Stability similarities between shells, cells and nano carbon tubes Y. Yin, H.-Y. Yeh and J. Yin Abstract: The similarity in stability characteristics between multiscale circular cylindrical structures is revealed. Two detailed structures are explored. One is the circular cylindrical shell on an engineering scale, and another is the circular cylindrical lipid bilayer vesicle on a micro- or nanoscale. The critical stability of the vesicle acted on by uniformly distributed radial pressure is analysed. The critical load of the vesicle is derived and compared with that of the thin shell. The astonishing similarity between them is disclosed. The possible applications of such similarity to biophysics, biology and biomedicine are presented.

1

Introduction

In past decades, the differences between multiscale structures and the size effects in small-scale structures have become one of the focuses in science and technology. A famous example concerns nano carbon tubes, the excellent mechanical and physical properties of which have drawn the attention of researchers throughout the world. Understanding the differences is important to enable us better to handle the marvellous properties of small-scale structures. When the differences between multiscale structures are emphasised, their similarities should not be neglected. Therefore the similarities between multiscale structures will be studied in this paper, namely, the similar stability characteristics of circular cylindrical shells on an engineering scale, circular cylindrical vesicles on a micro- or nanoscale and nano carbon tubes will be investigated. In engineering, shells are usually made from metals by metallurgical methods. In biophysics, vesicles or layer membranes are usually generated in aqueous solutions through the self-assembly of amphiphilic molecules with chains of a few nanometres. Shells are considered as isotropic solids, whereas vesicles are regarded as normalanisotropic liquid crystals. The characteristic diameter and thickness of shells are, respectively, in the order of metres and centimetres, whereas those of vesicles are, respectively, in the order of micro- (or nano-) metres and nanometres. The differences in the manufacture, materials, substructures and scales between shells and vesicles are so huge that any minor similarity between them seems to be unbelievable. However, similarities do exist, at least in stability characteristics. In addition to vesicles, nano carbon tubes are another kind of beautiful, small-scale structure. The stability similarity between shells and nano carbon tubes has been

discussed for a long time. In this paper, the similarity in the critical stabilities between shells, vesicles and nano carbon tubes will be further revealed, and possible applications of this similarity will be proposed. 2

Critical loads of circular cylindrical structures

2.1

Critical load of circular cylindrical shells

Suppose a circular cylindrical shell with radius R is loaded by uniformly distributed radial pressure p on the outer surface (Fig. 1). According to classical solid mechanics, there is a critical value pcr. Once the external load p approaches pcr, the shell will lose stability, and buckling will occur. This critical load has been proven to be [1] 3Kc R3

ð1Þ

Eh3 12ð1  m2 Þ

ð2Þ

pcr ¼ where Kc ¼

Kc is the bending rigidity of the shell’s vertical section; E and m are the Young’s modulus and Poisson’s ratio of the material, respectively; and h is the thickness of the shell. Equation (1) clearly shows that the critical load for circular cylindrical shells is proportional to Kc but inversely proportional to R3.

P

h R

r IEE, 2006 IEE Proceedings online no. 20050021 doi:10.1049/ip-nbt:20050021 Paper received 28th July 2005 Y. Yin and J. Yin are with the Department of Engineering Mechanics, School of Aerospace, FML, Tsinghua University, Beijing 100084, China H.-Y. Yeh is with the Department of Mechanical & Aerospace Engineering, California State University, Long Beach, California, 90840-4407, USA E-mail: [email protected]

Fig. 1 scale

Cross-section of circular cylindrical shell at engineering

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2.2 Critical load of circular cylindrical vesicles The general theory for the equilibrium and stability of lipid bilayer vesicles is as follows. The potential functional F is usually taken as [2–4]  ZZZ ZZ ZZ  1 kc ð2H c0 Þ2 þ kK dA þ Dp dV þl dA F¼ 2 V

A

A

ð3Þ where Dp ¼ pout  pin is the difference between the outer and inner pressure; l ¼ lin þ lout is the sum of the surface energy densities on the inner and outer surfaces; c0 is the spontaneous curvature; H and K are the mean curvature and Gauss curvature, respectively; and kc and k are the mean curvature rigidity and Gauss curvature rigidity, respectively. By minimising the potential functional, i.e. dð1Þ F ¼ 0, the equilibrium differential equation for vesicles [3, 4] can be ascertained as 2kc r2 H þ f ¼ 0

