Measurement of 15N csa/dipolar cross-correlation rates by means of Spin State Selective experiments

We propose a method for the determination of (15)N csa/dipolar cross-correlation rates based on the measurement of the two apparent transverse (or longitudinal) relaxation rates associated with each component of the nitrogen doublet (N(alpha) and N(beta)). This is achieved by inserting a spin state selective scheme in conventional inverse Carr-Purcell-Meiboom-Gill (or inversion-recovery) pulse sequence which allows for the edition of a HSQC-type spectrum for each of the spin states. Transverse cross-correlation rates necessitate two independent sets of measurements (for N(alpha) and N(beta), respectively), whereas for longitudinal cross correlation rates, besides N(alpha) and N(beta) measurements, the method requires the knowledge of both the (15)N longitudinal auto-relaxation rate and the longitudinal two-spin order (2NzHz) auto-relaxation rate. These additional parameters are mandatory because of the non-exponential behavior of the N(alpha) and N(beta) longitudinal decays. Conversely, the present method does not require any complex manipulation of 2D spectra, the cross-correlation rates being obtained from the difference of the two (N(alpha) and N(beta)) apparent relaxation rates. This approach is applied to (15)N-labelled ubiquitin at two different magnetic fields (9.4 T and 14.1 T).     

Long-term continuous partial nitritation-anammox reactor aeration optimization at different nitrogen loading rates for the treatment of ammonium rich digestate lagoon supernatant

Dissolved oxygen (DO) is an important parameter for partial nitritation-anammox process but previously not evaluated for the treatment of digested biosolid thickening lagoon supernatant. Using intermittent aeration we investigated nitrogen removal from such supernatant in an integrated fixed film activated sludge (IFAS) process operated under a variety of hydraulic retention times (1.2–2.5 days). The overall nitrogen removal rate (NRR) was significantly increased (P < 0.01) from 0.26 ± 0.01 kg N m⁻³ d^-1 at HRT of 2.5 days to 0.50 ± 0.01 kg N m^-3 d^-1 at HRT of 1.2 day. Higher nitrogen loading rates needed higher DO concentrations in order to cope with the increased oxygen demand by ammonium-oxidizing bacteria (AOB). Enhancing the DO concentration from 0.18 mg L^-1 to 0.35 mg L^-1 improved AOB activity. However, when the bulk liquid DO was in the range of 0.28−0.35 mg L^-1, anammox activity inhibition was observed associated with a significant free nitrous acid (FNA) accumulation (21.70 ± 4.10 μg L^-1). Batch studies confirmed the inhibition of anammox activity under high DO conditions (0.28−0.35 mg L^-1). Aeration strategies, other than increasing the DO set points, should be investigated in order to be able to work at high nitrogen loading rates without compromising anammox activity.     

Local mobility of 15N labeled biomolecules characterized through cross-correlation rates: Applications to paramagnetic proteins*

The mobility of 15N labeled proteins can be characterized by measuring the cross-correlation rates N,NI that govern the conversion of Zeeman order Nz of an amide 15N nucleus into longitudinal two-spin order 2NzIz involving the amide 15N and 1H nuclei. This represents an alternative to the measurement of 15N self-relaxation rates 1/T1 and 1/T2 or 1/T1. The rate of interconversion between Nz and 2NzIz is due to cross-correlation between fluctuations of different interactions and is not affected by a variety of relaxation mechanisms that contribute to the self-relaxation rates 1/T1, 1/T2 and 1/T1. Spin diffusion among protons, which affects the measurements, can be quenched by various means that are evaluated by experiments and simulations. By applying an off-resonance radio-frequency (RF) field in the vicinity of the nitrogen resonance, the spectral density function J() can be determined at the frequency origin and at the nitrogen Larmor frequency. The methods are applied to the paramagnetic High-Potential Iron-Sulfur Protein iso I (HiPIP I) from E. halophila in its reduced state.     

