Fracto‐mechanoluminescence induced by impulsive deformation of II–VI semiconductors

When II–VI semiconductors are fractured, initially the mechanoluminescence (ML) intensity increases with time, attains a maximum value I_m at a time t_m, at which the fracture is completed. After t_m, the ML intensity decreases with time, I_m increase linearly with the impact velocity v₀ and I_T initially increase linearly with v₀ and then it attains a saturation value for a higher value of v₀. For photoluminescence, the temperature dependence comes mainly from luminescence efficiency, η_o; however, for the ML excitation, there is an additional factor, r_t dependent on temperature. During fracture, charged dislocations moving near the tip of moving cracks produce intense electric field, causes band bending. Consequently, tunneling of electrons from filled electron traps to the conduction band takes place, whereby the radiative electron–hole recombination give rise to the luminescence. In the proposed mechanism, expressions are derived for the rise, the time t_m corresponding to the ML intensity versus time curve, the ML intensity I_m corresponding to the peak of ML intensity versus time curve, the total fracto‐mechanoluminescence (FML) intensity I_T, and fast and slow decay of FML intensity of II–VI semiconductors. The FML plays a significant role in understanding the processes involved in biological detection, earthquake lights and mine failure. Copyright © 2015 John Wiley & Sons, Ltd.     

Fracto‐mechanoluminescence and thermoluminescence properties of UV and γ‐irradiated Ca2Al2SiO7:Ce3+ phosphor

Ce³⁺‐doped calcium aluminosilicate phosphor was prepared by a combustion‐assisted method at an initiating temperature of 600°C. Structural characterization was carried out using X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The absorption spectra of Ca₂Al₂SiO₇:Ce³⁺ showed an absorption edge at 230 nm. The optical characterization of Ca₂Al₂SiO₇:Ce³⁺ phosphor was investigated in a fracto‐mechanoluminescence (FML) and thermoluminescence (TL) study. The peak of ML intensity increased as the height of impact of the moving piston increased. The TL intensity of Ca₂Al₂SiO₇:Ce³⁺ was recorded for different exposure times of UV and γ‐irradiation and it was observed that TL intensity was maximum for a UV irradiation time of 30 min and for a γ‐dose of 1180 Gy. The TL intensity had three peaks for UV irradiation at temperatures 82°C, 125°C and 203°C. Also the TL intensity had a single peak at 152°C for γ‐irradiation. The TL and ML emission spectra of Ca₂Al₂SiO₇:Ce³⁺ phosphor showed maximum emission at 400 nm. The possible mechanisms involved in the TL and ML processes of the Ca₂Al₂SiO₇:Ce³⁺ phosphor are also explained. Copyright © 2015 John Wiley & Sons, Ltd.     

Systematic study of photoluminescence,lyoluminescence and mechanoluminescence in Ce3+‐ and Eu3+‐activated Li3PO4 phosphors

Li₃PO₄ phosphor was prepared using a modified solid‐state diffusion technique. In this work, photoluminescence, lyoluminescence and mechanoluminescence studies were carried out in a Li₃PO₄ microcrystalline powder doped with different rare earths. In photoluminescence studies, characteristic emission of Ce and Eu was observed. The lyoluminescence glow curves of Li₃PO₄ microcrystals show that lyoluminescence intensity initially increases with time and then decreases exponentially. The decay time consists of two components for all masses. The dependence of decay time, especially the longer component, on mass has been investigated. Experiments on γ‐irradiated crystals have proved that the light emission originates from the recombination of released F‐centres with trapped holes (V₂‐centres) at the sulfuric acid–solid interface. Incorporation of bivalent alkali in solid lithium phosphate leads to an enhancement of lyoluminescence. A possible explanation for the experimental results has been attempted. The phosphor has a mechanoluminescence single glow peak. Mechanoluminescence intensity under various loading conditions was investigated. It is observed that mechanoluminescence intensity increases with increasing impurity concentration and increasing piston impact velocity. The results may be considered as only being of academic interest in solid‐state materials. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermoluminescence and photoluminescence studies on γ‐ray‐irradiated Ce3+,Tb3+‐doped potassium chloride single crystals

