Crystalline Lamellae Research Articles

Hierarchical structure of poly(ε-caprolactone) crystals on its copolymer poly(l-lactide-co-ε-caprolactone) fibers

In crystallization, heterogeneous structures of copolymers are employed to establish a hierarchical architecture comprising two polymers, this typically occurs on the surface of block copolymers or blended polymers. While hierarchical structures in block copolymer fibers are well-established and widely utilized, achieving a regular hierarchical structure on random copolymer fibers is both meaningful and challenging. Here, we present a case of forming a hierarchical structure on the surface of the random copolymer poly(L-lactide-co-caprolactone) (PLCL)fibers. The (ε-caprolactone)(CL) polymer chain segments of the random copolymer are released on the surface of the modified copolymer fiber using sodium hydroxide. Subsequently, poly(ε-caprolactone)(PCL) forms a shish kebab-like crystalline structure under the guidance of the CL segments. The CL segments act as crystalline precursors to induce the formation of heterogeneous PLCL/PCL shish kebab structures. The variation of CL segments on the fiber changes with modification time, leading to the formation of crystalline lamellae of different sizes, which had been confirmed by characterization techniques such as scanning electron microscope (SEM), 1H NMR, X-ray photoelectron spectra (XPS), differential scanning calorimetry (DSC), etc. The implementation of this heterogeneous structure provides possibilities for the implementation of hierarchical structure in random copolymers.

Constrained amorphous interphase in plasticized poly(lactic acid): Composition and tensile elastic modulus estimation

The study investigates the distribution of the plasticizers acetyl triethyl citrate (ATEC) and acetyl tributyl citrate (ATBC) in the mobile amorphous (MAF) and rigid amorphous (RAF) fractions of semi-crystalline plasticized poly (lactic acid) (PLA) containing 5 wt% of plasticizer. During crystallization, the ATEC and ATBC concentration in the MAF increases from 5 to about 8 wt%. At the end of crystallization, the plasticizers concentration in the RAF is lower than that in the MAF. The progressive decrease of the ATEC and ATBC concentration in the RAF region could be linked to the growth of subsidiary lamellae in more restricted amorphous areas. The study also introduces an estimation of the tensile elastic modulus of the RAF (ERAF) in semi-crystalline pure and plasticized PLA containing α-crystals. The mechanical model with crystalline lamellae perpendicular to the stress direction turned out to be the most appropriate arrangement to represent the morphological organization in PLA samples prepared by injection-moulding processing at high pressure. The mathematical procedure led to a crystal elastic modulus (EC) of the α-phase in excellent agreement with the theoretical value reported in the literature (EC = 14 GPa), and to an ERAF value around 5.5 GPa, for both pure and plasticized PLA, thus suggesting that both ATEC and ATBC do not exert plasticizing action on the RAF.

Luminescent and photoconductive liquid crystalline lamellar and helical network phases of achiral polycatenars

Lamellar and helical network phases of achiral polycatenars. Functional achiral triple chain π-conjugated rod-like molecules were investigated for their photoconductivity, photoluminescence, phosphorescence, and electroluminescence properties.

Polymer crystallization enabled excimer emission in anthracene-appended poly(ʟ-lactide)s

The design and development of solid-state excimer-emitters bear great potential for attaining efficient solid-state luminescent materials. In this study, we have synthesized anthracene-appended poly(ʟ-lactide)s (AAPs) to regulate the arrangement of anthracene moieties by controlling the crystallization and polymorphic form of covalently linked poly(ʟ-lactide) (PLLA). In the high molecular weight AAP, the fluorescence intensity mainly arises from the monomeric anthracene moieties, whereas in the low molecular weight AAP, the excimer emission was observed depending on the structure and morphology of covalently-linked PLLA. The monomeric emission is predominantly observed in amorphous polymer due to the molecular level dispersion of covalently-linked anthracene moieties throughout the polymer matrix. When the polymer was crystallized under different conditions, covalently-linked anthracene moieties were excluded from polymer crystals or crystalline lamellae and are located on the surface or at the interface, which is advantageous for regulating the geometry of anthracene moieties. In the case of single crystals of PLLA, covalently-linked anthracene moieties assemble on the surface and emit mainly in their monomeric state due to the lack of π-stacking. In the melt-crystallized sample (α form), covalently-linked anthracene moieties reside at the interface of crystalline and amorphous domains by either dipolar interactions or π-stacking and fluorescence arising from anthracene excimers and monomers. In the gel state (ε form), only the excimer emission was observed due to the effective interactions between the anthracene moieties in the presence of excess solvent in the amorphous domains. In this way, polymer crystallization played a significant role in determining the arrangement of covalently-linked anthracene moieties in AAP. This study reveals the role of polymer crystallization on the excimer evolution in fluorophore-appended semicrystalline polymers and provides new insight into the design and development of fluorophore-appended polymers for optoelectronic devices.

