGINEERING SCIENCE · 2019 · IF 3.372

Control of ice crystal growth and its effect on porous structure of chitosan cryogels

Haiyan Zhang,Chunjie Liu,Liang Chen,Bin Dai

We presented an improved preparation method to generate cryogels with controllable pore size. It included 5 stages: pre-cooling, pre-crystallization, crystal growth, freezing, and thawing (PPCFT); crystal growth was the key step. Chitosan (CS) cryogels with uniform and honeycomb-like structures were prepared with the method, and then the properties of these cryogels were studied. The results demonstrated that the mean pore diameters of CS cryogels were successfully controlled in a wide range (approximately 60–240 μm, by scanning electron microscope) by simply varying the temperature and time of crystal growth. The crystal growth law of this process was described by an empirical equation based on the classical theory for Ostwald ripening by Lifshitz, Slyozov, and Wagner (LSW). Furthermore, the hydrodynamics performance (permeability and column efficiency) of CS cryogel columns clearly varied with crystal growth conditions, while both the accessible porosity and water absorption ratio remained at a high level.

CAS / MDL: 9012-76-4 111-30-8
研究领域: 材料科学 · 生物医学工程
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Materials Today Communications · 2023 · IF 3.8

Study on preparation of aluminum fluoride from cryolite

Jiaming Li,Youjian Yang,Wenju Tao,Zhaowen Wang,Jiangyu Yu,Jiaxin Yang,Zhibo Liu

As China's aluminum electrolysis industry expanded its production capacity, it produced a large amount of bath materials– cryolite based molten salt, which is not utilized fast enough and piled up in aluminum factories. It is of great significance to find a proper way to process the accumulated bath materials. Through the method introduced in this paper, aluminum fluoride can be produced from cryolite-based electrolyte and fed back into the aluminum electrolysis cell as a necessary additive. This method includes four steps: Calcination of crystalline aluminum nitrate with cryolite. Cryolite and crystalline aluminum nitrate are mixed and preheated. The main chemical reaction that occurs in this step will produce sodium nitrate (NaNO 3 ), β-aluminum fluoride (β-AlF 3 ), chiolite (Na 5 Al 3 F 14 ) and the aluminum hydroxyfluoride hydrate (AHF). After calcination, the products are washed with water to separate soluble NaNO 3 from the other products. The insoluble products obtained after washing are calcined with ammonium bifluoride to convert AHF into AlF 3 . The mixture obtained after preheating is then washed with an aqueous solution of aluminum salt (such as Al(NO 3 ) 3 ) to remove Na 5 Al 3 F 14 . Aluminum fluoride of high purity is obtained in the end. Calcination step is the most important among the four steps. The effects of calcination temperature (85 – 135 ℃) and molar ratio of crystalline aluminum nitrate to cryolite (0.5 – 2) on the conversion rate of cryolite were studied. The experimental results show that the highest conversion rate of cryolite can reach 97.03%. Through SEM, EDS , ICP and other analysis methods, it was found the final products contained more than 98.8 wt% aluminum fluoride and less than 0.4 wt% sodium, and the average particle size of aluminum fluoride is approximately 15 – 20 µm.

CAS / MDL: 7784-27-2 13775-53-6
研究领域: 材料科学 · 化学工程
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Nature Communications · 2024 ·Vol. 15 ·期 1 ·1-9 · IF 14.7

Interfacial ice sprouting during salty water droplet freezing

Chu Fuqiang,Li Shuxin,Zhao Canjun,Feng Yanhui,Lin Yukai,Wu Xiaomin,Yan Xiao,Miljkovic Nenad

