Synthesis and thermal behaviour of salicylaldimine-based liquid crystalline symmetrical dimers

A series of symmetrical dimers consisting of salicylaldimine moieties connected by flexible alkylene central spacer via ether linkages has been synthesized. In order to validate the empirical rule suggested by Date et al. to account for the smectic behaviour of such dimers, the chain length of the terminal alkoxy chain has been kept constant (C₈) while the number of methylene units in the central spacer was varied from C₃ to C₁₁. Another aim of the present investigation was to understand structure-property relationship in these dimers in which the salicylaldimine mesogenic segment has been used for the first time in dimers. The mesomorphic behaviour of these dimers was evaluated using optical microscopy and differential scanning calorimetry and the structure of some of the mesophases has been further investigated with the help of X-ray diffraction. Our studies reveal that the dimers consisting of 3 to 8 methylene units in the flexible spacer show only smectic (smectic C and smectic A) phases. For the dimers containing 4, 6 and 8 methylene units in the central spacer, a unique filament growth pattern has been observed in the smectic A phase while cooling from the isotropic phase. The dimers containing of C₉ to C₁₁ methylene groups exhibit the nematic phase in addition to smectic modifications. This observation indicates that when the terminal chains are shorter than the spacer, the tendency to form smectic phases is not fully extinguished but is perhaps reduced.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

Self‐Assembly of Imidazolium‐Based Rodlike Ionic Liquid Crystals: Transition from Lamellar to Micellar Organization

By using aryl‐amination chemistry, a series of rodlike 1‐phenyl‐1H‐imidazole‐based liquid crystals (LCs) and related imidazolium‐based ionic liquid crystals (ILCs) has been prepared. The number and length of the C‐terminal chains (at the noncharged end of the rodlike core) and the length of the N‐terminal chain (on the imidazolium unit in the ILCs) were modified and the influence of these structural parameters on the mode of self‐assembly in LC phases was investigated by polarizing microscopy, differential scanning calorimetry, and X‐ray diffraction. For the single‐chain imidazole derivatives nematic phases (N) and bilayer SmA₂ phases were found, but upon increasing the number of alkyl chains the LC phases were lost. For the related imidazolium salts LC phases were preserved upon increasing the number and length of the C‐terminal chains and in this series it leads to the phase sequence SmA–columnar (Col)–micellar cubic (Cub_I/Pm3n). Elongation of the N‐terminal chain gives the reversed sequence. Short N‐terminal chains prefer an end‐to‐end packing of the mesogens in which these chains are separated from the C‐terminal chains. Elongation of the N‐terminal chain leads to a mixing of N‐ and C‐terminal chains, which is accompanied by complete intercalation of the aromatic cores. In the smectic phases this gives rise to a transition from bilayer (SmA₂) to monolayer smectic (SmA) phases. For the columnar and cubic phases the segregated end‐to‐end packing leads to core–shell aggregates. In this case, elongation of the N‐terminal chains distorts core–shell formation and removes Cub_I and Col phases in favor of single‐layer SmA phases. Hence, by tailoring the length of the N‐terminal chain, a crossover from taper‐shaped to polycatenar LC tectons was achieved, which provides a powerful tool for control of self‐assembly in ILCs.     

Non-symmetric chiral isoflavone dimers: synthesis,characterisation and mesomorphic behaviour

A new series of non-symmetric chiral isoflavone-based liquid crystalline dimers, α-(2-methylbutyl-4′-(4″-phenyloxy)benzoate)-ω-(3-(4′-decyloxyphenyl)-4H-1-benzopyran-4-one-7-oxy)alkanes, with 3–12 carbon atoms in the alkyloxy spacer, have been synthesised. A pronounced odd–even effect for the phase transition temperatures upon varying the spacer length was observed. The short dimers exhibited monolayer smectic A (SmA) and smectic C (SmC*) phases while for longer homologues a chiral nematic (N*) phase was found. The temperature range of the nematic phase was broadened with elongation of the alkyl spacer. Stabilisation of the nematic phase resulted from competition between the monolayer and intercalated smectic structures. The SmA–SmC* phase transition was second order for all studied compounds with a cross over to the de Vries type behaviour for the shortest homologue.     