Single crystals of KCl doped with Ce³⁺,Tb³⁺ were grown using the Bridgeman–Stockbarger technique. Thermoluminescence (TL), optical absorption, photoluminescence (PL), photo‐stimulated luminescence (PSL), and thermal‐stimulated luminescence (TSL) properties were studied after γ‐ray irradiation at room temperature. The glow curve of the γ‐ray‐irradiated crystal exhibits three peaks at 420, 470 and 525 K. F‐Light bleaching (560 nm) leads to a drastic change in the TL glow curve. The optical absorption measurements indicate that F‐ and V‐centres are formed in the crystal during γ‐ray irradiation. It was attempted to incorporate a broad band of cerium activator into the narrow band of terbium in the KCl host without a reduction in the emission intensity. Cerium co‐doped KCl:Tb crystals showed broad band emission due to the d–f transition of cerium and a reduction in the intensity of the emission peak due to ⁵D₃–⁷F_j (j = 3, 4) transition of terbium, when excited at 330 nm. These results support that energy transfer occurs from cerium to terbium in the KCl host. Co‐doping Ce³⁺ ions greatly intensified the excitation peak at 339 nm for the emission at 400 nm of Tb³⁺. The emission due to Tb³⁺ ions was confirmed by PSL and TSL spectra. Copyright © 2015 John Wiley & Sons, Ltd.     

Is the fracto‐mechanoluminescence of ZnS:Mn phosphor dominated by charged dislocation mechanism or piezoelectrification mechanism?

Mathematical approaches made for both the charged dislocation model and piezoelectrically induced electron bombardment model of fracto‐mechanoluminescence (FML), the luminescence induced by fracture of solids, in ZnS:Mn phosphor indicate that the piezoelectrically induced electron bombardment model provides a dominating process for the FML of ZnS phosphors. The concentration of 3000 ppm Mn²⁺ is optimal for ML intensity of ZnS:Mn phosphor. The decay time of ML gives the relaxation time of the piston used to deform the sample and the time t_m of maximum of ML is controlled by both the relaxation time of the piston and decay time of charges on the newly created surfaces of crystals. As the product of the velocity of dislocations and pinning time of dislocations gives the mean free path of a moving dislocation. Both factors play an important role in the ML excitation of impurity doped II–VI semiconductors. The linear increase of total ML intensity I_T with the impact velocity indicates that the damage increases linearly with impact velocity of the load. Thus, the ML measurement can be used remotely to monitor the real‐time damage in the structures, and therefore, the ML of ZnS:Mn phosphor has also the potential for a structural health monitoring system. Copyright © 2015 John Wiley & Sons, Ltd.     

Si‐Doping Mediated Phase Control from β‐ to γ‐Form Li3VO4 toward Smoothing Li Insertion/Extraction

The γ phase Li₃VO₄ which possesses higher ionic conductivity is more preferable for lithium ion batteries, but it is only stable at high temperature and would convert to low temperature β phase spontaneously when cooling down. Here, the phase control of Li₃VO₄ to stabilize its γ phase in room temperature is successfully mediated by introducing proper Si‐doping, and for the first time the electrochemical performances of γ‐Li₃VO₄ is investigated. It is found that pure γ‐Li₃VO₄ can be obtained in a doping ratio of x = 0.05–0.15 in Li_3+xV_1?xSi_xO₄ with addition of excess Li source in synthesis design. The doping mechanism and the energy changes are investigated in detail by using the first principle calculations, it reveals that an interstitial Li⁺ is formed with doping of Si⁴⁺ in Li₃VO₄ to balance the system charge. When served as an anode, the Si‐doped γ‐Li₃VO₄ shows much smoothed Li⁺ insertion/extraction and enhanced cycle stability with only a single pair of redox peaks, which behaves much different with the complex multicouples of redox peaks in typical β‐Li₃VO₄. These changes in electrochemical performances implies that γ‐Li₃VO₄ can effectively accommodate Li⁺ in an easier and more facile way and relieved structure stress during the charge/discharge process.     