Icing of seawater droplets is capable of causing catastrophic damage to vessels, buildings, and human life, yet it also holds great potential for enhancing applications such as droplet-based freeze desalination and anti-icing of sea sprays. While large-scale sea ice growth has been investigated for decades, the icing features of small salty droplets remain poorly understood. Here, we demonstrate that salty droplet icing is governed by salt rejection-accompanied ice crystal growth, resulting in freezing dynamics different from pure water. Aided by the observation of brine films emerging on top of frozen salty droplets, we propose a universal definition of freezing duration to quantify the icing rate of droplets having varying salt concentrations. Furthermore, we show that the morphology of frozen salty droplets is governed by ice crystals that sprout from the bottom of the brine film. These crystals grow until they pierce the free interface, which we term ice sprouting. We reveal that ice sprouting is controlled by condensation at the brine film free interface, a mechanism validated through molecular dynamics simulations. Our findings shed light on the distinct physics that govern salty droplet icing, knowledge that is essential for the development of related technologies.

研究领域: 物理化学 · 材料科学
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Small · 2024 · IF 13

Reversible Stacking and Delamination-Regulation of MXene via Controlled Freezing

Yanlin Zhang,Jinhao Hu,Guoying Bai

MXene's configuration, whether it is aggregated or dispersed in a monolayer, determines the specific application areas and even greatly influences the intrinsic properties of MXene. However, how to desirably control MXene's configuration is challenging. Here, a simple, additive-free, chemical reaction-free, and scalable strategy to optionally and reversibly regulate MXene's ordered stacking and delamination of MXene aggregates (AM) is reported. Just by controlled freezing of MXene aqueous dispersions, the aggregation percentage, delamination percentage, and interlayer spacing of AM can be finely tuned. Experimental results reveal that the freezing-induced aggregation and delamination effects can be explained by the squeezing action of growing ice grains on the MXene excluded/concentrated between ice grains and the expanding action caused by the ice formation between AM lamellae, respectively. The dominance between them depends on the freezing parameter-influenced ice nucleation sites, numbers, and ice grain sizes. This work not only contributes to the preparation, storage, and practical applications of MXene, but also opens a new and green avenue for controlling materials’ assembly structures.

CAS / MDL: 573-58-0 7789-24-4
研究领域: 材料科学 · 纳米技术 · 化学工程
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ACS Applied Nano Materials · 2024 · IF 5.3

Profiling the Morphology Effects of MoS2 Nanomaterials on Ice Suppression and Rapid Rewarming for Cryopreservation

Wei Han,Li Zhong,Jixiang Zhang,Yifang Li,Nian Li,Zhenyang Wang,Jun Zhao

With the booming development of nanotechnology, an increasing number of nanomaterials and engineering strategies are being used to explore the effective inhibition of ice crystals, thereby reducing ice damage to biological samples and improving the efficiency of cryopreservation. However, the ice-inhibiting effect of nanomaterial shapes and their corresponding photothermal behavior have rarely been studied in depth in cell cryopreservation applications. Here, molybdenum disulfide (MoS2) nanomaterials with different morphologies [nanosheets (NSs), nanoflowers (FLs), and nanomicrospheres (MSs)] were controllably synthesized by a hydrothermal method to profile the influence of MoS2 morphology on ice suppression and rapid rewarming. The prepared MoS2 nanomaterials exhibited excellent capabilities for regulating the nucleation temperature and recrystallization size of ice crystals, which varied with morphology (MSs > FLs > NSs). Unique surface morphology, more functional groups on the surface that could form hydrogen bonds with ice/water molecules, and the adsorption-inhibition mechanism contributed to the excellent ice regulation performance. Surprisingly, the photothermal effect of MoS2 MSs was also the best as the temperature could sharply rise from 24 to 82 °C under 808 nm laser irradiation for 1 min. Finally, using MoS2 MSs as a cryoprotectant (CPA) to cryopreserve A549 cells, a cell survival rate of 85.3% was still achieved even when MoS2 MSs replaced 90% of dimethyl sulfoxide in the CPA solution. Our work is the first to correlate the shape variations of nanomaterials with their regulation of ice crystal behavior during the freezing-thawing process and photothermal properties, synergistically improving the efficiency of cell cryopreservation. This study provides guidance for the practical design of nanomaterials for collaborative deicing.