Mesogenic Unsymmetric dimers containing cholesteryl ester and tolane moieties

Among unsymmetric oligomesogens, chiral dimers formed by connecting a cholesteryl ester fragment with various aromatic mesogenic cores through a polymethylene spacer have been attracting much attention due to their remarkable thermal behaviour. In particular, dimers containing a diphenylacetylene segment having an alkoxy chain have shown interesting mesomorphic behaviour. In view of this a new series of unsymmetric dimers consisting of a diphenylacetylene moiety having an alkyl chain and a cholesteryl ester unit joined through a paraffinic spacer have been synthesized and their liquid crystalline properties characterized. The lengths of the central methylene spacer (C₃, C₄, C₅ and C₇) as well as that of the alkyl chain (n-butyl, n-pentyl, n-hexyl and n-heptyl) have been varied to establish structure–property relationships. These investigations have revealed that all the dimers exhibit smectic A, twist grain boundary and chiral neamtic (N*) phases with the exception of one of the dimers for which only the N* phase was observed. Some differences in the mesomorphic properties of the unsymmetric dimers containing odd or even parity methylene spacers have been observed. The majority of dimers having an even (C₄) parity paraffinic spacer show a blue phase while the dimers with odd (C₃, C₅ and C₇) parity spacers exhibit the chiral smectic (SmC*) phase. In some cases, the SmC* phase exists well below (?60°C) and above room temperature.     

Liquid crystal dimers containing Cholesteryl and Triazole-containing mesogenic units

ABSTRACT

New liquid crystals categorised as cholesteryl dimers have been successfully synthesised through the reaction between cholesteryl 4-(prop-2-ynyloxy)benzoate moieties with n-azido(cholesteryloxy-carbonyl)alkane. All the dimers display enantiotropic mesophases. Whilst the odd-numbered dimers exhibit chiral nematic (N*), twisted grain boundary (TGB) and chiral smectic C (SmC*) phases, the even-numbered members from the same series show chiral smectic A and C. A detailed inspection on mesophase reveals that the chiral centres and the bent conformation of the odd-numbered members are essential for the induction of TGB phase. However, upon decreasing the temperature, the ratio of the transition temperatures (T_SmC*-SmA*/T_SmA*-I) is found to be 0.95, which indicate the second order transition according to the McMillan’s molecular theory. In addition, the X-ray diffraction study supports the presence of the smectic A phase on the even members rather than the N* by the appearance of the Bragg diffraction peaks at 190°C. A comparison study with the other analogues in which the cholesterol entity is substituted by azobenzene or biphenyl tails has been carried out to assess the relationship between the molecular structure and mesomorphic behaviour.     

Dimesogenic compounds consisting of cholesterol and azobenzene-based moieties: dependence of liquid crystal properties on spacer length and fluorination of the terminal chain

The liquid crystalline (LC) properties of two series of non-symmetric dimesogenic compounds consisting of cholesterol and azobenzene-based moieties interconnected by ω-oxyalkanoyl spacers of varying length are compared: one series (AOC-n) has an octyloxy chain attached to the azobenzene mesogen unit while the other (AOCF-n) has a perfluoroheptylmethyloxy chain. In general, compounds bearing the fluorinated alkoxy chain exhibited LC properties over a much broader temperature range than those with the alkoxy chain. In addition, the AOC-n series exhibited the chiral smectic C (SmC*), smectic A (SmA) and cholesteric (N*) phases depending on the length of the central spacer, whereas the AOCF-n series favoured the formation of only the SmA phase with the N* phase completely suppressed. Both series showed an odd-even dependence of the isotropization temperature on spacer length.     

Ferroelectric Liquid Crystals: Synthesis and Thermal Behavior of Optically Active,Three‐Ring Schiff Bases and Salicylaldimines

The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high‐resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end‐use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three‐ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)‐3,7‐dimethyloctyloxy and (3 R)‐3,7‐dimethyloctyloxy tails. To probe the structure–property correlations in each series, the length of the n‐alkoxy tail situated at the other end of the mesogens has been varied from n‐octyloxy to n‐dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X‐ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80–115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (P_S) in the range 69–96 nC cm^?2. The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite.     

