Synthesis and photophysical studies on a new fluorescent phenothiazine‐based derivative

A new typical phenothiazine compound functionalized with thienyl‐indandione derivative (PTZTID) was synthesized and characterized using spectral analysis (ultraviolet–visible (UV–vis) light, infrared (IR), ¹H nuclear magnetic resonance (NMR) and ¹³C NMR tools). The UV–vis absorption spectra of the PTZTID solution in 1,4‐dioxane showed two absorption bands attributed to localized aromatic π–π* transitions of conjugated aromatic moieties and intramolecular charge transfer with the characteristics of a π–π* transition. The fluorescence spectra exhibited a maximum emission wavelength at 580 nm. The effect of concentration on photophysical properties took the form of a minor hypsochromic shift, which was attributed to some extent to the occurrence of H‐type aggregation of the PTZTID derivative. Binary solvent effects on the spectroscopic behaviour of PTZTID were measured at different H₂O/1,4‐dioxane ratios. Similarly, when increasing the water content, a hypsochromic shift was observed that resulted from H‐type aggregation. Furthermore, geometry and electronic configurations of PTZTID were studied at density functional theory /B3LYP level and indicated that the compound had a nonplanar (butterfly structure).     

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.     

Unusual CD couplet pattern observed for the pi*<--n transition of enantiopure (Z)-8-methoxy-4-cyclooctenone: an experimental and theoretical study by electronic and vibrational circular dichroism spectroscopy and density functional theory calculation

Ultraviolet absorption (UV) and electronic circular dichroism (ECD) spectra of enantiopure (Z)-8-methoxy-4-cyclooctenone (MCO) were measured in hexane to give a normal single UV absorption band at 298 nm, which is assigned to the carbonyl's pi*<--n transition. Unexpectedly, the ECD spectrum exhibited an apparent couplet pattern with vibrational fine structures. Obviously, the conventional CD exciton coupling mechanism cannot be applied to this bisignate CD signal observed for single-chromophoric MCO. Variable temperature-ECD and vibrational circular dichroism (VCD) spectral measurements, simultaneous UV and ECD spectral band resolution, and density functional theory (DFT) calculations of energy and structure revealed that this apparent CD couplet originates from a rather complicated spectral overlap of more than three conformers of MCO, two of which exhibit mirror-imaged ECD spectra at appreciably deviated wavelengths. In the simultaneous band-resolution analysis, the observed UV and ECD spectra were best fitted to four overlapping bands. Two major conformers were identified by comparing the experimental IR and VCD spectra with the simulated ones, and the other two by comparing the observed UV and ECD spectra with the theoretical ones obtained by time-dependent DFT calculations. It was shown that the combined use of experimental ECD and VCD spectra and theoretical DFT calculations can give a reasonable interpretation for the Cotton effects of the conformationally flexible molecule MCO.     

Assessment of spectroscopic parameters of solvated Eu(dmh)3phen organometallic complex in various basic and acidic solvents

We report on the comprehension of novel europium activated hybrid organic Eu(dmh)₃phen (Eu: europium, dmh: 2,6‐dimethyl‐3,5‐heptanedione, phen: 1,10 phenanthroline) organo‐metallic complexes, synthesized at different pH values by the solution technique. Photo physical properties of these complexes in various basic and acidic solvents were probed by UV–vis optical absorption and photoluminescence (PL) spectra. Minute differences in optical absorption peaks with variable optical densities were encountered with the variation in solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid) media, revealing bathochromic shift in the absorption peaks. The PL spectra of the complex in various acidic and basic organic solvents revealed the position of the emission peak at 613 nm irrespective of the changes in solvents whereas the excitation spectrum almost matched with that of the UV–vis absorption data. The optical density was found to be maximum for the complex with pH 7.0 whereas it gradually decreased when pH was lowered to 6.0 or raised to 8.0 at an interval of 0.5, demonstrating its pH sensitive nature. Several spectroscopic parameters related to probability of transition such as absorbance A(λ), Napierian absorption coefficient α(λ), molecular absorption cross‐section σ(λ), radiative lifetime (τ₀) and oscillator strength (f) were calculated from UV–vis spectra. The relative intensity ratio (R‐ratio), calculated from the emission spectra was found to be almost the same in all the organic solvents. The optical energy gap, calculated for the designed complexes were found to be well in accordance with the ideal acceptance value of energy gap of the emissive materials used for fabrication of red organic light‐emitting diode (OLED). The relation between Stoke's shift and solvent polarity function was established by Lippert–Mataga plot. This remarkable independence of the electronic absorption spectra of Eu complexes on the nature of the solvent with unique emission wavelength furnishes its potential to serve as a red light emitter for solution processed OLEDs, display panels and solid‐state lighting.     