High-efficiency preparation of starch nanocrystals with small size and high crystallinity by ethanol-acid penetration and dry-heating pretreatment

Ethanol-acid penetration and drying-heating treatment was developed to shorten the preparation time and improve the quality of starch nanocrystals (SNCs). After treatment by optimized parameters, including 40 % ethanol solution, 10.6 mM chloric acid, and heating time of 1.5 h or 2.0 h, the starches exhibited weakened internal structure and relatively complete crystalline structure. Compared with the regular preparation of only acid hydrolysis, the regular final yield (8.5 % after 5 days) was reached in 48 h and 12 h of the starch heated at 1.5 h and 2.0 h, respectively. The micromorphology, molecular weight, and crystalline structure evaluation demonstrated that the collected nanoparticles were indeed SNCs with smaller size and higher relative crystallinity than regular SNCs. Further analysis found that the SNCs had better crystalline lamellae, higher thermal stability, and lower proportion of phosphorus and sulfur atoms than regular SNCs. This provided a potential method for the high-efficiency preparation of SNCs.

Intraspherulitic mechanical heterogeneities and microstructure of i-PP highlighted by nanoindentation and atomic force microscopy

This study quantifies elastic modulus heterogeneity at the intraspherulitic scale in semi-crystalline i-PP polymer using nanoindentation. Prior to mechanical characterization, Atomic Force Microscopy (AFM) is used to characterize the topography of the local micro- and nanostructure of the spherulites. Small indents provide 3–5 μm resolution maps within a spherulite, remaining unaffected by local roughness. The major findings highlight a clear relationship between microstructure and mechanical properties at this scale. Firstly, elastic modulus decreases from the spherulite center to the edges. Secondly, regions along the main growth axes exhibit higher modulus values, while areas around these axes are less stiff. Moreover, similar elastic properties are found at the ends of spherulite branches measured in a transverse and longitudinal orientation with respect to the growth axis. The difference in measured mechanical properties is attributed to the local density and orientation of crystalline lamellae, which in turn depend on the spherulite's growth stage.

Direct observation of radiation-induced graft polymerization on a polyethylene film

Radiation-induced graft polymerization is widely used in the synthesis of polymeric materials with various functionalities; however, the details of the reaction mechanism are still unresolved. Herein, the initial stage of the graft polymerization reaction was investigated through atomic force microscopy (AFM). We used glycidyl methacrylate (GMA) in methanol (monomer solution) and a high-density polyethylene (HDPE) film with a well-ordered lamellar structure as the substrate. Using polymer film surfaces with a maximum grafting degree of 0.5%, AFM can distinguish between crystalline and amorphous polyethylene (PE) phases as well as a grafted polymer GMA (PGMA) phase. The graft polymerization reaction started from the interface between the crystalline and amorphous PE phases. As the reaction proceeded, the PGMA covered the crystalline PE phase: i.e., the entire surface of the PE film were covered by the PGMA. Further, the crystalline lamellae of the PE film eventually became a scaffold for the formation of aggregates comprising grafted polymer chains alone. The graft polymerization reaction mechanism was explained by comparing the solubility parameters of the monomer solution, substrate, and grafted polymer chains. Understanding the reaction mechanism at a low grafting degree obtained in this study may contribute to enhancing the efficiency of the graft polymerization reaction on any polymeric material.