Effect of the Magnetic Field on the Supramolecular Structure of Chiral Smectic C Phases: 2H NMR Studies

We present a theoretical and experimental ²H NMR study of the effect of external magnetic fields on the supramolecular organization of chiral smectic liquid‐crystalline mesophases, such as SmC* and re‐entrant SmC*. Three experimental cases in which the supramolecular helical structure of the smectic C* phase is unwound by a magnetic field (H), parallel to the helical axes of this phase, are discussed in detail. Unwinding of the helical structure is described by using a theoretical model based on the Landau‐de Gennes theory, which allows us to explain the transition temperatures among the SmA, SmC*, and uSmC* phases. The energy‐density behavior in the vicinity of the transitions and the value of the critical magnetic field H_C for unwinding the helical structure are discussed by applying this model to three ferroelectric smectogens ( MBHB , 11EB1M7 , ZLL7/* ), which are studied by ²H NMR spectroscopy at different magnetic fields (from 2.4 to 9.4 Tesla). Furthermore, the tilt angle of the three smectogens in the SmC* phase has been directly evaluated, for the first time, by comparing the quadrupolar splittings at different magnetic fields. In one case, ²H NMR angular measurements are used to obtain the tilt angle in the re‐entrant smectic C phase.     

Influence of alkoxy tail length on the self‐organization of hairy‐rod polymers based on mesogen‐jacketed liquid crystalline polymers

A series of hairy‐rod polymers, poly{2,5‐bis[(4‐alkoxyphenyl)oxycarbonyl]styrenes} (P‐OCm, m = 1, 2, 4, 6, 8, 10, 12, 14, 16, and 18) were designed and successfully synthesized via free radical polymerization. The chemical structure of the monomers was confirmed by elemental analysis, ¹H NMR and ¹³C NMR. The molecular characterizations of the polymers were performed with ¹H NMR and gel permeation chromatography. The phase structures and transitions of the polymers were investigated by the combination of techniques including differential scanning calorimetry, wide‐angle X‐ray diffraction, polarized optical microscopy, and rheological measurement. The experimental results revealed that the self‐assembly behaviors of P‐OCm changed with the increase in m. First, the P‐OCm (m = 1, 2) showed only a stable liquid crystalline phase above T_g. Second, with the increasing length of alkoxy tails, the P‐OCm (m = 4, 6, 8) presented a re‐entrant isotropic phase above T_g and a liquid crystalline phase at higher temperature. Third, the P‐OCm (m = 10, 12, 14, 16, 18) exhibited an unusual re‐entrant isotropic phase which was separating SmA (in low temperature) and columnar phases (in high temperature). It was the first time that mesogen‐jacketed liquid crystalline polymers formed smectic phase, re‐entrant isotropic phase, and columnar phases in one polymer due to the microphase separation and the driving force of the entropy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,structure, and properties of chiral liquid crystal monomers and polymers based on menthol

To study structure–mesomorphism relationships of the monomers and polymers based on menthol, four new chiral monomers ( M₁ – M₄ ) and the corresponding homopolymers ( P₁ – P₄ ) with menthyl group were synthesized. Their chemical structures, formula, phase behavior, and thermal stability were characterized by FTIR, ¹H NMR, ¹³C NMR, elemental analyses, differential scanning calorimetry, polarizing optical microscopy, X‐ray diffraction, and thermogravimetric analysis. The selective reflection of light was investigated with ultraviolet/visible spectrometer. The influence of the mesogenic core rigidity, spacer length, and menthyl steric effect on the mesomorphism of M₁ – M₄ and P₁ – P₄ was examined. By inserting a flexible spacer between the mesogenic core and the terminal menthyl groups, four target monomers and polymers could form the expected mesophase. Moreover, their melting temperature (T_m), glass transition temperature (T_g), clearing temperature (T_i), and mesophase range (ΔT) increased with increasing the mesogenic core rigidity; whereas the T_m and T_g decreased, T_i and ΔT increased with an increase of the spacer length. M₁ and M₂ showed monotropic and enantiotropic cholesteric phase, respectively, whereas M₃ and M₄ all revealed chiral smectic C (SmC*), cholesteric and cubic blue phases. In addition, with increasing temperature, the selective reflection of light shifted to the long wavelength region at the SmC* phase range and to the short wavelength region at the cholesteric range, respectively. P₁ and P₂ only showed a smectic A (SmA) phase, whereas P₃ and P₄ exhibited the SmC* and SmA phases. All the obtained polymers had very good thermal stability. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012     