The use of growth and ingestion rates of Capitella sp. I as the bioassay approaches to determine the sediment quality of coastal wetlands of Taiwan

Food is a limiting factor for the deposit feeders. The availability of sediment nutrients thus has a tight relationship with the growth, survival and development of the animal. There are two purposes of this study: (1) to determine if the ingestion and growth rates can be used as a bioassay approach to assess the sediment nutrients; and (2) use the combination of bioassay approaches and chemical analyses to determine which chemical parameter is the better predicator of the sediment nutrients to the animals. In the preliminary study, the optimal growth length and average ingestion rate of Capitella sp. I were obtained from the laboratory. The standardized relationships of the growth and ingestion rates in response to different nutrients were prepared. Then, the sediments collected from different coastal wetlands in Western Taiwan were used in the feeding, growth experiments and chemical analyses. The comparisons were made between the field and laboratory experiments to determine the sediment nutrients in the wetland of Taiwan. In the growth rate standardized relationship, Capitella sp. I increased its growth rate with the total organic nitrogen (TON) concentration between 0 to 2.8 mgN·g sediment⁻¹, total organic carbon (TOC) concentration between 0 and 22.4 mgC·g sediment⁻¹, and enzymatically hydrolyzable amino acid (EHAA) concentration between 0 and 4.48 mg protein·g sediment⁻¹. After the nutrient concentrations exceed these values, the growth rates decreased gradually. In the ingestion rate standardized relationship, the animal increased its ingestion rate with the total organic nitrogen (TON) concentration between 0 and 2 mgN·g sediment⁻¹, total organic carbon (TOC) concentration between 0 and 14.1 mgC·g sediment⁻¹, and EHAA concentration between 0 and 3.2 mg protein·g sediment⁻¹. After the nutrient concentrations exceed these values, the ingestion rates also decreased. To determine which nutrient parameter is the best predictor for the sediment nutrient in the field, we first analyzed whether the data obtained from the laboratory fell within 99% confidence interval of the regression obtained from the field data. Then, to determine which parameter had the shortest perpendicular distance between the field and the laboratory regression curves. Both the growth and ingestion rates comparisons showed that the EHAA is the best candidate of the sediment nutrient of deposit feeders in the field. The results of this study proved tentatively that the growth and ingestion rates of Capitella sp. I can be used as the bioassay approaches to estimate the sediment nutrients. The combination of the bioassay approaches and the relevant chemical analyses allows us to determine the bioavailability fraction of sediment to the deposit feeders.     

Direct measurement of the 15N CSA/dipolar relaxation interference from coupled HSQC spectra

Here we propose a method for the measurement of the ¹⁵N CSA/dipolar relaxation interference based on direct comparison of the ¹⁵N doublet components observed in a ¹H-coupled ¹H-¹⁵N HSQC-type spectrum. This allows the determination of the cross-correlation rates with no need for correction factors associated with other methods. The signal overlap problem of coupled HSQC spectra is addressed here by using the IPAP scheme (Ottiger et al., 1998). The approach is applied to the B3 domain of protein G to show that the method provides accurate measurements of the ¹⁵N CSA/dipolar cross-correlation rates.     

Measurement of Dipolar Cross-Correlation in Methylene Groups in Uniformly 13C-, 15N-Labeled Proteins

A CC(CO)NH TOCSY-based 3D pulse scheme is presented for measuring (1)H-(13)C dipole-dipole cross-correlated relaxation at CH(2) positions in uniformly (13)C-, (15)N-labeled proteins. Simulations based on magnetization evolution under relaxation and scalar coupling interactions show that cross-correlation rates between (1)H-(13)C dipoles in CH(2) groups can be simply obtained from the intensities of (13)C triplets. The normalized cross-correlation relaxation rates are related to cross-correlation order parameters for macromolecules undergoing isotropic motion, which reflect the degrees of spatial restriction of CH(2) groups. The study on human intestinal fatty acid binding protein (131 residues) in the presence of oleic acid demonstrates that side chain dynamics at most CH(2) positions can be characterized for proteins less than 15 kDa in size, with the proposed TOCSY-based approach.     

A study of mobility and order in model membranes using 2H NMR relaxation rates and quadrupole splittings of specifically deuterated lipids

²H NMR spectra have been observed for several selectively deuterated phospholipid and fatty acid probes intercalated in the liquid crystalline phase of egg phosphatidylcholine in aqueous dispersion. For unsonicated lamellar dispersions and planar multibilayers, quadrupole splittings may be observed which lead directly to a value for the order parameter for the carbon-deuterium bond. Sonicated dispersions yield high-resolution spectra, from which spin-lattice relaxation rates and correlation times for rotational diffusion can be obtained. The presence of cholesterol in the dispersion has no effect on the quadrupole splittings and relaxation rates for ²H in the choline methyl groups, in contrast to its profound effect on the spectra for ²H in the hydrocarbon chains.     