Vibrational and chiroptical spectroscopic characterization of γ‐turn model cyclic tetrapeptides containing two β‐Ala residues

The optical spectroscopic characterization of γ‐turns in solution is uncertain and their distinction from β‐turns is often difficult. This work reports systematic ECD and vibrational circular dichroism (VCD) spectroscopic studies on γ‐turn model cyclic tetrapeptides cyclo(Ala‐β‐Ala‐Pro‐β‐Ala) ( 1 ), cyclo(Pro‐β‐Ala‐Pro‐β‐Ala) ( 2 ) and cyclo(Ala‐β‐Ala‐Ala‐β‐Ala) ( 3 ). Conformational analysis performed at the 6‐31G(d)/B3LYP level of theory using an adequate PCM solvent model predicted one predominant conformer for 1‐3 , featuring two inverse γ‐turns. The ECD spectra in ACN of 1 and 2 are characterized by a negative n→π* band near 230 nm and a positive π→π* band below 200 nm with a long wavelength shoulder. The ECD spectra in TFE of 1‐3 show similar spectra with blue‐shifted bands. The VCD spectra in ACN‐d₃ of 1 and 2 show a +/?/+/? amide I sign pattern resulting from four uncoupled vibrations in the case of 1 and a sequence of two positive couplets in the case of 2 . A ?/+/+/? amide I VCD pattern was measured for 3 in TFE‐d₂. All three peptides give a positive couplet or couplet‐like feature (+/?) in the amide II region. VCD spectroscopy, in agreement with theoretical calculations revealed that low frequency amide I vibrations (at ～1630 cm^?1 or below) are indicative of a C₇ H‐bonded inverse γ‐turns with Pro in position 2, while γ‐turns encompassing Ala absorb at higher frequency (above 1645 cm^?1). Chirality, 2010. © 2010 Wiley‐Liss, Inc.     

Lyoluminescence,thermoluminescence and mechanoluminescence studies in γ‐ray irradiated Dy3+ activated potassium chloride phosphor for accidental radiation dosimetry

The lyoluminescence (LL), thermoluminescence (TL) and mechanoluminescence (ML) of γ‐ray‐irradiated coloured powder of KCl:Dy (0.05–0.5 mol%) phosphors are reported in this paper. To understand the mechanism of LL and ML, the LL and ML spectra are compared with TL studies. The variation of intensity of respective luminescence with different γ‐ray doses and with different concentrations of Dy³⁺ ion doped in KCl is found to be similar in nature. The intensities differ from each other, but their nature is found to be similar with γ‐ray exposures. The ML glow peak intensity is linear up to high 1 kGy exposure as compared to LL (up to 0.5 kGy) and TL (up to 0.75 kGy) techniques. Therefore, according to our results, the recommendation is that KCl:Dy (0.1 mol%) phosphor prepared by wet chemical technique is useful for high‐dose measurements using the ML technique for accidental radiation dosimetry. Copyright © 2011 John Wiley & Sons, Ltd.     

Mechanoluminescence of SrAl2O4:Eu,Dy nanophosphors induced by low impact velocity

The present paper reports the impulsive excitation of mechanoluminescence (ML) in Sr_0.97Al₂O₄:Eu_0.01,Dy_0.02 nanophosphors prepared using a combustion technique. The phosphors are characterized using X‐ray powder diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM) and photoluminescence (PL). The XRD results show that the samples exhibit a monoclinic α‐phase in the crystal structure. The space group of SrAl₂O₄:Eu,Dy nanophosphors is monoclinic P2₁. The PL and ML spectra of SrAl₂O₄:Eu,Dy nanophosphors are excited using light with a wavelength of 365 nm and emission is found at 516 nm. The prepared nanophosphors exhibits an intense ML that can be seen in daylight with the naked eye. When a sample powder is deformed impulsively by the impact of a moving piston, the ML intensity initially increases linearly with time, attains a peak value, I_m, at time t_m, and then decreases with time. The peak ML intensity, I_m, and total ML intensity, I_T, increase linearly with applied pressure and impact velocity. The ML intensity decreases with successive impacts of load onto the phosphors, and the diminished ML intensity can be approximately recovered by UV irradiation. The activation energy using thermoluminescence is found to be 0.57 eV for SrAl₂O₄:Eu,Dy nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd.     

