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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ‐Alumina**

Abstract γ‐alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large‐scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ‐alumina that are responsible for its unique catalytic properties has remained obscure and controversial. By using combined infrared spectroscopy, electron microscopy and solid‐state nuclear magnetic resonance measurements we identify the octahedral, amphoteric (O) 5 Al(VI)‐OH sites on the (100) segments of massively restructured (110) facets on typical rhombus‐platelet γ‐alumina as well as the (100) segments of irrational surfaces (invariably always present in all γ‐alumina samples) responsible for its unique catalytic activity. Such (O) 5 Al(VI)‐OH sites are also present on the macroscopically defined (100) facets of γ‐alumina with elongated/rod‐like geometry. The mechanism by which these sites lose ‐OH groups upon thermal dehydroxylation resulting in coordinatively unsaturated penta‐coordinate Al +3 O 5 sites is clarified. These coordinatively unsaturated penta‐coordinate Al sites produce well‐defined thermally stable Al‐carbonyl complexes. Our findings contribute to the understanding of the nature of coordinatively unsaturated Al sites on the surface of γ‐alumina and their role as catalytically active sites.

Khivantsev, Konstantin↗
DOE OSTI2022

A Metal‐Organic Framework (MOF)‐Based Multifunctional Cargo Vehicle for Reactive‐Gas Delivery and Catalysis

Abstract The efficient delivery of reactive and toxic gaseous reagents to organic reactions was studied using metal‐organic frameworks (MOFs). The simultaneous cargo vehicle and catalytic capabilities of several MOFs were probed for the first time using the examples of aromatization, aminocarbonylation, and carbonylative Suzuki–Miyaura coupling reactions. These reactions highlight that MOFs can serve a dual role as a gas cargo vehicle and a catalyst, leading to product formation with yields similar to reactions employing pure gases. Furthermore, the MOFs can be recycled without sacrificing product yield, while simultaneously maintaining crystallinity. The reported findings were supported crystallographically and spectroscopically (e.g., diffuse reflectance infrared Fourier transform spectroscopy), foreshadowing a pathway for the development of multifunctional MOF‐based reagent‐catalyst cargo vessels for reactive gas reagents as an attractive alternative to the use of toxic pure gases or gas generators.

Kittikhunnatham, Preecha↗
DOE OSTI2022

Semiconducting Copolymers with Naphthalene Imide/Amide π‐Conjugated Units: Synthesis, Crystallography, and Systematic Structure‐Property‐Mobility Correlations

Abstract In a series of n‐type semiconducting naphthalene tetracarboxydiimide ( NDI )‐dithiophene ( T2 ) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1‐amino‐4,5‐8‐naphthalene‐tricarboxylic acid‐1,8‐lactam‐4,5‐imide) to 2 in NBA (naphthalene‐bis(4,8‐diamino‐1,5‐dicarboxyl)‐amide). As the NDI ‐ T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA . Electron mobility is greatest for N2200 (0.17 cm 2 V −1 s −1 ) followed by PNBL‐3,8‐T2 and PNBA‐2,6‐T2 (0.11 cm 2 V −1 s −1 ), 0.02 cm 2 V −1 s −1 in PNBL‐4,8‐T2 , and negligible in PNBA‐3,7‐T2 . Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL‐4,8‐T2 ), backbone planarity (optimum for PNBA‐2,6‐T2 and PNBL‐3,8‐T2 ), LUMO energy (optimum for N2200 ), π–π stacking distance (optimum for PNBA‐2,6‐T2 ), and film crystallinity (optimum for PNBA‐2,6‐T2 and N2200 ). These results offer generalizable insight into semiconducting copolymer design.

