Theoretical Study of the Conformations of Pustulan [(1⇒6)-β-D)-Glucan]

Abstract

The total potential energy including nonbondedJuntorsional and hydrogen bond contributions has been computed for pustulan, a (1?6) linked β-D-glucan polysaccharide, as a function of rotational angles φ, ψ, and ω The (φ, ψ, ω)-space contains many local minima and at least three distinct deep minima. Two minima at (φ, ψ, ω)=(25°,190°,gg) and (φ, ψ, ω)=(65°,150°,gg) of almost equal energies have helical parameters (n=5.2, A=1.0Å) and (n=3.2, h= 1.5Å), respectively. A third minimum at (φ, ψ, ω)=(40°,70°gt) leads to an extended zig-zag structure (n=2.2, h=2.2Å). Energy maps obtained for gentiobiose, the disaccharide of pustulan, also reveal many local minima and the small energy differences among them indicate that gentiobiose is extremely flexible. Gentiodextrins, a family of cyclic molecules of (l?6)-β-D- glucose residues, were also studied. Conformations free from steric hindrance were found for cyclic molecules with three to six glucose residues.     

Photosynthetic performance and resistance to photoinhibition of Zea mays L. leaves grown at sub-optimal temperature

The performance of the photosynthetic apparatus was examined in the third leaves of Zea mays L. seedlings grown at near-optimal (25 °C) or at suboptimal (15 °C) temperature by measuring chlorophyll (ChI) a fluorescence parameters and oxygen evolution in different temperature and light conditions. In leaf tissue grown at 25 and 15 °C, the quantum yield of PSII electron transport (ψ_PSII) and the rate of O₂ evolution decreased with decreasing temperature (from 25 to 4 °C) at a photon flux density of 125 μmol m^?2 s^?1. In leaves grown at 25 °C, the decrease of ψ_PSII correlated with a decrease of photochemical ChI fluorescence quenching (q_p), whereas in leaves crown at 15 °C q_p was largely insensitive to the temperature decrease. Compared with leaves grown at 25 °C, leaves grown at 15 °C were also able to maintain a higher fraction of oxidized to reduced Q_A (greater q_p) at high photon flux densities (up to 2000 μmol m^?2 s^?1), particularly when the measurements were performed at high temperature (25 °C). With decreasing temperature and/or increasing light intensity, leaves grown at 15 °C exhibited a substantial quenching of the dark level of fluorescence F₀ (q₀) whereas this type of quenching was virtually absent in leaves grown at 25 °C. Furthermore, leaves grown at 15 °C were able to recover faster from photo inhibition of photosynthesis after a photoinhibitory treatment (1200 μmol m^?2 s^?1 at 25, 15 or 6 °C for 8 h) than leaves grown at 25 °C. The results suggest that, in spite of having a low photosynthetic capacity, Z. mays leaves grown at sub optimal temperature possess efficient mechanisms of energy dissipation which enable them to cope better with photoinhibition than leaves grown at near-optimal temperature. It is suggested that the resistance of Z. mays leaves grown at 15 °C to photoinhibition is related to the higher content of carotenoids of the xanthophyll cycle (violaxanthin + antheraxanthin + zeaxanthin) measured in these leaves than in leaves grown at 25 °C.     

Crystallographic characterization of the α,γ C12 helix in hybrid peptide sequences