Potential of a dust grain in a nitrogen plasma with a condensed disperse phase at room and cryogenic temperatures

The first numerical study is presented of the self-consistent potential of a dust grain in a nitrogen plasma with a condensed disperse phase at room and cryogenic temperatures and at high gas pressures for which the electron and ion transport in the plasma can be described in the hydrodynamic approximation. It is shown that the potential of the dust grain is described with good accuracy by the Debye potential, in which case, however, the screening radius turns out to be larger than the electron Debye radius. The difference between the radii is especially large in a plasma with high ionization rates (about 10¹⁶–10¹⁸ cm^?3 s^?1) at room temperature. It is found that, in a certain range of the parameters of a nitrogen dusty plasma, the parameter describing the interaction between the grains exceeds the critical value above which one would expect the formation of plasma-dust structures such as Coulomb crystals. For a plasma at cryogenic temperature (T=77 K), this range is significantly wider.     

A New Methodology of Spatial Cross-Correlation Analysis

Spatial correlation modeling comprises both spatial autocorrelation and spatial cross-correlation processes. The spatial autocorrelation theory has been well-developed. It is necessary to advance the method of spatial cross-correlation analysis to supplement the autocorrelation analysis. This paper presents a set of models and analytical procedures for spatial cross-correlation analysis. By analogy with Moran’s index newly expressed in a spatial quadratic form, a theoretical framework is derived for geographical cross-correlation modeling. First, two sets of spatial cross-correlation coefficients are defined, including a global spatial cross-correlation coefficient and local spatial cross-correlation coefficients. Second, a pair of scatterplots of spatial cross-correlation is proposed, and the plots can be used to visually reveal the causality behind spatial systems. Based on the global cross-correlation coefficient, Pearson’s correlation coefficient can be decomposed into two parts: direct correlation (partial correlation) and indirect correlation (spatial cross-correlation). As an example, the methodology is applied to the relationships between China’s urbanization and economic development to illustrate how to model spatial cross-correlation phenomena. This study is an introduction to developing the theory of spatial cross-correlation, and future geographical spatial analysis might benefit from these models and indexes.     

Continuous polyhydroxybutyrate production from biogas in an innovative two-stage bioreactor configuration

Biogas biorefineries have opened up new horizons beyond heat and electricity production in the anaerobic digestion sector. Added-value products such as polyhydroxyalkanoates (PHAs), which are environmentally benign and potential candidates to replace conventional plastics, can be generated from biogas. This work investigated the potential of an innovative two-stage growth-accumulation system for the continuous production of biogas-based polyhydroxybutyrate (PHB) using Methylocystis hirsuta CSC1 as cell factory. The system comprised two turbulent bioreactors in series to enhance methane and oxygen mass transfer: a continuous stirred tank reactor (CSTR) and a bubble column bioreactor (BCB) with internal gas recirculation. The CSTR was devoted to methanotrophic growth under nitrogen balanced growth conditions and the BCB targeted PHB production under nitrogen limiting conditions. Two different operational approaches under different nitrogen loading rates and dilution rates were investigated. A balanced nitrogen loading rate along with a dilution rate (D) of 0.3 day⁻¹ resulted in the most stable operating conditions and a PHB productivity of ~53 g PHB m⁻³ day⁻¹. However, higher PHB productivities (~127 g PHB m⁻³ day⁻¹) were achieved using nitrogen excess at a D = 0.2 day⁻¹. Overall, the high PHB contents (up to 48% w/w) obtained in the CSTR under theoretically nutrient balanced conditions and the poor process stability challenged the hypothetical advantages conferred by multistage vs single-stage process configurations for long-term PHB production.     

施氮对高产小麦群体动态、产量和土壤氮素变化的影响

选用多穗型小麦品种豫麦49-198和大穗型小麦品种兰考矮早八,以河南温县和兰考为试验地点,在0、90、180、270、360Nkg.hm-2水平下,通过田间试验对小麦群体动态、产量和土壤氮素变化进行了研究.结果表明:两个品种小麦都是从出苗开始群体数量不断增加,到拔节期达到最大,然后开始下降.在不同施氮水平和试验点间,豫麦49-198在越冬期和返青期群体数量没有显著差异,拔节以后不同氮水平间群体数量差异显著;而兰考矮早八在所有生育时期,不同施氮水平间群体数量都没有显著差异.随氮肥用量的增加,小麦产量增加,但过量施氮则使小麦产量下降,豫麦49-198以270Nkg.hm-2水平下产量最高,在温县和兰考点分别为9523和9867kg.hm-2,兰考矮早八以180Nkg.hm-2水平下产量最高,在温县和兰考点分别为9258和9832kg.hm-2.随着氮肥用量的增加,土壤硝态氮含量和氮素表观损失增加,豫麦49-198在温县和兰考点的氮素表观损失分别占氮肥用量的32.56%～51.84%和-16.70%～42.60%,兰考矮早八则分别占氮肥用量的18.58%～52.94%和-11.50%～45.80%.在本研究条件下,兼顾产量和环境效应,0～90cm土壤硝态氮累积量不应超过120～140kg.hm-2,小麦氮用量不能超过180kg.hm-2.     