Chen, Yao↗
DOE OSTI2021

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ-Alumina

γ-alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large-scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ-alumina that are responsible for its unique catalytic properties has remained obscure and controversial. By using combined infrared spectroscopy, electron microscopy and solid-state nuclear magnetic resonance measurements we identify the octahedral, amphoteric (O) 5 Al(VI)-OH sites on the (100) segments of massively restructured (110) facets on typical rhombus-platelet γ-alumina as well as the (100) segments of irrational surfaces (invariably always present in all γ-alumina samples) responsible for its unique catalytic activity. Such (O) 5 Al(VI)-OH sites are also present on the macroscopically defined (100) facets of γ-alumina with elongated/rod-like geometry. The mechanism by which these sites lose -OH groups upon thermal dehydroxylation resulting in coordinatively unsaturated penta-coordinate Al +3 O 5 sites is clarified. These coordinatively unsaturated penta-coordinate Al sites produce well-defined thermally stable Al-carbonyl complexes. Overall, our findings contribute to the understanding of the nature of coordinatively unsaturated Al sites on the surface of γ-alumina and their role as catalytically active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Metal-Organic Framework (MOF)-Based Multifunctional Cargo Vehicle for Reactive-Gas Delivery and Catalysis

The efficient delivery of reactive and toxic gaseous reagents to organic reactions was studied using metal-organic frameworks (MOFs). The simultaneous cargo vehicle and catalytic capabilities of several MOFs were probed for the first time using the examples of aromatization, aminocarbonylation, and carbonylative Suzuki–Miyaura coupling reactions. These reactions highlight that MOFs can serve a dual role as a gas cargo vehicle and a catalyst, leading to product formation with yields similar to reactions employing pure gases. Furthermore, the MOFs can be recycled without sacrificing product yield, while simultaneously maintaining crystallinity. Our reported findings were supported crystallographically and spectroscopically (e.g., diffuse reflectance infrared Fourier transform spectroscopy), foreshadowing a pathway for the development of multifunctional MOF-based reagent-catalyst cargo vessels for reactive gas reagents as an attractive alternative to the use of toxic pure gases or gas generators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

Here, in a series of n-type semiconducting naphthalene tetracarboxydiimide (NDI)-dithiophene (T2) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1-amino-4,5-8-naphthalene-tricarboxylic acid-1,8-lactam-4,5-imide) to 2 in NBA (naphthalene-bis(4,8-diamino-1,5-dicarboxyl)-amide). As the NDI-T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA. Electron mobility is greatest for N2200 (0.17 cm 2 V –1 s –1 ) followed by PNBL-3,8-T2 and PNBA-2,6-T2 (0.11 cm 2 V –1 s –1 ), 0.02 cm 2 V –1 s –1 in PNBL-4,8-T2, and negligible in PNBA-3,7-T2. Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL-4,8-T2), backbone planarity (optimum for PNBA-2,6-T2 and PNBL-3,8-T2), LUMO energy (optimum for N2200), π–π stacking distance (optimum for PNBA-2,6-T2), and film crystallinity (optimum for PNBA-2,6-T2 and N2200). These results offer generalizable insight into semiconducting copolymer design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Trigonal Planar Bis (carbene)Cu(I) Complexes Enable Divergent H 2 Activation with H 2 O for Accelerated Olefin Hydrogenation

CuH-catalyzed olefin hydrogenation is rare compared to those of carbonyl-derived substrates. Olefin insertion into Cu–H to form Cu-alkyl is ubiquitous; however, subsequent H 2 activation remains unknown to our knowledge. Herein, we investigated the transformations of β-H elimination, H 2 cleavage, and catalytic olefin hydrogenation in a series of linear and trigonal planar Cu(I)-alkyl complexes supported by monodentate N-heterocyclic carbene and bidentate naphthyridine- bis (carbene) ligands, respectively. Contrary to unreactive linear species, trigonal planar variants promote β-H elimination, hydrogenolysis, and catalytic hydrogenation of unactivated alkenes at mild temperatures and H 2 pressure. The rare isolation of a naphthyridine- bis (carbene)CuH monomer further affirms two predominant competing pathways for H 2 cleavage of metal–ligand cooperativity at Cu(I)-alkyl or internal electrophilic substitution at Cu(I)-OH. Employing either isolated or in situ generated Cu(I)-OH complex, via protonolysis of alkyl precatalyst by adventitious water, significantly accelerated catalysis compared to that operating primarily by the metal–ligand cooperativity pathway. DFT calculations and energy decomposition analysis on the disparate β-H elimination reactivity between linear and trigonal planar tert-butyl complexes and the mechanism of H 2 activation at a hydroxide complex, indicate that coordination geometry at Cu(I) and properties of the naphthyridine- bis (carbene) ligand are integral to the transformations reported here.