The solid‐state conformations of two αγ hybrid peptides Boc‐[Aib‐γ⁴(R)Ile]₄‐OMe 1 and Boc‐[Aib‐γ⁴(R)Ile]₅‐OMe 2 are described. Peptides 1 and 2 adopt C₁₂‐helical conformations in crystals. The structure of octapeptide 1 is stabilized by six intramolecular 4 → 1 hydrogen bonds, forming 12 atom C₁₂ motifs. The structure of peptide 2 reveals the formation of eight successive C₁₂ hydrogen‐bonded turns. Average backbone dihedral angles for αγ C₁₂ helices are peptide 1 , Aib; φ (°) = ?57.2 ± 0.8, ψ (°) = ?44.5 ± 4.7; γ⁴(R)Ile; φ (°) = ?127.3 ± 7.3, θ₁ (°) = 58.5 ± 12.1, θ₂ (°) = 67.6 ± 10.1, ψ (°) = ?126.2 ± 16.1; peptide 2 , Aib; φ (°) = ?58.8 ± 5.1, ψ (°) = ?40.3 ± 5.5; ψ⁴(R)Ile; φ (°) = ?123.9 ± 2.7, θ₁ (°) = 53.3 θ 4.9, θ ₂ (°) = 61.2 ± 1.6, ψ (°) = ?121.8 ± 5.1. The tendency of γ⁴‐substituted residues to adopt gauche–gauche conformations about the C^α–C^β and C^β–C^γ bonds facilitates helical folding. The αγ C₁₂ helix is a backbone expanded analog of α peptide 3₁₀ helix. The hydrogen bond parameters for α peptide 3₁₀ and α‐helices are compared with those for αγ hybrid C₁₂ helix. Copyright © 2016 European Peptide Society and John Wiley & Sons.     

Polarized fluorescence photobleaching recovery for measuring rotational diffusion in solutions and membranes.

A variation of fluorescence photobleaching recovery (FPR) suitable for measuring the rate of rotational molecular diffusion in solution and cell membranes is presented in theory and experimental practice for epi-illumination microscopy. In this technique, a brief flash of polarized laser light creates an anisotropic distribution of unbleached fluorophores which relaxes by rotational diffusion, leading to a time-dependent postbleach fluorescence. Polarized FPR (PFPR) is applicable to any time scales from seconds to microseconds. However, at fast (microsecond) time scales, a partial recovery independent of molecular orientation tends to obscure rotational effects. The theory here presents a method for overcoming this reversible photobleaching, and includes explicit results for practical geometries, fast wobble of fluorophores, and arbitrary bleaching depth. This variation of a polarized luminescence "pump-and-probe" technique is compared with prior ones and with "pump-only" time-resolved luminescence anisotropy decay methods. The technique is experimentally verified on small latex beads with a variety of diameters, common fluorophore labels, and solvent viscosities. Preliminary measurements on a protein (acetylcholine receptor) in the membrane of nondeoxygenated cells in live culture (rat myotubes) show a difference in rotational diffusion between clustered and nonclustered receptors. In most experiments, signal averaging, high laser power, and automated sample translation must be employed to achieve adequate statistical accuracy.     

Analyse conformationnelle de la N-méthylamide de l'acide L-pyroglutamique par diffusion Rayleigh depolarisée,spectroscopie de vibration et calcul de l'energie conformationnelle

Conformational analysis of N-methylamide of pyroglutamic acid has been performed by theoretical energy calculations and experimental physical techniques, namely, laser Raman spectroscopy and depolarized Rayleigh scattering. The two theoretically predicted conformations are evidenced in crystalline state (ψ₁ = +169°) and in aqueous solution (ψ₁ ? ?20°). This study confirms the interest of a careful vibrational analysis of peptides and N-deuterated derivatives for providing an estimate of the dihedral angle ψ. The relationship between amide III frequency and ψ values is emphasized.     

A new stem hygrometer, corrected for temperature gradients and calibrated against the pressure bomb

Abstract A simple stem hygrometer for attachment to a bared section of sapwood or a cross-sectional cut end of a shoot is described. Two welded chromelconstantan thermocouples inside the chamber, one touching the sample and the other in the chamber air, allowed measurement of and correction for the temperature gradient between the sample and the dewpoint measuring junction. The instrument was attached to the cut end of an apical shoot of Thuja occidentalis L. protuding from a Scholander-Hammel pressure bomb. Cut-end water potential (ψ_hyg), measured using the stem hygrometer, was compared to xylem pressure potential (ψ_xp) while the latter was manipulated in the pressure bomb. After an initial equilibration time of 3–4 h, hygrometer equilibrium values were achieved within 1.5–4.0 min of changing ψ_xp in the pressure bomb. The half-time (ψ_1/2) for vapour pressure equilibration was 15–40 s. Stable temperature gradients between the sample and dewpoint measuring junction of 0.01–0.1°C were measured. Correcting ψ_hyg for the temperature gradient resulted in excellent agreement with ψ_xp.     