High-pressure pasting performance and multilevel structures of short-term microwave-treated high-amylose maize starch

Microwave treatment is an environmentally friendly method for modification of high-amylose maize starch (HAMS). Here, the effects of short-time (≤120 s) microwave treatment on the structure and pasting of two types of HAMSs, Gelose 50 (HAMSI) and Gelose 80 (HAMSII), with apparent amylose content (AAC) of 45 % and 58 %, respectively, was studied using a multiscale approach including X-ray scattering, surface structures, particle size distribution, molecular size distributions and high temperature/pressure Rapid Visco Analysis (RVA)-4800 pasting. As compared to starch with no amylose (waxy maize starch, WMS) and 25 % amylose content (normal maize starch, NMS), HAMSI underwent similar structural and pasting changes as WMS and NMS upon microwave treatment, and it might primarily be attributed to the amylopectin fraction that was affected by cleavage of the connector chains between double helices and backbone chains, which decreased the crystallinity and thickness of the crystalline lamellae. However, the multi-scale structure of HAMSII was almost unaffected by this treatment. The pasting properties of fully gelatinized HAMSI starch showed a decrease in RVA-4800 peak and final viscosities after microwave treatment. In contrast, for HAMSII starch, the microwave treatment led to an increase in these viscosities. The combined results highlight the influence of varying AAC on the effects of microwave-mediated modification, leading to diverse alterations in the structure and functionality of starches.

Shortening growth year improves functional features of kudzu starch by tailoring its multi-scale structure

Kudzu is usually consumed at different growth years, yet the influences of growth years on its multi-scale structures and physicochemical features have not been fully disclosed. In this study, those influences occurred on kudzu starches (KS2, KS10, KS30 and KS50, isolated using precipitation method) were investigated. The granules size, crystallinity, short-range ordered structure, amylose content, intermediate and longer amylose chains reduced but the average thickness of crystalline lamella increased as the rise of growth years. KS2 had lower content of defective crystal structure and higher content of near-perfect crystal structure. Those signified that bulk density of molecules packing into starch substrate was higher for KS2, which was not beneficial for water molecules and enzymes entering into starch granules and thus elevated pasting temperature and reduced digestion rate. Besides, reduced proportions of defective ordered structures and enhanced lipid-amylose complex also reduced digestion rate. Both the peak and breakdown viscosity were in order of KS2 > KS10 > KS30 ≈ KS50. And KS2, KS10, and KS30 exhibited enhanced retrogradation tendency during cooling than KS50 as evidenced by the relative higher setback viscosity. Those results are favor for rational screen and usage of kudzu starch resources with different growth years for food applications.

Effects of elevated nitrogen fertilizer on the multi-level structure and thermal properties of rice starch granules and their relationship with chalkiness traits.

Chalkiness in rice reduces its market value and affects consumer acceptance. Research on the mechanism of chalkiness formation has focused primarily on the activity of key enzymes of carbon metabolism and starch accumulation. The relationship between the formation of chalkiness induced by N fertilizer and rice starch's multi-level structure and thermal properties still needs to be fully elucidated. In this study, the rates of chalky grains and degree of chalkiness decreased with the increase in N fertilizer dosage. This was attributed to an increased proportion of short chains, ordered structure carbon chains, small starch granules, and branched starches, and a higher degree of crystallinity and ΔHg in protein, and a decreased proportion of amylose, large starch granules, and weighted average diameter of starch granule surface area and volume. Application of N fertilizer promoted an increased proportion of short-branched chain amylopectin to develop a more ordered carbohydrate structure and crystalline lamella. These effects enhanced the normal development and compactness of starch granules in grains, and improved their arrangement morphology, thereby reducing the chalkiness in rice. These changes in starch multi-level structure and protein improve the physicochemical characteristics of starch and enhance the fullness, crystallinity and compactness of starch granules, while synergistically increasing the regularity and homogeneity of starch granules and thus optimizing the stacking pattern of starch granules, leading to a reduction in rice chalkiness under nitrogen fertilization and thus improving the appearance of rice. © 2023 Society of Chemical Industry.

Improving beta phase of spin coated PVDF thin films by doping with silver nanoparticles

This research deals with the effect of process parameters of spin coating such as spinning speed, weight composition of silver nanoparticles (AgNP), and annealing duration on the phase change of polyvinylidene fluoride (PVDF) thin films. FTIR spectroscopy along with XRD confirmed the transformation of α to β-phase in the PVDF thin films. The spin coated films exhibited higher β-fraction than that of the pristine PVDF. The β-fraction in the thin films was mainly influenced by the addition of AgNP. The DSC results showed decrease in crystallinity from 63.74 to 53.21% with increase in spinning speed from 1000 to 3000 rpm due to the over-stretching of crystalline lamellae.

Novel PEG6000-Silica-MWCNTs Shape-Stabilized Composite Phase-Change Materials (ssCPCMs) for Thermal-Energy Storage.