Experimental and theoretical studies of vacuum-ultraviolet electronic circular dichroism of hydroxy acids in aqueous solution

The electronic circular dichroism (ECD) spectra of three L-hydroxy acids (L-lactic acid, (+)-(S)-2-hydroxy-3-methylbutyric acid, and (-)-(S)-2-hydroxyisocaproic acid) were measured down to 160 nm in aqueous solution using a vacuum-ultraviolet ECD spectrophotometer. To assign the two positive peaks around 210 and 175 nm and the one negative peak around 190 nm in the observed spectra, the ECD spectrum of L-lactic acid was calculated using time-dependent density functional theory (DFT) for the optimized structures by DFT and a continuum model. The observed ECD spectrum was successfully reproduced as the average spectrum for four optimized structures with seven water molecules that localized around the COO(-) and OH groups of L-lactic acid. The positive peak around 210 nm and the negative peak around 185 nm in the calculated spectrum were attributable to the nπ* transition of the carboxyl group, with the latter peak also being influenced by the ππ* transition of the carboxyl group; however, the positive peak around 165 nm involved unassignable higher energy transitions. The comparison of the calculated ECD spectra for L-lactic acid and L-alanine revealed that the network with loose hydrogen bonding around the COO(-) and OH groups is responsible for the flexible conformation of hydroxy acids and complicated side-chain dependence of ECD spectra relative to amino acids.     

Circular Dichroism Spectroscopy Study of Crystalline‐to‐Amorphous Transformation in Chiral Platinum(II) Complexes

Two couples of enantiomeric platinum(II) complexes: Pt(L_1a)Cl ( 1a ), Pt(L_1b)Cl ( 1b ) and Pt(L_1a)(C ≡ C ? Ph) ( 2a ), Pt(L_1b)(C ≡ C ? Ph) ( 2b ) (L_1a = (+)‐1,3‐di‐(2‐(4,5‐pinene)pyridyl)benzene, L_1b = (?)‐1,3‐di‐(2‐(4,5‐pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X‐ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline‐to‐amorphous transformation. The crystalline solids, grinding‐induced amorphous powders, and vapor‐induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid‐state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra. Chirality 25:384–392, 2013. © 2013 Wiley Periodicals, Inc.     

Circular dichroism calculation for random-coil polypeptide chains

A method of calculation of the circular dichroism (CD) of random-coil polypeptides has been developed by means of a Monte-Carlo approach to the treatment of statistical systems and exciton theory of optical activity of polymers. The contribution of π–π^* and n–π^* amide transitions to the CD has been taken into account. The π–π^* transition gives rise to two CD bands: a negative short-wavelength band and a weak positive long-wavelength one. The n –π^* transition gives rise to one negative CD band.     