Comparison of luminescence property of gamma‐ray irradiated Tb3+‐doped and Ce3+ co‐doped potassium halide single crystals

Single crystals of KCl and KBr singly and doubly doped with Tb³⁺ and Ce³⁺, respectively, were successfully grown using the Bridgeman technique. This work reports the comparative luminescence behavior and optical absorption characterization of non‐irradiated and γ‐ray‐irradiated single crystals of these materials. The existing defect and the defect created by γ‐ray irradiation were monitored by optical absorption spectra. The excitation and emission spectra of these materials were measured at room temperature with a spectrofluorometer and the pertaining results were compared. The F‐band comparison was made when bleached with F‐light for 2 mins. The trap‐level changes in KCl and KBr when it is singly and doubly doped enabled us to draw conclusions on the nature of the defect and on the recombination processes involved.     

γ‐Secretase Inhibition Induces Muscle Hypertrophy in a Notch‐Independent Mechanism

A wide variety of cellular processes and signaling events are regulated by the proteolytic enzyme γ‐secretase. Notch‐1 is one of the substrates of γ‐secretase and its role in the regulation of muscle differentiation has been well described. Importantly, besides Notch‐1, a number of proteins have been identified to undergo proteolysis by γ‐secretase. To date, the specific role of γ‐secretase during embryonic skeletal muscle differentiation has not been studied. Therefore, we address this question through the analysis of in vitro grown chick myogenic cells during the formation of multinucleated myotubes. The γ‐secretase inhibitor DAPT (N‐N[‐(3,5‐Difluorophenacetyl‐l ‐alanyl)]‐S‐328 phenylglycine‐t‐butyl‐ester) induces muscle hypertrophy. Knockdown of Notch‐1 using siRNA specific to chick shows no significant effect in myotube size, suggesting that γ‐secretase‐dependent effects on muscle hypertrophy in chick myogenic cells are Notch‐1‐independent. We also investigate the effects of γ‐secretase inhibition in the whole proteomic profile of chick myogenic cells. We identified 276 differentially expressed proteins from Label‐free proteomic approach. Data overview of interaction network obtained from STRING show that after γ‐secretase inhibition cells exhibited imbalance in protein metabolism, cytoskeleton/adhesion, and Sonic Hedgehog signaling. The collection of these results provides new insights into the role of γ‐secretase in skeletal muscle hypertrophy.     

Highly Air‐Stable Single‐Crystalline β‐CsPbI3 Nanorods: A Platform for Inverted Perovskite Solar Cells

The synthesis of single‐crystalline β‐CsPbI₃ perovskite nanorods (NRs) using a colloidal process is reported, exhibiting their improved photostability under 45–55% humidity. The crystal structure of CsPbI₃ NRs films is investigated using Rietveld refined X‐ray diffraction (XRD) patterns to determine crystallographic parameters and the phase transformation from orthorhombic (γ‐CsPbI₃) to tetragonal (β‐CsPbI₃) on annealing at 150 °C. Atomic resolution transmission electron microscopy images are utilized to determine the probable atomic distribution of Cs, Pb, and I atoms in a single β‐phase CsPbI₃ NR, in agreement with the XRD structure and selected area electron diffraction pattern, indicating the growth of single crystalline β‐CsPbI₃ NR. The calculation of the electronic band structure of tetragonal β‐CsPbI₃ using density functional theory (DFT) reveals a direct transition with a lower band gap and a higher absorption coefficient in the solar spectrum, as compared to its γ‐phase. An air‐stable (45–55% humidity) inverted perovskite solar cell, employing β‐CsPbI₃ NRs without any encapsulation, yields an efficiency of 7.3% with 78% enhancement over the γ‐phase, showing its potential for future low cost photovoltaic devices.     

Evaluation of trapping parameters of γ‐rays irradiated Dy3+‐doped LaPO4 phosphors