Denitrification and Nitrogen Fixation in Alaskan Continental Shelf Sediments

Rates of nitrogen fixation and denitrification were measured in Alaskan continental shelf sediments. In some regions, rates of nitrogen fixation and denitrification appeared to be equal; in other areas, rates were significantly different. Potential rates of denitrification were found to be limited primarily by the available nitrate substrate. Major regional differences in rates of denitrification were not statistically significant, but significant differences were found for nitrogen fixation rates in different regions of the Alaskan continental shelf. Estimated net losses of nitrogen from Bering Sea sediments were calculated as 1.8 × 10¹² g of N/yr. Experimental exposure of continental shelf sediments to petroleum hydrocarbons reduced rates of nitrogen fixation and denitrification in some cases but not others. Long-term exposure was necessary before a reduction in nitrogen fixation rates was observed; unamended rates of denitrification but not potential denitrification rates (NO₃⁻ added) were depressed after exposure to hydrocarbons.     

Gypsy moth invasion in North America: A simulation study of the spatial pattern and the rate of spread

Gypsy moth is regarded as one of the top most harmful invasive species. Its invasion in the northeastern US has led to widespread forest defoliation, wildlife disruption and even a change in biogeochemical conditions over the area of 10⁶ km². Spread of gypsy moth has a few distinct features such as a patchy spatial distribution of the gypsy moth population, which is largely uncorrelated to the environmental heterogeneity, and a high variability (almost over an order of magnitude) in the spread rates. These features are usually explained by human-assisted dispersal, e.g. when masses of gypsy moth eggs are inadvertently transported by cars and vehicles. This theory, however, somewhat disagrees with the existence of the strong Allee effect that tends to wipe out small new colonies. In this paper, we suggest an alternative explanation that the patchy structure can result from the interplay between two natural factors such as wind dispersal and viral infection. In order to check this hypothesis, we describe the gypsy moth spread with a diffusive SI model and study its properties by means of extensive computer simulations. Interestingly, in a certain parameter range our model shows formation of spatial patterns that are qualitatively similar to those observed in the field. To find out the relevant parameter range, we make a careful review of available literature sources. For biologically meaningful parameter values, we then show that the rates of gypsy moth spread predicted by our model are in good agreement with the lower band of the rates observed in nature.     

蚂蚁筑巢对西双版纳热带森林土壤有机氮矿化的影响

蚂蚁作为生态系统工程师能够调节土壤微生物及理化环境,进而对热带森林土壤有机氮矿化速率及其时间动态产生显著影响。以西双版纳白背桐热带森林群落为研究对象,采用室内需氧培养法测定土壤有机氮矿化速率,比较蚁巢和非蚁巢土壤有机氮矿化速率的时间动态,揭示蚂蚁筑巢活动引起土壤无机氮库、微生物生物量碳及化学性质改变对有机氮矿化速率时间动态的影响。结果表明：（1）蚂蚁筑巢显著影响土壤有机氮矿化速率（P<0.01）,相较于非蚁巢,蚁巢土壤有机氮矿化速率提高了261%;（2）土壤有机氮矿化速率随月份推移呈明显的单峰型变化趋势,即6月最大（蚁巢1.22 mg kg^-1 d^-1、非蚁巢0.41 mg kg^-1 d^-1）,12月最小（蚁巢0.82 mg kg^-1 d^-1、非蚁巢0.18 mg kg^-1 d^-1）;（3）两因素方差分析表明,不同月份及不同处理对土壤有机氮矿化速率、NH₄-N及NO₃-N产生显著影响（P<0.05）,但对NO₃-N的交互作用不显著;（4）蚂蚁筑巢显著提高了无机氮库（NH₄-N与NO₃-N）、微生物生物量碳、有机质、水解氮、全氮及易氧化有机碳等土壤养分含量,而降低了土壤pH值;（5）回归分析表明,铵态氮和硝态氮对土壤有机氮矿化速率产生显著影响,分别解释87.89%、61.84%的有机氮矿化速率变化;（6）主成份分析表明NH₄-N、微生物生物量碳及有机质是影响有机氮矿化速率时间动态的主要因素,而全氮、NO₃-N、易氧化有机碳、水解氮及pH对土壤有机氮矿化速率的影响次之,且pH与土壤有机氮矿化速率呈显著负相关。总之,蚂蚁筑巢活动主要通过影响土壤NH₄-N、微生物生物量碳及有机质的状况,进而调控西双版纳热带森林土壤有机氮矿化速率的时间动态。研究结果将有助于进一步提高对土壤氮矿化生物调控机制的认识。     