ð4Þ

f ¼ Dp  2lH þ kc ð2H  c0 Þð2H 2 þ c0 H  2KÞ ð5Þ RR In [5], the geometrical constraint equation, A fdA ¼ 0, was revealed and proven to be valid for any closed vesicle. For a vesicle with constant kc, Dp, l and c0, this geometrical constraint equation becomes ZZ ZZ 2l þ kc c20 4kc HdA  H ðH 2  KÞdA Dp ¼ A A A



2kc c0 A

A

ZZ

ð6Þ

KdA A

The critical criterion for a vesicle to lose stability can be derived from the second variation of the potential functional dð2Þ F ¼ 0

ð7Þ

For a vesicle at critical stability, (4), (6) and (7) should be observed simultaneously. As far as a circular cylindrical vesicle with radius r is concerned (Fig. 2), we have f ¼ Const. Thus (4) will be met automatically if (6) is satisfied. Therefore the critical load can be derived from the combination of (6) and (7). Equation (6) is transformed into c20 

1 2ðDpr þ lÞ þ ¼0 r2 kc

ð8Þ

The deformation mode c in the cross-section and along the normal direction of the circular cylindrical vesicle’s surface

is usually taken as [4] X am eimy c¼

2r p

ð9Þ

Note that the spontaneous curvature c0 is the only physical quantity that could not be measured directly by experiment [5]. Thus, by combining (7)–(9) and cancelling out c0, we can obtain the final form of the critical criterion   X kc 2 2 ð2Þ 2 d F ¼p jam j ðm  1Þ Dp þ 3 ðm  1Þ ¼ 0 r m ð10Þ At the lowest order of the deformation mode (i.e. m ¼ 2), the critical criterion for the stability of circular cylindrical vesicles can be further written as 3kc ¼0 ð11Þ r3 At last, the critical load for circular cylindrical vesicles can be determined Dp þ

3kc ð12Þ r3 Equation (12) clearly discloses that the critical load for circular cylindrical vesicles is proportional to the curvature rigidity kc but inversely proportional to r3. ðDpÞcr ¼

2.3 Critical load of single-wall nano carbon tubes By treating the Lenosky lattice model [6] as a continuous one, Ou-yang et al. derived the curvature elastic energy for a single-wall nano carbon tube [7]  ZZ  1 2  kct ð2H Þ þ kt K dA Et ¼ ð13Þ 2 A

Detailed formulations for the elastic modus kct and kt can be seen in [7]. According to the authors’ experience, the spontaneous curvature c0 in (3) is necessary to keep the equilibrium and stability theory for vesicles to self-assemble. This may also be true for the nano carbon tubes. Thus the spontaneous curvature c0t for the nano carbon tube is introduced, and (13) can be slightly modified as  ZZ  1 2  kct ð2H  c0t Þ þ kt K dA Et ¼ ð14Þ 2 A

Suppose that a uniform radial pressure p is loaded on the outer surface of the nano carbon tube (Fig. 3), then the total potential functionality of the tube can be constructed from (14) as follows  ZZ  ZZZ 1 2  kct ð2H  c0t Þ þkt K dA þ p dV ð15Þ Ft ¼ 2 V

A

p

out

0  y  2p

m

Because (15) is almost the same as (3), the critical load for the nano carbon tubes can be deduced in the same way as that for vesicles in Section 2.2: 3kct ð16Þ pcr ¼ 3 r

in

3

Comparisons and discussions

3.1 Similarity between critical loads for multiscale structures Fig. 2 Cross-section of circular cylindrical vesicle at micro- or nanoscale 8

The three critical loads are similar both in form and in content, as shown in (1), (12) and (16). Here, we focus on (1) for shells and (12) for vesicles as we consider why such a IEE Proc.-Nanobiotechnol., Vol. 153, No. 1, February 2006