Enhancement of photosynthesis in Sorghum bicolor by ultraviolet radiation

We assessed the influence of ultraviolet radiation (UV) on net photosynthetic CO₂ assimilation rate (P_n) in Sorghum bicolor, with particular attention to examining whether UV can enhance P_n via direct absorption of UV and absorption of UV‐induced blue fluorescence by photosynthetic pigments. A polychromatic UV response spectrum of leaves was constructed by measuring P_n under different UV supplements using filters that had sharp transmission cut‐offs from 280 to 382 nm, against a background of non‐saturating visible light. When the abaxial surface was irradiated, P_n averaged 4.6% higher with the UV supplement that cut‐off UV at 311 nm, compared to lower and higher UV wavelength supplements. This former supplement differed from higher wavelength supplements by primarily providing more UV between 320 and 350 nm. To assess the possibility of direct absorption of UV by photosynthetic pigments, we measured the absorbance of extracted chlorophylls. Chlorophyll a had absorbance peaks at 340 and 389 nm that were 49 and 72% of that at the sorét peak. Chlorophyll b had absorbance peaks at 315 and 346 nm that were both 35% of that at the sorét peak. Since the epidermis transmits some UV, the strong UV absorbance of chlorophyll implies a potential role for irradiance beyond the bounds of the conventionally defined photosynthetically active radiation waveband (400–700 nm). To assess the role of absorption of UV‐induced blue fluorescence, we measured the UV‐induced fluorescence excitation and emission spectra of leaves. Abaxial excitation peaked at 328 nm, while emission peaked at 446 nm. In this analysis, we used our abaxial fluorescence excitation spectrum and the UV photosynthetic inhibition spectrum of Caldwell et al. (1986) to weight the UV irradiance with each cut‐off filter, thereby estimating the potential contribution of UV‐induced blue fluorescence to photosynthesis and the inhibitory effects of UV irradiance on photosynthesis, respectively. With a non‐saturating visible background, we estimate that the absorption of UV‐induced blue fluorescence and the direct absorption of UV by photosynthetic pigments maximally enhanced photosynthesis by about 1% each with the UV supplement that cut‐off UV at 311 nm. We suggest that a portion of the incident UV on the S. bicolor leaves was used to drive photosynthesis.     

Synthesis,Structural Characterization,and Chiroptical Studies of Bidentate Salen‐Type Lanthanide (III) Complexes

The salen‐type ligand prepared with (R,R) diphenylethan‐1,2‐diamine and salicylaldehyde provides stable and inert complexes KLnL₂ upon simple reaction with lanthanide halides or pseudohalides LnX₃ (Ln = Tb³⁺‐Lu³⁺; X = Cl^? or TfO^?) of its potassium salt. All the complexes were completely characterized through nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) in the UV and some (Er³⁺, Tm³⁺, Yb³⁺) also with Near‐IR ECD (NIR‐ECD) and luminescence (Tb³⁺, Tm³⁺). Careful analysis of the NMR shifts demonstrated that the complexes are isostructural in solution and afforded an accurate geometry. This was further confirmed by means of Density Functional Theory (DFT) optimization of the Lu³⁺ complex, and by comparing the ligand‐centered experimental and time‐dependent TD‐DFT computed UV‐ECD spectra. As final validation, we used the NIR‐ECD spectrum of the Yb³⁺ derivative calculated by means of Richardson's equations. The excellent match between calculated and experimental ECD spectra confirm the quality of the NMR structure.  Chirality 27:857–863, 2015. © 2015 Wiley Periodicals, Inc.     

Reinvestigation of the visible absorption bands of the 2,2′-bipyrimidine complexes W(CO)4(bpym) and (μ-bpym)[M(CO)4]2 (M=Mo, W) with resonance Raman spectroscopy; the emission spectrum of (μ-bpym)[Mo(CO)4]2

The character of the two lowest energy transitions of W(CO)₄(bpym) and (μ-bpym)[M(CO)₄]₂ (M=Mo, W) were established with resonance Raman spectroscopy. According to these spectra the two bands belong to MLCT transitions to different π* orbitals of the bpym ligand. Contrary to expectations it is not the first (lowest energy) but the second and more intense electronic transition which, according to the resonance Raman spectra, is directed to the lowest lying π* orbital (b_2u*, LUMO) of these complexes. This interpretation explains the different band intensities and the untypically low g values of the ESR signals of corresponding anion radicals. Excitation of (μ-bpym)[Mo(CO)₄]₂ in CH₂Cl₂ at 400 nm produced a weak emission with an onset at 700 nm. According to the excitation spectrum, this emission originates from the lowest MLCT-excited state of the complex.     