Quantitative estimation of magnitude and orientation of the CSA tensor from field dependence of longitudinal NMR relaxation rates

A method is presented that makes it possible to estimate both the orientation and the magnitude of the chemical shift anisotropy (CSA) tensor in molecules with a pair of spin 1/2 nuclei, typically ¹³C-¹H or ¹⁵ N-¹H. The method relies on the fact that the longitudinal cross-correlation rate as well as a linear combination of the autorelaxation rates of longitudinal heterospin magnetization, longitudinal two-spin order and longitudinal proton magnetization are proportional to the spectral density at the Larmor frequency of the heterospin. Therefore the ratio between the cross-correlation rate and the above linear combination is independent of the dynamics. From the field dependence of the ratio both the magnitude and the orientation of the CSA tensor can be estimated. The method is applicable to molecules in all motional regimes and is not limited to molecules in extreme narrowing or slow tumbling, nor is it sensitive to chemical exchange broadening. It is tested on the 22 amino acid residue peptide motilin, selectively ¹³ C labeled in the ortho positions in the ring of the single tyrosine residue. In the approximation of an axially symmetric ¹³C CSA tensor, the symmetry axis of the CSA tensor makes an angle of 23° ± 1° to the ¹³ C-¹H bond vector, and has a magnitude of 156 ± 5 ppm. This is in close agreement with solid-state NMR data on tyrosine powder [Frydman et al. (1992) Isr. J. Chem., 32, 161–164].     

The biogeochemistry of nitrogen in freshwater wetlands

The biogeochemistry of N in freshwater wetlands is complicated by vegetation characteristics that range from annual herbs to perennial woodlands; by hydrologic characteristics that range from closed, precipitation-driven to tidal, riverine wetlands; and by the diversity of the nitrogen cycle itself. It is clear that sediments are the single largest pool of nitrogen in wetland ecosystems (100's to 1000's g N m^-2) followed in rough order-of-magnitude decreases by plants and available inorganic nitrogen. Precipitation inputs (< 1–2 g N m^-2 yr^-1) are well known but other atmospheric inputs, e.g. dry deposition, are essentially unknown and could be as large or larger than wet deposition. Nitrogen fixation (acetylene reduction) is an important supplementary input in some wetlands (< < 1–3 g N m^-2 yr^-1) but is probably limited by the excess of fixed nitrogen usually present in wetland sediments.Plant uptake normally ranges from a few g N m^-2 yr^-1 to 35 g N m^-2 yr^-1 with extreme values of up to 100g N m^-2 yr^-1 Results of translocation experiments done to date may be misleading and may call for a reassessment of the magnitude of both plant uptake and leaching rates. Interactions between plant litter and decomposer microorganisms tend, over the short-term, to conserve nitrogen within the system in immobile forms. Later, decomposers release this nitrogen in forms and at rates that plants can efficiently reassimilate.The NO₃ formed by nitrification (< 0.1 to 10 g N m^-2 yr^-1 has several fates which may tend to either conserve nitrogen (uptake and dissimilatory reduction to ammonium) or lead to its loss (denitrification). Both nitrification and denitrification operate at rates far below their potential and under proper conditions (e.g. draining or fluctuating water levels) may accelerate. However, virtually all estimates of denitrification rates in freshwater wetlands are based on measurements of potential denitrification, not actual denitrification and, as a consequence, the importance of denitrification in these ecosystems may have been greatly over estimated.In general, larger amounts of nitrogen cycle within freshwater wetlands than flow in or out. Except for closed, ombrotrophic systems this might seem an unusual characteristic for ecosystems that are dominated by the flux of water, however, two factors limit the opportunity for N loss. At any given time the fraction of nitrogen in wetlands that could be lost by hydrologic export is probably a small fraction of the potentially mineralizable nitrogen and is certainly a negligible fraction of the total nitrogen in the system. Second, in some cases freshwater wetlands may be hydrologically isolated so that the bulk of upland water flow may pass under (in the case of floating mats) or by (in the case of riparian systems) the biotically active components of the wetland. This may explain the rather limited range of N loading rates real wetlands can accept in comparison to, for example, percolation columns or engineered marshes.     