This paper describes the preparation of new PEG6000-silica-MWCNTs composites as shape-stabilized phase change materials (ssPCMs) for application in latent heat storage. An innovative method was employed to obtain the new organic-inorganic hybrid materials, in which both a part of the PEG chains, used as the phase change material, and a part of the hydroxyl functionalized multiwall carbon nanotubes (MWCNTs-OH), used as thermo-conductive fillers, were covalently connected by newly formed urethane bonds to the in-situ-generated silica matrix. The study's main aim was to investigate the optimal amount of PEG6000 that can be added to the fixed sol-gel reaction mixture so that no leakage of PEG occurs after repeated heating-cooling cycles. The findings show that the optimum PEG6000/NCOTEOS molar ratio was 2/1 (~91.5% PEG6000), because both the connected and free PEG chains interacted strongly with the in-situ-generated silica matrix to form a shape-stabilized material while preserving high phase-transition enthalpies (~153 J/G). Morphological and structural findings obtained by SEM, X-ray and Raman techniques indicated a distribution of the silica component in the amorphous phase (~27% for the optimum composition) located among the crystalline lamellae built by the folded chains of the PEG component. This composite maintained good chemical stability after a 450-cycle thermal test and had a good storage efficiency (~84%).

High-performance organic solar cell and self-power photodetector with chemically robust, near-infrared acceptor enabled by strengthening interfacial contact and compositional modulation

Non-fullerene acceptors (NFAs) have significantly contributed to the advancement of organic optoelectronic devices. However, their undesirable chemical reaction with adjacent interfacial layers and weak absorption in near infrared (NIR) region limit the further improvement of device performance. Herein, we employed chemically robust and NIR-responsive O6T-4F as NFA and enhanced the performance of both organic solar cells (OSCs) and organic photodetectors (OPDs) by interfacial engineering and compositional modulation. Bathocuproine cathode interfacial layer strengthens the interfacial contact due to the strong mechanical adhesion with active layer. Incorporating an appropriate content of PC61BM in the active layer promotes the molecular ordering and tunes the orientation of O6T-4F from flat-on and edge-on lamellar crystalline to J-type π-π stacking, thereby extending the absorption spectrum from 950 nm to 1050 nm. Moreover, ternary blend film approaches intrinsic type semiconductor, achieving an extremely low dark current. As a result, the optimized OSCs achieve a power conversion efficiency of 13.23% while the corresponding self-powered OPDs render an impressive detectivity of 1.10 × 1014 Jones at 840 nm and over 1.10 × 1013 Jones in a wide wavelength range (330–1050 nm). Finally, we realized high-quality visible and NIR imaging with 80 × 260 pixels using the fabricated OPD. Our work demonstrates that combined strengthening interfacial contact and compositional modulation is an effective strategy to improve the performance of both OSCs and OPDs.

High strength porous ceramics and its potential in adsorption and building materials: A short process to co-disposal secondary aluminum dross and quicklime

Porous ceramics with hierarchical pore and high strength were prepared by secondary aluminum dross and quicklime as main raw materials. The influence of quicklime content and thermal treatment on the porosity, pore morphology, compressive strength and bulk density of porous ceramics has been investigated. Scanning electron microscopy, computed tomography, x-ray diffraction and thermal analysis were used to characterize the microstructure, phase transition and high-temperature reaction of the samples. The formation temperature of the liquid phase in the micro-region starts at around 973 °C, close to the temperature at which the mixture starts to produce the liquid phase as calculated by FactSage7.1 software. The achieved porous ceramics exhibited excellent compressive strength of 12.4–51.0 MPa at a relatively high porosity of 63.7%-79.6%. Furthermore, the potential application of the obtained porous ceramics as adsorbent was verified by the adsorption of malachite green solution. Due to the high connectivity of the pores and the presence of a large number of thin lamellar crystalline phases, the adsorption rate of the sample to malachite green solution can be as high as 98.4%.

A Mechanistic Study on the Fluidization and Enhancement Effects of Cineole Toward Stratum Corneum Intercellular Lamellar Lipids: A Liquid Crystalline Model Approach.