Design of Peptides Using α,β-Dehydro-residues: Synthesis,Crystal Structure and Molecular Conformation of N-Boc-L-Val-ΔPhe–ΔPhe-L-Ala-OCH3

To obtain general rules of peptide design using α,β-dehydro-residues, a sequence with two consecutive ΔPhe-residues, Boc-L -Val-ΔPhe–ΔPhe- L -Ala-OCH₃, was synthesized by azlactone method in solution phase. The peptide was crystallized from its solution in an acetone/water mixture (70:30) in space group P6₁ with a=b=14.912(3) Å, c= 25.548(5) Å, V=4912.0(6) ų. The structure was determined by direct methods and refined by a full matrix least-squares procedure to an R value of 0.079 for 2891 observed [I?3σ(I)] reflections. The backbone torsion angles ?₁=?54(1)°, ψ₁= 129(1)°, ω₁=?177(1)°, ?₂ =57(1)°, ψ₂=15(1)°, ω₂ =?170(1)°, ?₃=80(1)°, ψ₃ =7(2)°, ω₃=?177(1)°, ?₄ =?108(1)° and ψ^T₄=?34 (1)° suggest that the peptide adopts a folded conformation with two overlapping β-turns of types II and III′. These turns are stabilized by two intramolecular hydrogen bonds between the CO of the Boc group and the NH of ΔPhe³ and the CO of Val¹ and the NH of Ala⁴. The torsion angles of ΔPhe² and ΔPhe³ side chains are similar and indicate that the two ΔPhe residues are essentially planar. The folded molecules form head-to- tail intermolecular hydrogen bonds giving rise to continuous helical columns which run parallel to the c-axis. This structure established the formation of two β-turns of types II and III′ respectively for sequences containing two consecutive ΔPhe residues at (i+2) and (i+3) positions with a branched β-carbon residue at one end of the tetrapeptide.     

Comparison of thermostability of PSII between the chromatic and green leaf cultivars of <Emphasis Type="Italic">Amaranthus tricolor</Emphasis> L.

In the present study, we investigated the antioxidative potential in leaves of the chromatic (CC) versus green (GC) Amaranthus tricolor L. under moderate high-temperature stress at 45°C. Before heat stress, CC had significantly higher levels of betacyanins [about 3.2 mg g⁻¹(FM)] than the green [1.8 mg g⁻¹(FM) (p<0.01), while similar chlorophyll (Chl) content [about 2 mg g⁻¹(FM)] was observed between both cultivars. After exposure to high temperature (45°C) for 6 days, betacyanins in leaves of CC were remarkably increased (about 2 times of that in control samples grown at 30°C). In contrast, betacyanins in GC significantly decreased by 56% in comparison with that of the control. Chl level in CC was higher than that in GC after heat stress for 6 days. Flavonoids and total phenolics in both cultivars were increased, but much more in CC. Significantly less H₂O₂ accumulation was observed in the leaves and stems of CC than in those of GC under heat stress. Interestingly, much stronger circadian oscillation in fluorescence was observed in both cultivars after treatment at 45°C, which suggested that heat stress stimulates endogenous rhythms of photosystem II (PSII). Under moderate high-temperature stress, Chl fluorescence parameters F_v/F_m (maximum quantum yield of PSII), q_P (coefficient of photochemical quenching), Φ_PSII (effective PSII quantum yield), and ETR (electron transport rate) exhibited a gradual decrease, NPQ (nonphotochemical quenching) showed a slight increase followed by a gradual decline, whereas F_o (minimum fluorescence of a dark-adapted leaf) increased continuously. In contrast to GC, after 120 h of high-temperature treatment, CC exhibited significantly lower Fo level, and higher levels of F_v/F_m and NPQ. It is clear that PSII in CC was more stable than that in GC. The results indicate that betacyanins are an effective antioxidant, and probably contribute greatly to the higher thermal stability of PSII and higher tolerance to heat stress.     