Photosynthesis and nitrogen utilization in exponentially growing nitrogen-limited cultures of Lemna gibba

The photosynthetic performance and nitrogen utilization of Lemna gibba L. G3 adapted to limited nitrogen supply was studied. The plants were adapted to two levels of nitrogen limitation where the nitrogen addition rates were calculated to sustain relative growth rates (RGR) of 0.15 day^?1 and 0.25 day^?1, respectively. The photosynthetic performance of these cultures was compared to nitrogen-sufficient cultures with an average RGR of 0.32 day^?1. Plants transferred from nitrogen-sufficient conditions attained RGR values corresponding to the nitrogen addition rates after 6 to 10 days. Light-saturated net photosynthesis declined during adaptation according to the drop in growth rate, and a concomitant decrease in the respiration rate was recorded. The efficiency of net photosynthesis on a dry weight basis increased with increased nitrogen supply, whereas it was the same in all cultures when expressed on a chlorophyll basis. The light compensation point was unaffected by the nitrogen regime. Limited nitrogen supply resulted in an increased proportion of dry matter in the roots, which led to decreased leaf area ratios. The net assimilation rates also decreased, but not to the same extent as the leaf area ratios. Growth-limiting amounts of nitrogen were added to the cultures once daily, and the net influx of N was higher than the requirement for N, also in adapted cultures with a steady growth rate. This resulted in transient, periodic fluctuations in the NO₃^?, NH₄⁺ and amino acid pools. Also the rates of NO₃^? reduction and NH₄⁺ assimilation fluctuated as did the amino acid assimilation which paralleled NH₄⁺ assimilation. The role of flux rates over the plasmalemma and tonoplast for control of nitrogen assimilation rates are discussed.     

Noises-induced regime shifts and -enhanced stability under a model of lake approaching eutrophication

In this paper, we study the lake eutrophication by using a stochastic model that includes both input noise and recycling noise. The effects of the input noise (α), the recycling noise (D) and the cross-correlation between two noises (λ) in the model are discussed, respectively. Our results show: (i) the noise-induced ecological bistability (EB) expands in comparison with the deterministic case; (ii) noises still can induce EB when the recycling parameter r < 0.5; (iii) the noises can cause the regime shifts from the eutrophic state to the oligotrophic one (noise-induced oligotrophy); and (iv) the input noise can accelerate regime shifts from the oligotrophic state to the eutrophic one for the case of zero or small cross-correlation. Moreover, for the case of higher cross-correlation intensity, the mean first passage time (MFPT) as a function of α exhibits a maximum, which identifies the input noise-enhanced stability (NES) of the oligotrophic state. Finally, for whatever value of cross-correlation intensity, the theoretical results show that the recycling noise can accelerate regime shifts from the oligotrophic state to the eutrophic one.     

An investigation of the dynamics of spermine bound to duplex and quadruplex DNA by <Superscript>13</Superscript>C NMR spectroscopy

A detailed analysis of the ¹³C relaxation of ¹³C-labelled spermine bound to duplex and quadruplex DNA is presented. T₁, T₂ and heteronuclear NOE data were collected at four ¹³C frequencies (75.4, 125.7, 150.9 and 201.2 MHz). The data were analyzed in terms of a frequency-dependent order parameter, S ²(ω), to estimate the generalized order parameter and the contributions to the relaxation from different motional frequencies in the picosecond–nanosecond timescale and from any exchange processes that may be occurring on the microsecond–millisecond timescale. The relaxation data was surprisingly similar for spermine bound to two different duplexes and a linear parallel quadruplex. Analysis of the relaxation data from these complexes confirmed the conclusions of previous studies that the dominant motion of spermine is independent of the macroscopic tumbling of the DNA and has an effective correlation time of ∼50 ps. In contrast, spermine bound to a folded antiparallel quadruplex had faster relaxation rates, especially R ₂. As with the other complexes, a fast internal motion of the order of 50 ps makes a substantial contribution to the relaxation. The generalized order parameter for spermine bound to duplex DNA and the linear quadruplex is small but is larger for spermine bound to the folded quadruplex. In the latter case, there is evidence for exchange between at least two populations of spermine occurring on the microsecond–millisecond timescale. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.