COMBINATION OF FLOW CYTOMETRY AND SINGLE CELL ABSORPTION SPECTROSCOPY TO STUDY THE PHYTOPLANKTON STRUCTURE AND TO CALCULATE THE CHL A SPECIFIC ABSORPTION COEFFICIENTS AT THE TAXON LEVEL1

The phytoplankton community structure of a hypertrophic lake was quantitatively determined with the aid of flow cytometry. The flow cytometry signals were calibrated to obtain cell‐specific information, such as the chl a content and the biovolume per cell. The reliability of this method was tested with laboratory cultures. The results of the phytoplankton structure in a hypertrophic lake with respect to chl distribution in the different algal groups obtained by flow cytometry were compared with the results from HPLC pigment fingerprinting. Both methods yield the percentage contribution of the different algal groups to total chl a. The chl a specific absorption coefficient of the phytoplankton (a^*_Phy) was determined via visible (VIS) spectroscopy of samples taken from a hypertrophic lake (Auensee) in 2003. The results indicated that a^*_Phy of the total cell suspension is dependent on the phytoplankton structure as well as on environmental factors. The linear relationship between a^*_Phy at 675 nm and the product of the chl a content per cell and the biovolume offered the possibility to normalize phytoplankton absorption spectra to acquire the taxon‐specific a^*_Phy. The estimated a^*_Phy (675 nm) values were used to normalize single cell absorption spectra at this wavelength to obtain the a^*_Phy between 400 and 750 nm for representatives of the major algal groups. Our measurements show that the absorption coefficient for the whole phytoplankton community varies within the season. Finally, we used the a^*_Phy and the chl a distribution to calculate the light absorption of each algal group in the hypertrophic lake.     

Synthesis and luminescence of Eu3+‐doped in triple phosphate Ca8MgBi(PO4)7 with whitlockite structure

Triple whitlockite‐type structure‐based red phosphors Ca₈MgBi_1?x(PO₄)₇:xEu³⁺ (x = 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80 and 1.00) were synthesized by a conventional solid‐state reaction route and characterized by their X‐ray crystal structures. The X‐ray diffraction (XRD) patterns, Fourier transform infrared spectra, morphologies, photoluminescence spectra, UV/Vis reflectance spectra, decay times and the International Commission on Illumination (CIE) chromaticity coordinates of Ca₈MgBi_1?x(PO₄)₇:xEu³⁺ were analyzed. Eu‐doped Ca₈MgBi(PO₄)₇ phosphors exhibited strong red luminescence with peaks at 616 nm due to the ⁵D₀ → ⁷ F₂ electric dipole transition of Eu³⁺ ions after excitation at 396 nm. The UV/Vis spectra indicated that the band gap of Ca₈MgBi_0.30(PO₄)₇:0.70Eu³⁺ is larger than that of Ca₈MgBi(PO₄)₇. The phosphor developed in this study has great potential as a red‐light‐emitting phosphor for UV light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,characterization and luminescent properties of europium complexes with 2,4,6‐tris‐(2‐pyridyl)‐s‐triazine as highly efficient sensitizers

Using 2,4,6‐tris‐(2‐pyridyl)‐s‐triazine (TPTZ) as a neutral ligand, and p‐hydroxybenzoic acid, terephthalic acid and nitrate as anion ligands, five novel europium complexes have been synthesized. These complexes were characterized using elemental analysis, rare earth coordination titrations, UV/vis absorption spectroscopy and infrared spectroscopy. Luminescence spectra, luminescence lifetime and quantum efficiency were investigated and the mechanism discussed in depth. The results show that the complexes have excellent emission intensities, long emission lifetimes and high quantum efficiencies. The superior luminescent properties of the complexes may be because the triplet energy level of the ligands matches well with the lowest excitation state energy level of Eu³⁺. Moreover, changing the ratio of the ligands and metal ions leads to different luminescent properties. Among the complexes, Eu₂(TPTZ)₂(C₈H₄O₄)(NO₃)₄(C₂H₅OH)·H₂O shows the strongest luminescence intensity, longest emission lifetime and highest quantum efficiency. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and photoluminescence of EuII in barium zinc orthosilicate: a novel green color emitting phosphor for white‐LEDs