Helix-Forming tendencies of amino acids depend on their sequence contexts: Tripeptides AFG and FAG show incipient β-bulge formation in their crystal structures

Many of the theoretical methods used for predicting the occurrence of α-helices in peptides are based on the helical preferences of amino acid monomer residues. In order to check whether the helix-forming tendencies are based on helical preferences of monomers only or also on their sequence contexts, we synthesized permuted sequences of the tripeptides GAP, GAV, and GAL that formed crystalline helices with near α-helical conformation. The tripeptides AFG and FAG formed good crystals. The x-ray crystallographic studies of AFG and FAG showed that though they contain the same amino acids as GAF but in different sequences, they do not assume a helical conformation in the solid state. On the other hand, AFG and FAG, which contain the same amino acids but in a different sequence, exhibit nearly the same backbone torsion angles corresponding to an incipient formation of a β-bulge, and exhibit nearly identical unit cells and crystal structures. Based on these results, it appears that the helix-forming tendencies of amino acids depend on the sequence context in which it occurs in a polypeptide. The synthetic peptides AFG (L -Ala-L -Phe-Gly) and FAG (L -Phe-L -Ala-Gly), C₁₄H₁₉N₃O₄, crystallize in the orthorhombic space group P2₁2₁2₁, with a = 5. 232(1), b = 14. 622(2), c = 19. 157(3) Å, D_x = 1.329 g cm^?3, Z = 4, R = 0.041 for 549 reflections for AFG, and with a = 5. 488(2), b = 14.189 (1), c = 18.562(1) Å, D_x = 1.348 g cm^?3, Z = 4, R = 0.038 for 919 reflections for FAG. Unlike the other tripeptides GAF, GGV, GAL, and GAI, the crystals of AFG and FAG do not contain water molecule, and the molecules of AFG or FAG do not show the helical conformation. The torsion angles at the backbone of the peptide are ψ₁ = 144. 5(5)°; ?₂, ψ₂ = ?98.1(6)°, ?65.2(6)° ?₃, ψ₁₃, ψ₃₁ = 154.1(6)°, ?173.6(6)°, 6.9(8)° for AFG; and ψ₁ = 162.6(3)°; ?₂, ψ₂ = ?96.7(4)°, ?46.3(4)°; ?₃, ψ₁₃, ψ₃₁ = 150.1(3)°, ?168.7(3)°, 12.2(5)° for FAG. The conformation angles (? ψ) for residues 2 and 3 for both AFG and FAG show incipient formation of an β-bulge. © 1993 John Wiley & Sons, Inc.     

Water Potential and Component Potentials in Expanded and Unexpanded Leaves of Two Xeric Grasses

Water (ψ), osmotic (ψ_s+ψ_m) and pressure (ψ_p) potentials were measured in three leaf regions of Agropyron dasystachyum and A. smithii grown in the field. Spanner-type thermocouple psychrometers were used to measure ψ and (ψ_m+ψ_m). Absolute water content (AWC) was measured gravimetrically. The ψ and ψ_p were slightly lower in the emerging leaf blade (EBI) than in the last fully emerged leaf blade (FEBI); (ψ_s+ψ_m) and AWC were similar in the two regions. A gradient as large as 0.7 MPa was observed between the EBI and the base of the same emerging leaf (EBs); the latter included the meristematic regions. Although (ψ_s+ψ_m) and ψ_p were generally higher in the EBs, the gradients diminished as the level of stress increased in the shoot. Under moderate water stress the ψ_p of the EBs remained constant relative to the ψ_p in the exposed blades. The large ψ gradient within the growing leaf could have resulted from high resistance imposed by poor vascular development in the intercalary meristem. Ability to maintain a relatively large ψ gradient may be of general significance in buffering the growing region of xeric grass leaves from extreme, short-term fluctuations in water stress that occur in exposed leaf blades.     