Thermoluminescence (TL) materials are widely used in radiation measurements. The best‐known applications of TL materials are in the dosimetry of ionizing radiation, and in CTV screen phosphors, scintillators, X‐ray laser materials, etc. The TL glow curve and its kinetic parameters for annealed LaPO₄ at different constant temperatures and for Dy³⁺‐doped LaPO₄ phosphors irradiated by gamma‐rays are reported here. The samples were irradiated using a ⁶⁰Co gamma‐ray source at a dose of 10 Gy and the heating rate used for TL measurements was 5ºC/s. The samples were characterized using X‐ray diffraction (XRD), Fourier transform infrared, transmission electron microscopy and TL techniques. The XRD pattern shows that the prepared phosphor has a good crystalline structure with an average crystallite size of ~ 18 nm. The samples show good TL peaks for 0.05, 0.1 and 0.2 mole % doping concentrations of Dy³⁺ ions and anneal above 400ºC. The TL glow curve characteristics of annealed LaPO₄ and Dy³⁺‐doped LaPO₄ were analyzed and trapping parameters calculated using various methods. All TL glow curves obey the second‐order kinetics with a single glow peak, which reveals that only one set of trapping parameter is set for a particular temperature. The TL sensitivity was found to depend upon the annealing temperature and Dy³⁺ doping concentration. The prepared sample may be a new nano phosphor and be useful in TL dosimetry. Copyright © 2014 John Wiley & Sons, Ltd.     

The stress response neuropeptide CRF increases amyloid‐β production by regulating γ‐secretase activity

The biological underpinnings linking stress to Alzheimer's disease (AD) risk are poorly understood. We investigated how corticotrophin releasing factor (CRF), a critical stress response mediator, influences amyloid‐β (Aβ) production. In cells, CRF treatment increases Aβ production and triggers CRF receptor 1 (CRFR1) and γ‐secretase internalization. Co‐immunoprecipitation studies establish that γ‐secretase associates with CRFR1; this is mediated by β‐arrestin binding motifs. Additionally, CRFR1 and γ‐secretase co‐localize in lipid raft fractions, with increased γ‐secretase accumulation upon CRF treatment. CRF treatment also increases γ‐secretase activity in vitro, revealing a second, receptor‐independent mechanism of action. CRF is the first endogenous neuropeptide that can be shown to directly modulate γ‐secretase activity. Unexpectedly, CRFR1 antagonists also increased Aβ. These data collectively link CRF to increased Aβ through γ‐secretase and provide mechanistic insight into how stress may increase AD risk. They also suggest that direct targeting of CRF might be necessary to effectively modulate this pathway for therapeutic benefit in AD, as CRFR1 antagonists increase Aβ and in some cases preferentially increase Aβ42 via complex effects on γ‐secretase.     

Photoluminescence imaging of europium (III)‐doped γ‐Al2O3 nanofiber structures

Aluminium oxide (Al₂O₃) has widely been used for catalysts, insulators, and composite materials for diverse applications. Herein, we demonstrated if γ‐Al₂O₃ was useful as a luminescence support material for europium (Eu) (III) activator ion. The hydrothermal method and post‐thermal treatment at 800°C were employed to synthesize Eu(III)‐doped γ‐Al₂O₃ nanofibre structures. Luminescence characteristics of Eu(III) ions in Al₂O₃ matrix were fully understood by taking 2D and 3D‐photoluminescence imaging profiles. Various sharp emissions between 580 to 720 nm were assigned to the ⁵D₀→⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu(III) activators. On the basis of X‐ray diffraction crystallography, Auger elemental mapping and the asymmetry ratio, Eu(III) ions were found to be well doped into the γ‐Al₂O₃ matrix at a low (1 mol%) doping level. A broad emission at 460 nm was substantially increased upon higher (2 mol%) Eu(III) doping due to defect creation. The first 3D photoluminescence imaging profiles highlight detailed understanding of emission characteristics of Eu(III) ions in Al oxide‐based phosphor materials and their potential applications.     

Luminescence study of Dy or Ce activated LiCaBO3 phosphor for γ‐ray and C5+ ion beam irradiation

The photoluminescence and thermoluminescence characteristics of rare earths (Dy or Ce) activated LiCaBO₃ phosphors have been studied. Phosphors were synthesized by modified solid state synthesis. The phosphors were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and thermoluminescence (TL) for structural, morphological and luminescence studies. Dy³⁺ activated LiCaBO₃ shows emission at 486 and 577 nm due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transition, respectively, whereas the PL emission spectra of Ce³⁺ activated LiCaBO₃ phosphor shows a broad band peaking at 432 nm, which is due to the transition from 5d level to the ground state of the Ce³⁺ ion. The thermoluminescence study was also carried out for both these phosphors for γ‐ray irradiation and carbon beam irradiation. Linearity was studied for a 0.4–3.1 Rad dose γ‐rays. Linear behaviour over this dose range was observed. Gamma ray‐irradiated phosphors were shown to be negligible fading upon storage. All the samples were also studied for 75 MeV C⁵⁺ ion beam exposure in the range of 3.75 × 10¹² – 7.5 × 10¹³ ion cm^–2 fluence. In addition to this, trapping parameters of all the samples were also calculated using Chen's peak shape method. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of 2‐oxoamides based on sulfonamide analogs of γ‐amino acids and their activity on phospholipase A2