A Twist‐Bend Nematic (NTB) Phase of Chiral Materials

New chiral dimers consisting of a rod‐like and cholesterol mesogenic units are reported to form a chiral twist‐bend nematic phase (N_TB*) with heliconical structure. The compressibility of the N_TB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the N_TB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non‐chiral compounds (ca. 10 nm).     

Ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid with non‐fluorinated or semi‐fluorinated alkanes at a chiral terminal chain

Two series of ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid, with non‐fluorinated or semi‐perfluorinated alkanes positioned at a chiral terminal chain, have been synthesized and characterized by differential scanning calorimetry, polarizing optical microscopy and electro‐optical measurements. The non‐fluorinated compounds, 1‐hexyl (S)‐2‐{6‐[4‐(4‐alkanoyloxyphenyl)benzoyloxy]‐2‐napthyl}propionates exhibit rich mesomorphism—the BP_II, N*, TGB_A*, SmA* and SmC* phases. The fluorinated compounds display only the SmA* and SmC* phases, suggesting that the fluorination promotes the formation of smectic phases. In addition, the SmA* and SmC* phases of the fluorinated compounds have enhanced thermal stability as compared with the corresponding phases of the non‐fluorinated compounds. The spontaneous polarization (P _s values) for the non‐fluorinated compounds are higher than those of the fluorinated compounds at any reduced temperature below the SmA*–SmC* transition. The electro‐optical responses measured for these compounds in the ferroelectric phase displayed thresholdless, V‐shaped switching.     

Anomalous behaviour in the SmA*–SmCA* pre‐transitional regime of a chiral swallow‐tailed antiferroelectric liquid crystal

The temperature‐ and electric field‐dependent dielectric relaxation and polarisation of a new chiral swallow tailed antiferroelectric liquid crystal, i.e. 1‐ethylpropyl (S)‐2‐{6‐[4‐(4′‐decyloxyphenyl)benzoyloxy]‐2‐naphthyl}propionate (abbreviated as EP10PBNP), were investigated. The electric field‐induced dielectric loss spectra of EP10PBNP revealed electroclinic and anomalous dielectric behaviour in the chiral smectic A (SmA*)–chiral antiferroelectric smectic C (SmC_A*) pre‐transitional regime. From an analysis of thermal hysteresis of the dielectric constant, electric field‐induced polarisation and dielectric loss spectra, the appearance of a ferrielectric‐like mesophase is observed followed by an unstable SmC_A* phase in the SmA*–SmC_A* pre‐transitional regime.     

Liquid crystal dimers possessing chiral rod-like anisometric segments: synthesis, characterization and electro-optic behaviour

Several new optically active liquid crystal dimers comprising pro-mesogenic cholesterol and a chiral diphenylacetylene (tolane) segment, covalently linked in an end-to-end fashion through a flexible spacer, have been synthesized and investigated for their mesomorphic behaviour with the aid of optical, calorimetric and X-ray diffraction studies. Five unsymmetrical dimers, designed on the basis of recent work, involve molecular structural variations of the tolane mesogenic entity with a view to stabilizing a wide thermal range smectic A (SmA) phase featuring the electroclinic effect. Three different chiral chains, namely, (S)-1-methylheptyloxy, (S)-2-methylbutyloxy, (3S)-3,7-dimethyloctyloxy, with or without polar (nitro or fluoro) lateral substituents, were incorporated, while keeping the length (C₆) of the spacer constant. As expected, all the dimers exhibited a SmA phase. A few also showed chiral nematic (N*) and/or twist grain boundary and/or chiral smectic C (SmC*) phases. Remarkably, some of these oligomesogens, upon melting, had a stable SmA phase over a wide thermal interval (100-150°C); this state seems to be stable for a long period of time. Electro-optic studies, including optical tilt angle as well as temporal response as a function of temperature, were carried out in the SmA phase. The SmC* phase was also investigated for its electrical switching and optical tilt angle, as well as spontaneous polarization as a function of temperature. These studies showed that the mesophase response to an applied field is weak and is independent of variations in the dimer investigated.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd-even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd–even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