A ratiometric fluorescence strategy based on copper nanoclusters/carbon dots for sensitive detection of doxorubicin

Sensitive detection of doxorubicin (DOX) is critical for clinical theranostics. A novel ratiometric fluorescence strategy based on the inner filter effect (IFE) has been established for the sensitive detection of DOX by designing a ratiometric fluorescence probe. In the presence of DOX, the fluorescence intensity of copper nanoclusters (CuNCs) at 485 nm decreases, and the fluorescence intensity of carbon dots at 560 nm increases. Therefore, DOX can be quantitatively detected by measuring the ratio of the fluorescence intensities at 560 and 485 nm (F₅₆₀/F₄₈₅). The F₅₆₀/F₄₈₅ ratio exhibits a linear correlation with the DOX concentration in the range from 1.0 × 10⁻⁸ M to 1.0 × 10⁻⁴ M with the detection limit of 3.7 nM. Furthermore, this method was also successfully applied to the analysis of DOX in human plasma samples, affording an effective platform for drug safety management.     

中亚热带森林转换对土壤可溶性有机质数量与光谱学特征的影响

选取中亚热带福建三明格氏栲天然林及其转换而成的木荷、锥栗及福建柏等3种人工林表层土壤(0—10 cm)可溶性有机质(DOM)为对象,对其数量和光谱学特征进行了研究,以探讨森林转换对土壤DOM的影响。结果表明,天然林转换成上述3种人工林后,0—5 cm土壤可溶性有机碳(DOC)浓度显著降低(P0.05),降低程度分别为66.1%,69.9%及29.4%,可溶性有机氮(DON)浓度也有所下降;除福建柏外,其余两种人工林5—10 cm土壤DOC及DON浓度均低于天然林。各林分0—5 cm土壤DOC及DON浓度均高于5—10 cm土层。两个土层中,天然林土壤DOM的芳香化及腐殖化程度均显著高于人工林(P0.05),但荧光效率值低于人工林;荧光光谱图显示,天然林土壤DOM在芳香性脂肪族及木质素类复杂结构荧光基团处的吸收大于人工林;各林分土壤DOM傅里叶红外光谱出现吸收谱带的位置相似,其中吸收强度最大的为形成氢键的—OH的伸缩振动,此外还有芳香性CC伸缩振动、有机羧酸盐COO-反对称伸缩振动、碳水化合物中烷氧基C—O的振动等,人工林土壤DOM中碳水化合物的比例增加是其结构简单的主要原因。土壤DOM中结构复杂、分子量大的组分不易向下迁移;天然林与人工林间土壤DOM数量及光谱学特征的差异主要与凋落物输入及营林措施的干扰有关;本研究所涉及的3种人工林中,福建柏更有利于土壤养分的累积。     

Examination by the molecular orbital method of the intrinsic conformation preferences of nucleic acid sequence]

This paper reports a systematic PCILO study of the conformation of the nucleic acid backbone. The authors principally studied the ω′ and ω phosphodiester torsion angles of the disugar triphosphate model as a simultaneous function of (1) the sugar nature, ribose or deoxyribose, (2) the different combinations of the sugar ring puckers C(2′)-endo-C(2′)-endo, C(3′)-endo-C(3′)-endo, C(3′)-endo-C(2′)-endo, and C(2′)-endo-C(3′)-endo, and (3) the different conformations around the ψ(C4′–C5′) exocyclic bond. The dependence of the (ω′,ω) conformational energy maps upon these different factors, is discussed. The results are in very good agreement with the observed structures of ribonucleic (RNA10, RNA11, A′-RNA12, tRNA^Phe) and deoxyribonucleic acids (D-DNA, C-DNA 9.3, B-DNA 10, A-DNA 11). Thus the validity of this model, the disugar triphosphate unit, is ensured. The main conclusions that can be drawn from this systematic study are the following:

• 1 The torsion around P-05′ (angle ω) is, as a general rule, more flexible than the torsion around P-03′ (angle ω′).
• 2 There is no notable difference between the ribose–triphosphate units and the deoxyribose–triphosphate units for the C(3′)-endo–C(3′)-endo and C(3′)-endo–C(2′)-endo sugar puckers.
• 3 The deoxyribose–triphosphate units with C(2′)-endo–C(2′)-endo and C(2′)-endo–C(3′)-endo sugar puckers show much more ω′ flexibility than the ribose–triphosphate units with the same sugar puckers and cis position for the 2′hydroxyl group.
• 4 The preferred values of ω′ are independent of the sugar nature (ribose or deoxyribose) and of ψ values; they are correlated with the sugar pucker of the first sugar-phosphate unit:
  • C(3′)-endo-C(3′)-endo and C(3′)-endo-C(2′)-endo puckers ? ω′ ? 240° (g^? region)
  • C(2′)-endo-C(2′)-endo and C(2′)-endo-C(3′)-endo puckers ? ω′ 180° (t region)
• 5 The preferred values of ω are independent of the nature and the puckering of the sugars; they are correlated with the rotational state of the torsion angle ψ(C4′–C5′): ψ ? 60° (gg) ? ω ? 300° (g^?), ψ ? 180° (gt) or 300° (tg) ? ω ? 60° (g⁺)

     

Photosynthetic Potential and its Association with Lipid Peroxidation in Response to High Temperature at Different Leaf Ages in Maize

High temperature generally constrains plant growth and photosynthesis in many regions of the world; however, little is known about how photosynthesis responds to high temperature with regard to different leaf ages. The synchronous changes in gas exchange and chlorophyll fluorescence at three leaf age levels (just fully expanded, mature, and older leaves) of maize (Zea mays L.) were determined at three temperatures (30°C as a control and 36 and 42°C as the higher temperatures). High temperature significantly decreased the net CO₂ assimilation rate (A), stomatal conductance (g _s), maximal efficiency of photosystem II (PSII) photochemistry (F _v/F _m), efficiency of excitation energy capture by open PSII reaction centers ( F^￠_\textv /F^￠_\textm F^{\prime}_{\text{v}} /F^{\prime}_{\text{m}} ), photochemical quenching of variable chlorophyll fluorescence (q _P), and the electron transport rate (ETR), whereas minimal fluorescence yield (F ₀) and nonphotochemical quenching of variable chlorophyll fluorescence (q _N) were increased. The youngest fully expanded leaves had higher A, ETR, and q _P compared with older leaves. Higher temperature with old leaves led to significant malondialdehyde (MDA) accumulation, a proxy for lipid peroxidation damage from active oxygen species (AOS). MDA content was significantly negatively correlated with A, F _v/F _m, F^￠_\textv /F^￠_\textm F^{\prime}_{\text{v}} /F^{\prime}_{\text{m}} , and q _P. Thus, the results suggest that photosynthetic potentials, including stomatal regulation and PSII activity, may be restricted at high temperature, together with increasing cell peroxidation, which may be closely associated with leaf age.     

Chilling stress and chilling tolerance of sweet potato as sensed by chlorophyll fluorescence

We studied changes in the chlorophyll (Chl) fluorescence components in chilling-stressed sweet potato (Ipomoea batatas L. Lam) cv. Tainung 57 (TN57, chilling-tolerant) and cv. Tainung 66 (TN66, chilling-susceptible). Plants under 12-h photoperiod and 400 μmol m⁻² s⁻¹ irradiance at 24/20 °C (day/night) were treated by a 5-d chilling period at 7/7 °C. Compared to TN66, TN57 exhibited a significantly greater basic Chl fluorescence (F₀), maximum fluorescence (F_m), maximum fluorescence yield during actinic irradiation (F_m′ ), and the quantum efficiency of electron transport through photosystem 2, PS2 (Φ_PS2). Chilling stress resulted in decrease in the potential efficiency of PS2 (F_v/F_m), Φ_PS2, non-photochemical fluorescence quenching (NPQ), non-photochemical quenching (q_N), and the occurrence of chilling injury in TN66. Chilling increased the likelihood of photoinhibition, characterized by a decline in the Chl fluorescence of both cultivars, and photoinhibition during low temperature stress generally occurred more rapidly in TN66.     