A variety of lipophilic 2‐oxoamides containing sulfonamide analogs of γ‐amino acids as well as acyl sulfonamides of γ‐aminobutyric acid were synthesized. Their ability to inhibit intracellular GIVA cPLA₂ and GVIA iPLA₂ as well as secreted GV sPLA₂ was evaluated. The sulfonamide group seems a bioisosteric group suitable to replace the carboxyl group in 2‐oxoamide inhibitors of GVIA cPLA₂. Copyright © 2008 European Peptide Society and John Wiley & Sons, Ltd.     

Adiposity and β‐Cell Function: Relationships Differ With Ethnicity and Age

The prevalence of type 2 diabetes is higher among African Americans (AA) vs. European Americans (EA), is highest at middle age, and is related to obesity. This study was conducted to test the hypothesis that the association of adiposity (percent body fat (%fat)) with indexes of insulin sensitivity (S_I) and β‐cell function would differ with ethnicity and age. Subjects were 168 healthy, normoglycemic AA and EA girls and women aged 7–12 years, 18–32 years, and 40–70 years. An intravenous glucose tolerance test (IVGTT) was used to assess indexes of insulin secretion and action: S_I, acute C‐peptide secretion (X0); basal, first‐phase, second‐phase, and total β‐cell responsivity to glucose (PhiB, Phi1, Phi2, and Phi_TOT, respectively); and the disposition index (DI = S_I × Phi_TOT). %Fat was assessed with dual energy X‐ray absorptiometrys. Adiposity was significantly associated with S_I among EA (?0.57, P < 0.001) but not AA (?0.20, P = 0.09). Adiposity appeared stimulatory to β‐cell function in the two groups of younger subjects and in EA, but inhibitory in postmenopausal women, particularly AA postmenopausal women. Among AA postmenopausal women, %fat was inversely associated with Phi1 (r = ?0.57, P < 0.05) and Phi_TOT (r = ?0.68, P < 0.01). These results suggest that the impact of adiposity on insulin secretion and action differs with age and ethnicity.     

Synthesis,characterization and thermoluminescence studies of (ZnS)1‐x(MnTe)x nanophosphors

The present paper reports the thermoluminescence (TL) of (ZnS)_1‐x(MnTe)_x nanophosphors that were prepared by a wet chemical synthesis method. The structure investigated by X‐ray diffraction patterns confirms the formation of a sphalerite phase whose space group was found to be F 3m. From XRD, TEM and SEM analyses the average sizes of the particles were found to be 12 nm, 11 nm and 15 nm, respectively. Initially the TL intensity increased with increasing values of x because the number of luminescence centres increased; however, for higher values of x the TL intensity decreased because of the concentration quenching. Thus the TL, mechanoluminescence and photoluminescence intensities are optimum for a particular value of x, that is for x = 0.05. Thermoluminescence of the (ZnS)_1‐x (MnTe)_x nanophosphor has not been reported previously. There were two peaks seen in the thermoluminescence glow curves in which the first peak lay at 105–100 °C and the second peak lay at 183.5–178.5 °C. The activation energies for the first and second peaks were found to be 0.45 eV and 0.75 eV, respectively.     

S‐ to N‐Acyl transfer in S‐acylcysteine isopeptides via 9‐, 10‐, 12‐, and 13‐membered cyclic transition states

S‐Acyl cysteine peptides containing α‐, β‐ or γ‐amino acid residues undergo long‐range S‐ to N‐acyl transfer to give analogs of native tripeptides and tetrapeptides containing additional carbon atoms in the chain. The ease of intramolecular S → N‐acyl transfer relative to intermolecular transacylation is favored increasingly for 9 < 12 < 13 ~ 10‐membered cyclic transition states; the observed order is explained on conformational and intermolecular interaction considerations. Copyright © 2012 European Peptide Society and John Wiley & Sons, Ltd.