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similarity exists. First, the surface tension disappears in the formulation of critical load for circular cylindrical vesicles. At micro- or nanoscales, surface tensions usually play important roles. Fortunately, the terms related to the surface tension l cancel each other out during the derivation process. Therefore l does not occur in (12), which makes the above similarity possible. Secondly, the global geometric structures are similar. Both the shell and the vesicle have circular cylindrical surfaces. Thirdly, the material property is similar. Both the shell and the vesicle are treated as elastic: the former is an elastic cylinder, and the latter is an elastic nano membrane. Fourthly, the deformation modes are similar. Both the shell and the vesicle are assumed to lose stability in the cross-section and along the normal direction of the surface. The similarity between the critical loads is of importance: it enables us to use the knowledge about the stability of shells to control the stability of vesicles. From (1) and (12), two controlling routes are disclosed. The first way is to control the rigidity. In a shell, the rigidity is proportional to h3. Thus a very effective way to change the rigidity is to vary the thickness of the shell. Similarly, in a vesicle, the thickness of the lipid bilayer will also be a vital factor. To increase the stability, amphiphilic molecules with longer chains should be selected for self-assembly of vesicles. The second way is to adjust the radius. This will be the most effective way, because the critical loads are inversely proportional to R3 or r3. Thus, in engineering, the stability of a shell will be noticeably improved if its radius is reduced. In biophysics, this is also true: vesicles with smaller radius will have much larger critical load and much better stability.

3.2

Measurement of the curvature rigidity

In a thin shell, the elastic modulus Kc is easy to determine, because both E and m in (2) can be measured by conventional tensile experiment. However, for a vesicle at a micro- or nanoscale, the curvature rigidity kc is about the order of 1013 erg. Such a small physical quantity is very difficult to measure. To obtain accurate kc, precise and expensive experimental facilities and researchers with superb experimental skills are necessary. Fortunately, (12) initiates the idea of measuring kc by conventional technologies and methods: 1 ð17Þ kc ¼ ðDpÞcr r3 3 At the instant when the vesicle loses stability, r can be recorded under microscope. ðDpÞcr can be computed from the measured osmotic pressure. Thus kc can be easily calculated from (17). The above idea may be applicable to nano carbon tubes. A circular cylindrical lipid bilayer vesicle at nanoscale is comparable with a nano carbon tube: the former is geometrically a circular cylinder, and so is the latter. The former is an ordered arrangement of amphiphilic molecules, whereas the latter is an ordered network of carbon atoms. As mentioned above, the curvature rigidity for the former is a minor physical quantity and can be measured easily at the critical state. Similarly, the curvature rigidity for the latter is also a minor physical quantity and can also be measured accurately by making full use of its critical stability. This judgment may be heuristic. In past years, one of the focuses on the mechanical properties of nano carbon tubes involved determining the elastic modulus through the measurement of tensile rigidity. Although intensive experiments have been performed, the measured accuracy for the tensile rigidity of nano carbon tubes are still inadequate, and the data obtained are still very divergent. This may be because the

tensile rigidity of the tube-like atom-network is very sensitive to defects such as dislocations or mismatches between carbon atoms. Instead of the tensile rigidity, the curvature rigidity of nano carbon tubes can be recorded from (16) 1 ð18Þ kct ¼ pcr r3 3 If the elastic modulus is calculated from the curvature rigidity, then the accuracy can be improved to a large extent.