ALMO-EDA↗
DOE OSTI2025

Polysulfamates as “Macroisosteres” of Polyurethanes with Improved Degradability

Abstract Addressing the environmental persistence of plastics requires the development of next‐generation polymers that combine high performance with enhanced degradability. Progress toward this grand challenge has been impeded, in part, by the absence of a general blueprint for the macromolecular design of such materials. Herein, we introduce a “macroisostere” design strategy, where the carbonyl group (–CO–) in polyurethanes (PUs) is replaced with a sulfonyl group (–SO 2 –), resulting in a virtually unknown family of polymers called polysulfamates. This approach, inspired by the use of bioisosteres in drug discovery, aims to preserve key interchain interactions that contribute to thermomechanical performance while enhancing the hydrolytic lability of the polymer backbone. The optimization of a Sulfur(VI) Fluoride Exchange (SuFEx) polymerization allowed the synthesis of ten polysulfamates structurally analogous to common PUs. Comparative analysis of one PU and its polysulfamate analog showed that this isosteric substitution increases thermal stability, slightly lowers the glass transition temperature, and retains similar hardness and reduced Young's modulus. Notably, the S(VI)‐based polysulfamate demonstrated significantly enhanced hydrolytic degradability. These results highlight the potential of the “macroisostere” approach as a generalizable strategy for designing high‐performance, degradable alternatives to traditional plastics.

Chemistry↗
DOE OSTI2025

Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol

Abstract These studies reveal the first structure ofClostridium acetobutylicumalcohol dehydrogenase (CaADH), a protein exhibiting remarkable substrate promiscuity and stereochemical fidelity. The CaADH enzyme is utilized here for synthesizing 20 potential aryl isoserine side chains for the Taxotere family of tubulin‐binding chemotherapeutics. The approach involves dynamic reductive kinetic resolution (DYRKR) upon the corresponding α‐chloro‐β‐keto esters, showing high D‐synstereoselectivity, including those leading to the clinically relevant milataxel (Ar = 2‐furyl) and simotaxel (Ar = 2‐thienyl) side chains. Furthermore, various cross‐coupling chemistries performed on thep‐bromophenyl isoserine side chain significantly enhance the structural diversity of the taxoid side chain library obtained (16 additional taxoid side chains). The CaADH structure is notable: (i) the nicotinamide cofactor is bound in ananti‐conformation, with the amide carbonyl occupying the ketone binding pocket, and (ii) a flexible loop near the active site likely contributes to the remarkable substrate promiscuity observed in CaADH. We present our perspective on the dynamic nature of the CaADH active site through molecular dynamics simulation, proposing a halogen bonding model as a potential mechanism for the remarkable selectivity for an (S)‐configured C─Cl bond, in addition to the D‐facial selectivity, demonstrated across 20 diverse substrates by this remarkable short‐chain dehydrogenase enzyme.