研究领域: 材料科学 · 生物技术 · 纳米医学
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Frontiers in Cell and Developmental Biology · 2025 · IF 4.3

Effect of low-frequency assisted ultrasonic on cryopreservation of L-02 hepatocyte cells

Weijie Li,Xi Yang,Wenyan Bi,Liyong Song,Baolin Liu

Developing bioartificial liver and hepatocyte transplantation technology causes increasing hepatocyte cell demand. Effective long-term hepatocyte cell preservation methods are necessary to promote. Progressive cooling is a key preservation technology for cell banks. However, the cell solution needs to be supercooled in a slow freezing process. The high degree of supercooling possibly induces uncontrollable intracellular ice formation. This work designs an ultrasonic ice-seeding system for L-02 hepatocyte cell preservation, reducing supercooling and improving cell survival rate. The effect of ultrasonic intensities on the hepatocyte’s survival rate was investigated and optimized. The results prove the calorimetric method can efficiently measure the ultrasonic intensity dissipated in the hepatocyte cell preservation solution. When the ultrasonic intensity is 0.0329 W/cm 2 ∼ 0.4316 W/cm 2 , the hepatocyte survival rate is over 90%. There is no significant difference between experiment groups (p < 0.05) when the ultrasonic intensity is larger than 0.4316 W/cm 2 . The hepatocyte cell survival rate reduced significantly with the increase of ultrasonic intensity. The 7-day hepatic function indicator experiment results indicate that the ultrasonic ice seeding has the weakest impact on hepatocyte cells in the four groups. The secretion of urea, albumin and glucose proved that ultrasonic ice seeding technology does not affect cell secretion and has an enormous advantage in cryopreservation. It can be widely applied to cell freezing fields.

CAS / MDL: 67-68-5
研究领域: 生物技术 · 医学工程
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MACROMOLECULAR MATERIALS AND ENGINEERING · 2016 ·Vol. 301 ·期 6 ·659-664 · IF 2.834

Synthesis of Hydrophobic Polymeric Cryogels with Supermacroporous Structure

Xilu Chen,Weiwei Sui,Dayong Ren,Yuanyuan Ding,Xiaoli Zhu,Zhiyong Chen

A versatile approach to synthesis of hydrophobic polymeric cryogels is proposed using acetic acid crystals instead of ice crystals as porogen through cryo-polymerization. In the range of 60 to 90 vol% of acetic acid, polymerization at ambient temperature gives rise to particulate polymers in beaded or amorphous shape, while polymerization at 4 °C, lower than the melting point of acetic acid (16.6 °C), leads to the formation of cryogel-like monoliths with supermacroporous structure, which is mainly ascribed to cryo-concentration effect. According to the measurements by scanning electron microscopy and mercury intrusion porosimetry, the dried samples are supermacroporous with pore size mainly ranging from several micrometers to several hundred micrometers, which can be feasible for rapid mass transfer. The forming cryogels display a superfast responsiveness to organic solvents, possibly stemming from their supermacroporosity and distinctive hydrophobicity.

CAS / MDL: 1321-74-0 142-90-5
研究领域: 材料科学 · 化学工程
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COMPOSITES SCIENCE AND TECHNOLOGY · 2022 · IF 9.879

Creating controllable three-dimensional microstructures on the surface of carbon fibers by manipulating ice crystallization to improve interfacial properties of composites

Baowei Qiu,Baolin Qiu,Tong Sun,Jixiang Li,Qian Zou,Shengtai Zhou,Huawei Zou,Mei Liang

In nature, ice had a rich variety of shapes because of different growing conditions. Inspired by nature, we constructed controllable three-dimensional microstructures on the surface of carbon fibers (CFs) using water-based epoxy (WEP) by manipulating ice crystallization. The morphology of three-dimensional microstructures was tuned by manipulating the growth of ice crystallization. Briefly, the surface of CFs sized by WEP exhibited micro-spherical and layered morphologies after being treated by freeze-drying and unidirectional freeze-drying (bottom-up), respectively. The modified surface had ultra-high roughness, which could enhance the mechanical interlocking force between CFs and host matrix and improve the interfacial properties of composites. Furthermore, the resultant composites treated by unidirectional freeze-drying showed robust interfacial shear strength (72.27 MPa), which was increased by 60.18% compared to unmodified CFs. This strategy opened a feasible avenue for creating controllable three-dimensional structures on the surface of CFs.