A series of Eu²⁺‐activated barium orthosilicates (BaZnSiO₄) were synthesized using a high‐temperature solid‐state reaction. A photoluminescence excitation study of Eu²⁺ shows a broad absorption band in the range of 270–450 nm, with multiple absorption peak maxima (310, 350 and 400 nm) due to 4f–5d electronic transition. The emission spectra of all the compositions show green color emission (in the spectral region 450–550 nm with a peak maximum at 502 nm and a shoulder at ~ 490 nm) with appropriate Comission Internationale de l'Eclairage (CIE) color coordinates. The two emission peaks are due to the presence of Eu²⁺ in two different Ba sites in the BaZnSiO₄ host lattice. The energy transfers between the Eu²⁺ ions in BaZnSiO₄ host are elucidated from the critical concentration quenching data based on the electronic multipolar interaction. All Eu²⁺‐activated BaZnSiO₄ phosphor materials can be efficiently excited in the ultraviolet (UV) to near UV‐region (270–420 nm), making them attractive candidate as a green phosphor for solid state lighting–white light‐emitting diodes.     

Vacuum-ultraviolet circular dichroism of sodium hyaluronate oligosaccharides and polymer segments

The CD spectrum of an enzymatically derived sodium hyaluronate (NaHA) segment preparation with chain length 18 ± 3 disaccharide units [NaHAseg, ( NaGlcUA GlcNAc)_15–20°. NaGlcUA, sodium D -glucuronate; GlcNAc, 2-acetamido-2-deoxy-D -glucose] in H₂O was recorded to 180 nm using a computer-controlled vacuum-uv CD instrument. Near 190 nm the spectrum is of low intensity, similar to the sum of the free monosaccharide contributios, attributed to the π–π* transitions of the acetamido and carboxylate substituents. In contrast, much smaller oligosaccharides, also derived from high-molecular-weight NaHA by enzymatic digestions, show CD spectra in H₂O with prominent bands centered near 190 nm. The oligosaccharide spectra can be matched as linear combinations of interior sugar residue (? NaHAseg) and end sugar residue CD contributions. End residues from oligosaccharides of the type (NaGlcUA-GlcNAc)_n show a negative CD band near 190 nm. End residues from oligosaccharides of the reverse sequence (GlcNAc-NaGlcUA)_n show a positive CD band near 190 nm. Averaging of the two end-residue spectral contributions yields an approximate match for the spectrum of NAHAseg below 200 nm. It is proposed that the low intensity CD of NaHA in the π–π* region is the result of large-magnitude, oppositely signed contributions, which can be visulized by studying oligosaccharides.     

Theoretical pi-pi absorption, circular dichroic, and linear dichroic spectra of collagen triple helices

Absorption, CD, and LD spectra of the π-π* transition near 200 nm are calculated for poly(Gly-X-Y) (X,Y = Gly, Ala, Pro) in four conformations proposed for collagen like triple helices in the recent literature. A dipole interaction model is used with the same optical paramenters as in previous studies of polypeptide spectra. The CD spectra are sensitive to backbone structure and amino acid composition, although the experimentally observed negative peak near 200 nm is a general feature of most the calculated spectra. Interchain interactions significantly affect the CD spectra in most cases. Calculations for (Gly-Pro-Ala)₃ and (Gly-Ala-Pro)₃ in the triple helical structure of Fraser, MacRae, and Suzuki [(1979) J. Mol. Biol. 129 , 463–481] show absorption, CD, and LD spectra in fairly good agreement with experiment. The characteristics of the π-π* normal modes responsible for the calculated spectra are compared with those of the component bands resolved from the experimental spectra of collagen by Mandel and Holzwarth [(1973) Biopolymers 12 , 655–674].     