Observation of a sterically unfavorable side-chain conformation in a leucyl residue: Crystal and molecular structure of L-leucyl–L-leucine · DMSO solvate

The crystal structure of a dipeptide L -leucyl–L -leucine (C₁₂H₂₄N₂O₃) has been determined. The crystals are monoclinic, space group P2₁, with a = 5.434(4) Å, b = 15.712(7) Å, c = 11.275(2) Å, β = 100.41(1)°, and Z = 2. The crystals contain one molecule of dimethyl sulfoxide (DMSO) as solvent of crystallization for each dipeptide molecule. The structure has been solved by direct methods and refined to a final R index of 0.059 for 920 reflections (sinθ/λ ? 0.60 Å^?1) with I ? 2σ (I). The trans peptide unit shows substantial degree of non-planarity (Δω = 14°). The peptide backbone adopts an extended conformation with torsion angles of ψ₁ = 138(1)°, ω₁ = 166(1)°, ?₂ = ? 149.3(7)°, ψ₂₁ = 164.2(7)°, and ψ₂₂ = ? 15(1)°. For the first leucyl residue, the side-chain conformation is specified by the torsion angles ¹χ₁ = 176.7(7)°, ¹χ₂₁ = 62(1)°, ¹χ₂₂ = ? 177.4(8)°; the second leucyl residue adopts a Sterically unfavorable conformation with ²χ₁ = 61(1)°, ²χ₂₁ = 97(1)°, and ²χ₂₂ = ?151(1)°. The packing involves head-to-tail interaction of peptide molecules and segregation of polar and nonpolar regions. The DMSO molecule is strongly hydrogen bonded to the terminal NH group. © 1994 John Wiley & Sons, Inc.     

In vivo analysis of chlorophyll <Emphasis Type="Italic">a</Emphasis> fluorescence induction

Quantitative characteristics of photosynthetic electron transport were evaluated in vivo on the basis of the multi-exponential analysis of OJIP fluorescence transients induced by saturating actinic light. The OJIP fluorescence curve F(t), measured in Chlamydomonas reinhardtii cells, was transformed into the (1 − F _O/F(t)) × (F _V /F _M)⁻¹ transient, which is shown to relate to PS 2 closure. We assumed that kinetics of PS 2 closure during OJIP rise reflects time-separated processes related to the establishment of redox equilibrium at the PS 2 acceptor side (OJ), PQ pool (JI), and beyond Cyt b/f (IP). Three-exponential fitting was applied to (1 − F _O/F(t)) × (F _V /F _M)⁻¹ transient to obtain lifetimes and amplitudes of the OJ, JI, and IP components of PS 2 closure, which were used to calculate overall rates of reduction and re-oxidation of the PS 2 acceptor side, PQ pool, and intermediates beyond Cyt b/f complex. The results, obtained in the presence of inhibitors, oxidative reagents, and under different stress conditions prove the suggested model and characterize the introduced parameters as useful indicators of photosynthetic function.     

Chlorophyll fluorescence quenching and violaxanthin deepoxidation of FBPase antisense plants at low light intensities and low temperatures