The stratum corneum (SC) serves as the primary barrier for permeation in human skin. Penetration enhancers, such as 1,8-cineole, are utilized to enhance the permeation of drugs. Cineole increases the permeation of chemicals through different mechanisms. However, its mechanism, particularly at high concentrations, has not been well-studied and is the subject of the present investigation. In continuation of our previous studies, the present investigation aims to elucidate the mechanism of action and concentration dependency of the effects of 1,8-cineole on the structure, diffusional properties, and partitioning behavior of the SC at high concentrations. This will be achieved through lamellar liquid crystalline models and ex-vivo skin studies. A lamellar liquid crystalline lipid matrix model in the presence (25 - 90%, w/w) and absence of cineole was prepared from SC lipids and characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and polarized light microscopy (PLM) studies. Release of the model lipophilic drug (diazepam) from cineole and cineole-treated matrices and the permeation of the drug from cineole and cineole-containing matrices (as a vehicle similar to the stratum corneum lipids) through excised rat skin were studied. Drug assay was performed by HPLC. The PLM, DSC, and X-ray studies showed that the model matrix had a lamellar gel-liquid crystalline structure, and cineole fluidized the structure concentration-dependently and created other mesomorphic textures, such as myelinic figures. Release experiments showed that diffusion coefficients remained almost constant at high cineole concentrations of 40-90%, suggesting similar fluidization states. Skin permeation studies indicated that the diffusion coefficient (estimated from lag-time) increased concentration-dependently and played a role in permeability coefficient (Kp) increments alongside the increased partitioning of the model drug into the skin. Data suggest that high concentrations of cineole at the skin surface might not provide enough cineole in the skin for full fluidization, despite the similarity of the vehicle to SC lipids and even at high concentrations. The enhancement effect of cineole is concentration-dependent and might reach maximum fluidization at certain concentrations, but this maximum might not be easily achievable when cineole is used in formulations as pure or in a vehicle.

A Mechanistic Study on the Fluidization and Enhancement Effects of Cineole Toward Stratum Corneum Intercellular Lamellar Lipids: A Liquid Crystalline Model Approach

Background: The stratum corneum (SC) serves as the primary barrier for permeation in human skin. Penetration enhancers, such as 1,8-cineole, are utilized to enhance the permeation of drugs. Cineole increases the permeation of chemicals through different mechanisms. However, its mechanism, particularly at high concentrations, has not been well-studied and is the subject of the present investigation. Objectives: In continuation of our previous studies, the present investigation aims to elucidate the mechanism of action and concentration dependency of the effects of 1,8-cineole on the structure, diffusional properties, and partitioning behavior of the SC at high concentrations. This will be achieved through lamellar liquid crystalline models and ex-vivo skin studies. Methods: A lamellar liquid crystalline lipid matrix model in the presence (25 - 90%, w/w) and absence of cineole was prepared from SC lipids and characterized by X-ray diffraction, differential scanning calorimetry (DSC), Thermogravimetric Analysis (TGA), and Polarized Light Microscopy (PLM) studies. The release of the model lipophilic drug (diazepam) from cineole and cineole-treated matrices and the permeation of the drug from cineole and cineole-containing matrices (as a vehicle similar to the stratum corneum lipids) through excised rat skin were studied. A drug assay was performed by HPLC. Results: The PLM, DSC, and X-ray studies showed that the model matrix had a lamellar gel-liquid crystalline structure, and cineole fluidized the structure concentration dependently and created other mesomorphic textures, such as myelinic figures. Release experiments showed that diffusion coefficients remained almost constant at high cineole concentrations of 40-90%, suggesting similar fluidization states. Skin permeation studies indicated that the diffusion coefficient (estimated from lag-time) increased concentration-dependently and played a role in permeability coefficient (Kp) increments alongside the increased partitioning of the model drug into the skin. Data suggest that high concentrations of cineole at the skin surface might not provide enough cineole in the skin for full fluidization, despite the similarity of the vehicle to SC lipids and even at high concentrations. Conclusions: The enhancement effect of cineole is concentration-dependent and might reach maximum fluidization at certain concentrations, but this maximum might not be easily achievable when cineole is used in formulations as pure or in a vehicle.

Nanometric and Macroscopic Electroactive Response of P(VDF-co-TrFE) Copolymers and P(VDF-ter-TrFE-ter-CTFE) Terpolymers

The knowledge and the improvement of the electric responsiveness of P(VDF-co-TrFE) copolymer and P(VDF-ter-TrFE-ter-CTFE) terpolymer films are essential for their application in electronic devices. Many factors affect the performances of these electroactive films, such as the chemical composition and the thermal treatment. In this article, the response to an external electric field of copolymer and terpolymer films at both the nanometric and macroscopic scales is studied. The response at the nanometric scale is analyzed by piezoresponse force microscopy on thin films (∼100 nm thick), while that at the macroscopic scale is analyzed by measuring the electric displacement–electric field loops on thick films (∼20 μm thick). The effect of the chemical composition (CTFE content) is found to be crucial, both at the nanometric and macroscopic scales, in defining the electroactive behavior of the samples, while the thermal treatment seems more exacerbated at the nanometric scale. The orientation, shape, and size of the crystalline lamellae affect the orientation of the electric dipoles, which are thus more or less sensitive to the applied electric field. The controlled growth of edge-on lamellar stacks, obtained after crystallization from the melt at low cooling rates, provides a better piezoresponse of the film.