3.3

Potential applications to cells

In biophysics and biology, vesicles are usually regarded as an idealised model for cell membranes. Hence, the quantified results for vesicles above may help us to understand and control cell behaviours. The critical load for vesicles in (12) may be useful in explaining the stability of cells and answering why the characteristic size for living cells in animals or plants is very small (usually a few micrometres). According to (12), cells of a large size possess low critical load and poor stability. Thus minor disturbances such as a fluctuation in temperature around the membrane can cause large cells to lose stability. To keep living systems stable, the size of cells must be strictly limited. In short, cells of small size are the inevitable results of life’s evolution and nature’s selection. Unlike vesicles with single-phase molecules, cell membranes are composed of multiphase molecules, such as amphiphilic molecules, cholesterol molecules, proteins, enzymes and so on. On the one hand, different phases have different flexibilities, and different distributions of phases will lead to membranes with different flexibilities. On the other hand, the flexibility of a phase can be affected by environment (e.g. the environment-induced phase transformations in proteins). In short, the flexibilities of cell membranes are controllable. Because a membrane’s flexibilities are closely related to its curvature rigidities, the critical load for cells can also be changed through biological, physical, chemical and mechanical methods. For example, some intercalated cholesterol molecules and some external chemical or medical substances such as drug particles can interact with cell membranes. These interactions can either strengthen or weaken the rigidity of cells and therefore increase or decrease their stability. It is important to understand all the factors that affect the stability of cells. In some cases, we want cells to be more stable, whereas, in other cases, we wish to destroy the stability of cells, such as cancer cells. Cancer cells can be destroyed through various methods, such as chemical, biological (e.g. molecule and gene technology, biological nanotechnology), mechanical and physical methods. Among them, mechanical and physical methods may have a special attraction. In clinical cures, most of the chemical or isotopic treatments for cancer cells inevitably produce side effects that always lead to irreversible deterioration in body health. However, with the aid of mechanical and physical methods, side effects can be reduced during cancer treatment processes. At present, such kinds of method have involved combining advanced laser technology with modern biological nanotechnology. Now, a new mechanical and physical method for abolishing cancer cells can be exploited, i.e. destroying their stability by altering their physical environment or changing their rigidity. Another key point again concerns the curvature rigidity kc. Biologically and medically, it is important to confirm kc as accurately as possible. Usually, the curvature rigidity of a

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cancer cell membrane is different from that of a normal one. If a doctor wants to kill the cancer cell but keep the normal one unharmed, he needs to distinguish more accurately the rigidities of the two cells. Besides, if we try to deliver medicine from the outside to the inside of the cancer cell, we find that the interactions between the medical particles and the cell can vary the rigidity of the membrane. If we know exactly the influence of such interactions on the membrane’s rigidity, we can control quantitatively the dosage of medicine and approach optimum efficiency in curing cancer cells. 4

Conclusions

The similarity in the stability characteristics of thin shells and lipid bilayer vesicles does exist. This quantified similarity enables us to understand better the stability characteristics of vesicles at micro- or nanoscales and provides beneficial enlightenment with regard to curing cancer cells. Furthermore, the simple, precise and quantified method to measure a vesicle’s curvature rigidity (about of 1013 erg) can be used for reference in understanding the

10

mechanical properties of carbon nano tubes and can be broadly applied to various fields, such as biophysics, biology and biomedicine as well.

5

References

1 Timoshenko, S.P.: ‘Strength of materials (part II): advanced theory and problems’ (D. Van Nostrand Company, 3rd edn., 1957), pp. 162–164 (Chinese edition) 2 Helfrich, W.: ‘Elastic properties of lipid bilayers, theory and possible experiments’, Z. Naturuforsch, 1973, 28C, pp. 693–703 3 Zhong-can, O.-Y. et al.: ‘Geometric methods in the elastic theory of membranes in liquid crystal phases’ (Word Scientific, Singapore, New Jersey, London, Hong Kong, 1999), pp. 71–96 4 Zhong-can, O.-Y., and Helfrich, W.: ‘Bending energy of vesicle membranes: general expressions for the first, second and third variations of the shape energy and applications to spheres and cylinders’, Phys. Rev., 1989, A39, pp. 5280–5288 5 Yin, Y., and Yin, J.: ‘Geometrical constraint equations and geometrically permissible condition for vesicles’, Chinese Physics Lett., 2004, 24, pp. 2057–2058 6 Lenosky, T., and Gonze, X.: ‘Energetics of negatively curved graphitic carbon’, Nature, 1992, 355, pp. 333–335 7 Zhong-can, O.-Y. et al.: ‘Coil formation in multishell carbon nanotubes: competition between curvature elasticity and interlayer adhesion’, Phys. Rev. Lett., 1997, 78, pp. 4055–4058

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Stability similarities between shells, cells and nano ...

membranes are usually generated in aqueous solutions through the self-assembly of ..... problems' (D. Van Nostrand Company, 3rd edn., 1957), pp. 162–164. (Chinese edition) ... Jersey, London, Hong Kong, 1999), pp. 71–96. 4 Zhong-can ...

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