研究领域: 材料科学 · 表面工程
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FOOD CHEMISTRY · 2025 · IF 9.8

Unveiling the impact of high pressure and low temperature coupling on gelatin gel properties

Sinan Zhang,Hosahalli S. Ramaswamy,Ting Xiao,Lihui Hu,Yuxiao Mao,Songming Zhu,Ying Liu,Yong Yu

Balancing shelf life extension and food quality is a key challenge in food processing. Conventional air freezing (CAF) methods inhibit microbial growth but often create large ice crystals that damage food texture, nutrition, flavor, and water holding capacity. High-pressure and low-temperature coupling (HPLT) technologies, such as pressure-shift freezing (PSF) and pressure-assisted freezing (PAF), offer innovative solutions to these limitations. This study explores the effects of HPLT on gelatin gel, focusing on ice crystal morphology, mechanical properties, and water distribution. PSF and PAF produce smaller, more uniform ice crystals, reducing structural damage and preserving gel strength and texture. HPLT also decreases water loss, enhancing gel integrity during freezing. These results demonstrate HPLT's potential to revolutionize frozen food processing, minimizing quality degradation, reducing food waste, and promoting global food security.

研究领域: 食品科学 · 生物物理学
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ACS Nano · 2018 · IF 13.709

Crystallization-Induced Morphological Tuning Toward Denim-like Graphene Nanosheets in a KCl-Copolymer Solution

Yaxin Chen,Liluo Shi,Qiong Yuan,Ang Li,Shaozhuan Huang,Hui Ying Yang,Xiaohong Chen,Jisheng Zhou,Huaihe Song

Although nucleation and crystallization in solution-processed materials synthesis is a natural phenomenon, the morphology design of graphene nanosheets by controlling the dual crystallization has not been established. In this work, we systematically demonstrate how the dual crystallization of ice and potassium chloride induces the morphological variation of the freeze-dried scaffold from fractal structure toward stepped sheet-like structure. A denim-like graphene nanosheet (DGNS) has been fabricated by annealing the F127-coated stepped sheet-like scaffold in nitrogen. DGNS shows parallel and straight stripes with an average stripe spacing of 10 nm. When used as a lithium-ion battery anode, DGNS possesses a superhigh reversible capacity of 1020 mAh g–1 at the current density of 1 A g–1 after 600 cycles. This work reports the control of dual crystallization of ice and salt crystals and provides an efficient way to design the morphology of two-dimensional materials by adjusting the crystallization.

CAS / MDL: 7447-40-7 57-50-1
研究领域: 材料科学 · 能源科学
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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2016 · IF 2.933

Freeze casting of composite system with stable fiber network and movable particles

Xiaoxia Hu,Lina Yang,Lingyu Li,Dieni Xie,Haiyan Du

Freeze casting was employed to fabricate alumina fiber-based porous ceramics . The binder particles were rejected by ice crystals from the gaps of the network to fibers and bonded them to obtain strong and light network. The effects of fiber character, cooling temperature and slurry viscosity on the structure formation were investigated. The structure and properties of the fibrous porous ceramics were determined by two factors: the fiber network and the dispersion of binders. The cooling temperature and slurry viscosity affected the dispersion of the particles rejected by the solidification front while the fiber length affected the fiber network. The material with optimal properties was obtained with 5   wt% PVA, 5   wt% silica sol and 1 vol% alumina fibers when freezing at −20   °C. The bulk density was 0.199   g/cm 3 and the specific strength was 3.860   N   m/kg.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 陶瓷工程
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