A model for the reproduction of amylopectin cluster by coordinated actions of starch branching enzyme isoforms.

Amylopectin is a highly branched glucan which accounts for approximately 65-85% of starch in most plant tissues. It is crucially important to understand the biosynthetic process of this glucan in regulating the structure and functional properties of starch granules. Currently, the most accepted ideas of structural feature and biosynthesis of amylopectin are that amylopectin is composed of a branched element called "cluster" and that the essential process of amylopectin biosynthesis is to reproduce a new cluster from the existing cluster. The present paper proposes a model explaining the whole process of amylopectin biosynthesis as to how the new cluster is reproduced by concerted actions of multiple isoforms of starch biosynthetic enzymes, particularly by combinations of distinct roles of starch branching enzyme (BE) isoforms. This model proposes for the first time the molecular mechanism as to how the formation of a new cluster is initiated, and the reason why BEI can play a major role in this step. This is because BEI has a rather broad chain-length preference compared to BEIIb, because a low preference of BEI for the substrate chain-length is advantageous for branching a couple of elongated chains that are not synchronously formed and thus these chains having varied lengths could be safely attacked by this isoform. On the contrary, it is unlikely that BEIIb is involved in this reaction because it can react to only short chains having degree of polymerization of 12-14. BEIIa is possibly able to complement the role of BEI to some extent, because BEIIa can attack basically short chains but its chain-length preference is lower compared with BEIIb. The model implies that the first branches mainly formed by BEI to construct the amorphous lamellae whereas the second branches predominantly formed by BEIIb are located mainly in the crystalline lamellae. This paper provides new insights into the roles of BEI, BEIIb, and BEIIa in amylopectin biosynthesis in cereal endosperm.

Molecular Simulations of Controlled Polymer Crystallization in Polyethylene.

Multilamella polymer crystals are grown from the melt for the first time, in molecular dynamics simulations of a united-monomer model, with in excess of 1500000 united-monomers. Two-component systems comprised of equal weight fractions of 2000 united-monomer long chains and 200 united-monomer short chains are considered, with varying numbers of short butyl branches placed along the long chains. Utilizing two different cooling protocols, continuous-cooling and self-seeding, drastically different multilamella structures are revealed, which depend heavily on the branch content and crystallization protocol used. By self-seeding, well-aligned multilamella crystals are grown, which more clearly reveal the subtle alterations an increasing number of branches create on the size and shape of the crystallites in the early stages of spherulite formation. Under continuous cooling, this observation is almost completely obscured. At maximum thickness, chain portions as long as 100 united-monomers (200 carbons) are extended inside the crystalline lamella.

Changes in Structural and Thermodynamic Properties of Starch during Potato Tuber Dormancy.

The main reserve polysaccharide of plants-starch-is undoubtedly important for humans. One of the main sources of starch is the potato tuber, which is able to preserve starch for a long time during the so-called dormancy period. However, accumulated data show that this dormancy is only relative, which raises the question of the possibility of some kind of starch restructuring during dormancy periods. Here, the effect of long-term periods of tuber rest (at 2-4 °C) on main parameters of starches of potato tubers grown in vivo or in vitro were studied. Along with non-transgenic potatoes, Arabidopsis phytochrome B (AtPHYB) transformants were investigated. Distinct changes in starch micro and macro structures-an increase in proportion of amorphous lamellae and of large-sized and irregular-shaped granules, as well as shifts in thickness of the crystalline lamellae-were detected. The degree of such alterations, more pronounced in AtPHYB-transgenic tubers, increased with the longevity of tuber dormancy. By contrast, the polymorphic crystalline structure (B-type) of starch remained unchanged regardless of dormancy duration. Collectively, our data support the hypothesis that potato starch remains metabolically and structurally labile during the entire tuber life including the dormancy period. The revealed starch remodeling may be considered a process of tuber preadaptation to the upcoming sprouting stage.