Chromophoric dissolved organic matter (CDOM) absorption characteristics in relation to fluorescence in Lake Taihu,China, a large shallow subtropical lake

Absorption measurements from chromophoric dissolved organic matter (CDOM) and their relationships with dissolved organic carbon (DOC) and fluorescence were studied in Lake Taihu, a large, shallow, subtropical lake in China. Absorption spectra of lake water samples were measured from 240 nm to 800 nm. Highest values of a(λ), DOC and F _n (355) occurred near the river inflow to Meiliang Bay and decreased towards the central lake basin. A significant spatial difference was found between Meiliang Bay and the central lake basin in absorption coefficient, DOC-specific absorption coefficient, exponential slope coefficient, DOC concentration and fluorescence value. The spatial distribution of CDOM suggested that a major part of CDOM in the lake was from river input. CDOM absorption coefficients were correlated with DOC over the wavelength range 280–500 nm, and a(355) was also correlated with F _n (355), which showed that CDOM absorption could be inferred from DOC and fluorescence measurement. The coefficient of variation between a(λ) and DOC concentration decreased with increase in wavelength from 240 nm to 800 nm. Furthermore, a significant negative linear relationship was recorded between S value and CDOM absorption coefficient, as well as DOC-specific absorption coefficient. S value and DOC-specific absorption coefficient were used as a proxy for CDOM composition and source. Accurate CDOM absorption measurements are very useful in explaining UV attenuation and in developing, validating remote sensing model of water quality in Lake Taihu.     

Eu3+‐activated Y2MoO6: a narrow band red‐emitting phosphor with strong near‐UV absorption

Near‐UV excited narrow line red‐emitting phosphors, Eu³⁺‐activated Y₂MoO₆ systems, were synthesized using a simple molten salt reaction. The structure and photoluminescence characteristics were investigated using X‐ray powder diffraction, UV–Vis absorption and fluorescent spectrophotometry. The excitation spectra show strong broad‐band absorptions in the near‐UV to blue light regions which match the radiation of near‐UV light‐emitting diode chips well. Under excitation of either near‐UV or blue light, intense red emission with a main peak of 611 nm is observed, ascribed to the ⁵D₀–⁷F₂ transition of Eu³⁺ ions; the optimal doping concentration is 20 mol%. The chromaticity coordinates (x = 0.65, y = 0.34) of the as‐obtained phosphor are very close to the National Television Standard Committee standard values (x = 0.67, y = 0.33). All these characteristics suggest that this material is a promising red‐emitting phosphor candidate for white‐LEDs based on near‐UV LED chips. Copyright © 2012 John Wiley & Sons, Ltd.     

Optical activity of simple cyclic amides in solution

The cyclic dipeptide, L -alanylglycyl anhydride, has been studied by optical rotatory dispersion; both L -alanylglycyl anhydride and the lactam, L -3-aminopyrrolidin-2-one, have been studied by circular dichroism. In hydroxylic solvents the circular dichroism spectra of 3-aminopyrrolidin-2-one can be attributed to an n–π* transition near 220 mμ and a π–π* transition near 190 mμ. In these solvents the optical activity of L -alanylglycyl anhydride can be explained as being due to contributions of n–π* transitions and a split π–π* transition. In acetonitrile, however, the circular dichroism spectrum of 3-aminopyrrolidin-2-one shows an additional apparent minimum near 200 mμ. The CD spectrum of the dipeptide is also quite distinctive in this solvent. The possible nature of the band at 200 mμ and the implications of these findings are discussed.     

Absolute Configuration of Oplopanone Derivatives From Serphidium stenocephalum: ECD Spectra of Acyclic Ketones With Front‐Octant Contributions

The electronic circular dichroism (ECD) spectra of two sesquiterpenoids ( 1 and 2 ) related to oplopanone, obtained from a methanolic extract of the plant Serphidium stenocephalum (Artemisia stenocephala), were measured and reproduced by means of time‐dependent density functional theory (TDDFT) calculations, establishing their absolute configuration. The application of ketone octant rule for carbonyl n‐π* ECD band to compounds 1 and 2 , which include an acyclic carbonyl group, was critically assessed. The peculiar oplopanone skeleton makes a straightforward application of the octant rule impossible, because of the uncertainty related to the shape of the so‐called third nodal surface separating front and back octants. The various group contributions to the carbonyl n‐π* ECD band were estimated with TDDFT calculations on selected molecular models obtained by consecutive dissections from 1 . Chirality 26:39–43, 2013. © 2013 Wiley Periodicals, Inc.