Genetically modified potato (Solanum tuberosum L. cv. Desiree) and tobacco (Nicotiana tabacum cv. Samsun N.N.) plants were used to analyze the effects exerted by the chloroplastic (cp) fructose- 1,6-bisphosphatase (FBPase) on the regulation of light energy discrimination at the level of photosystem II. The cp-FBPase activity was progressively inhibited by an mRNA antisense to this FBPase. The chlorophyll fluorescence quenching parameters of these transgenic plants were compared to those of wild-type and transgenic plants that were acclimated to low temperatures. In particular various lines of the transgenic potato and tobacco plants were exposed to a temperature treatment of 10 and 20°C for 10 days. Light intensities were kept low to reduce photoinhibition so that we could analyze exclusively the effects of a modification in the carbon fixation cycle on the chlorophyll fluorescence quenching parameters. The photon flux densities (PFDs) employed at the level of the middle leaves of all plants were set to two different values of 10 μmol m^?2 s^?1 and 50 μmol m^?2 s^?1. Subsequent to this 10-day acclimation the chlorophyll-fluorescence parameters of all plants were measured. Photoinhibition as expressed by the F_y/F_m ratio was minor in plants subjected to a PFD of 10 μmol m^?2 s^?1. Higher photon fluence rates of 50 μmol m^?2 s^?1 at temperatures of 10°C gave rise to a significant reduction in the F_y/F_m ratios obtained from the transgenic plants which were characterized by a restriction in cp-FBPase capacity to 20% of normal activity. Furthermore, a progressive inhibition of the cp-FBPase activity induced an amplified nonphotochemical quenching of chlorophyll fluorescence with in the genetically manipulated species (except at 10°C and 50 μmol m^?2 s^?1). The increase in nonphotochemical quenching depended upon light and temperature. Photochemical quenching of light quanta within the antisense plants declined relative to that in the wild type. To further characterize the mechanisms producing higher levels of nonphotochemical fluorescence quenching. we analyzed several of the xanthophyll cycle pigments. The deepoxidation state of the xanthophyll cycle pigments in potato plants increased with attenuating FBPase activities under all conditions. For tobacco plants, this elevation of the deepoxidation state was only observed at a PFD of 50 μmol m^?2 s^?1.     

Modelling the effect of soil moisture on germination and emergence of wheat and sugar beet with the minimum number of parameters

Soil moisture and temperature, sowing depth and penetration resistance affect the time and percentage of seedling emergence, which are crucial for the simulation of drought‐limited crop production. The aim of this research was to measure the effect of soil water potential on germination and emergence, shoot and root elongation rates (SER and RER) of two different seed/crop types. Sugar beet and durum wheat seeds were sown into two soils (clay and loam), submitted to five matric potentials (?0.01, ?0.1, ?0.2, ?0.4 and ?0.8 MPa) and incubated at constant temperature (25°C) and humidity. Cumulative count analysis was used to estimate parameters of the distribution of germination or emergence times for each box of beet or wheat seeds and to derive estimates for base potentials (ψ_b), hydrothermal times (H) and numbers of viable units. In a second experiment, NaCl solution was used to mimic the soil matric potentials to estimate potential RER and SER. Germination of sugar beet was slightly more sensitive to matric potential than durum wheat (ψ_b of ?1.13 and ?1.23 MPa, respectively). H_(g) was longer for sugar beet than for durum wheat (67 vs 47 MPa °Cd). For emergence ψ_b was similar for both seed types and soils but hydrothermal times (H_(e)) were 40 MPa °Cd higher for sugar beet than for wheat. Emergence was about 20 MPa °Cd earlier in loam than in clay. SER measured in soils were similar for both crops and for durum wheat it agreed with those determined in NaCl solution. RER and SER fell with decreasing osmotic potential to approximately 20% of their maximum values (1.03 mm h^?1 and 0.57 mm h^?1, respectively). Seedling viability decreased with decreasing matric potential and more in clay than in loam soil and more for sugar beet than durum wheat. Seed and soil aggregate size are discussed with respect to the effects of water diffusion and soil–seed contact on germination and emergence modelling.     

Type II β-turn conformation of pivaloyl-L-prolyl-α-aminoisobutyryl-N-methylamide: Theoretical,spectroscopic, and X-ray studies

Pivaloyl-L -Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD₃)₂SO solution, by ¹H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol^?1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P2₁ with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are ?_Pro = ?57.8°, ψ_Pro = 139.3°, ?_Aib = 61.4°, and ψ_Aib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.