Optically active,mesogenic lanthanide complexes: design,synthesis and characterisation

The synthesis, molecular structural characterisation and mesomorphic behaviour of lanthanidomesogens with the formula [LnL(LH)₂ ][X]₂ are reported. These mesogens were derived from ligands (LH- n ) formed by covalently linking the pro-mesogenic cholesterol segment with the N-(n-decyl)salicylaldimine core through either an even-parity (4-oxybutanoyloxy/6-oxyhexanoyloxy/8-oxyoctanoyloxy) or an odd-parity (5-oxypentano-yloxy) spacer. These ligands were designed based on the recently conceived concept of decoupling the anisometric segment from the metal-coordinating site by a flexible spacer to account for the stabilisation of nematic and/or smectic phases at lower temperatures. The even parity spacer ligands are polymesomorphic whereas the odd parity analogue exhibits only the chiral nematic phase. In contrast, the complexes display solely the smectic A phase indicating that the variation in the nature of lanthanide has no influence on the general phase behaviour of the complexes. The clearing temperatures of both the ligands and the complexes display an odd-even effect; the even members show relatively higher transition temperatures.     

Azobenzene‐containing LC polymethacrylates highly photosensitive in broad spectral range

Two photosensitive chiral liquid crystalline azobenzene‐containing polymethacrylates having different length of flexible spacer connecting chromophores with backbone were synthesized and their phase behavior and photo‐optical properties were studied. Both polymers consist of lateral methyl substituents in ortho‐position of azobenzene chromophores providing high photosensitivity even in red spectral region as well as high thermal stability of photoinduced Z‐form of azobenzene chromophores. It is shown, that smectic phase (SmA*) formation in films of polymer with longer spacer predetermines its quite unusual spectral response to UV and subsequent visible light actions. The SmA* phase promotes spontaneous homeotropic alignment of azobenzene chromophores in polymer films. UV‐irradiation induces not only E‐Z isomerization but also results in disruption of homeotropic alignment, whereas subsequent visible light action enables to obtain films with the low degree of chromophores orientation. The photo‐orientation phenomena under the action of polarized light of different wavelength on polymer films were studied. The possibility of using red polarized light of moderate intensity for optical photorecording on polymer films is demonstrated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2962–2970     

Indirect reversed‐phase high‐performance liquid chromatographic and direct thin‐layer chromatographic enantioresolution of (R,S)‐Cinacalcet

Enantioresolution of the calcimimetic drug (R,S)‐Cinacalcet was achieved using both indirect and direct approaches. Six chiral variants of Marfey's reagent having l ‐Ala‐NH₂, l ‐Phe‐NH₂, l ‐Val‐NH₂, l ‐Leu‐NH₂, l ‐Met‐NH₂ and d ‐Phg‐NH₂ as chiral auxiliaries were used as derivatizing reagents under microwave irradiation. Derivatization conditions were optimized. Reversed‐phase high‐performance liquid chromatography was successful using binary mixtures of aqueous trifluoroacetic acid and acetonitrile for separation of diastereomeric pairs with detection at 340 nm. Thin silica gel layers impregnated with optically pure l ‐histidine and l ‐arginine were used for direct resolution of enantiomers. The limit of detection was found to be 60 pmol in HPLC while in TLC it was found to be in the range of 0.26–0.28 µg for each enantiomers. Copyright © 2010 John Wiley & Sons, Ltd.