Chemistry↗
DOE OSTI2025

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants↗
DOE OSTI2023

Three-dimensional Polymers as Organic Cathodes for Affordable and Sustainable Sodium/Potassium-ion Batteries

Redox-active polymers (RAPs) are promising organic electrode materials for affordable and sustainable batteries due to their flexible chemical structures and negligible solubility in the electrolyte. Developing high-dimensional RAPs with porous structures and crosslinkers can further improve their stability and redox capability by reducing the solubility and enhancing reaction kinetics. Further, this work reports two three-dimensional (3D) RAPs as stable organic cathodes in Na-ion batteries (NIBs) and K-ion batteries (KIBs). Carbonyl functional groups are incorporated into the repeating units of the RAPs by the polycondensation of Tetrakis(4-aminophenyl)methane and two different dianhydrides. The RAPs with interconnected 3D extended conjugation structures undergo multi-electron redox reactions and exhibit high performance in both NIBs and KIBs in terms of long cycle life (up to 8000 cycles) and fast charging capability (up to 2 A g -1 ). The results demonstrate that developing 3D RAPs is an effective strategy to achieve high-performance, affordable, and sustainable NIBs and KIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Realization of an Asymmetric Non‐Aqueous Redox Flow Battery through Molecular Design to Minimize Active Species Crossover and Decomposition

Abstract This communication presents a mechanism‐based approach to identify organic electrolytes for non‐aqueous redox flow batteries (RFBs). Symmetrical flow cell cycling of a pyridinium anolyte and a cyclopropenium catholyte resulted in extensive capacity fade due to competing decomposition of the pyridinium species. Characterization of this decomposition pathway enabled the rational design of next‐generation anolyte/catholyte pairs with dramatically enhanced cycling performance. Three factors were identified as critical for slowing capacity fade: (1) separating the anolyte–catholyte in an asymmetric flow cell using an anion exchange membrane (AEM); (2) moving from monomeric to oligomeric electrolytes to limit crossover through the AEM; and (3) removing the basic carbonyl moiety from the anolyte to slow the protonation‐induced decomposition pathway. Ultimately, these modifications led to a novel anolyte–catholyte pair that can be cycled in an AEM‐separated asymmetric RFB for 96 h with >95 % capacity retention at an open circuit voltage of 1.57 V.

Shrestha, Anuska↗
DOE OSTI2022

E ‐selective Semi‐hydrogenation of Alkynes under Mild Conditions by a Diruthenium Hydride Complex

Abstract The synthesis, characterization and catalytic activity of a new class of diruthenium hydrido carbonyl complexes bound to the t Bu PNNP expanded pincer ligand is described. Reacting t Bu PNNP with two equiv of RuHCl(PPh 3 ) 3 (CO) at 140 °C produces an insoluble air‐stable complex, which was structurally characterized as [Ru 2 ( t Bu PNNP)H(μ‐H)Cl(μ‐Cl)(CO) 2 ] ( 1 ) using solid‐state NMR, IR and X‐ray absorption spectroscopies and follow‐up reactivity. A reaction with KO t Bu results in deprotonation of a methylene linker to produce [Ru 2 ( t Bu PNNP * )H(μ‐H)(μ‐O t Bu)(CO) 2 ] ( 3 ) featuring a partially dearomatized naphthyridine core. This enables metal‐ligand cooperative activation of H 2 analogous to the mononuclear analogue, [Ru( t Bu PNP*)H(CO)]. In contrast to the mononuclear system, the bimetallic analogue 3 catalyzes the E ‐selective semi‐hydrogenation of alkynes at ambient temperature and atmospheric H 2 pressure with good functional group tolerance. Monitoring the semi‐hydrogenation of diphenylacetylene by 1 H NMR spectroscopy shows the intermediacy of Z ‐stilbene, which is subsequently isomerized to the E ‐isomer. Initial findings into the mode of action of this system are provided, including the spectroscopic characterization of a polyhydride intermediate and the isolation of a deactivated species with a partially hydrogenated naphthyridine backbone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

17 O NMR Spectroscopy Reveals CO 2 Speciation and Dynamics in Hydroxide-Based Carbon Capture Materials

Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17 O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO 2 capture systems by 17 O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO 2 capture products, finding that 17 O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO 2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs) – MFU-4l and KHCO 3 -cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning force fields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO 3 -CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO 2 capture materials by 17 O NMR.

NMR spectroscopy↗
DOE OSTI2025

Unraveling Electronic Effects that Influence the Bimolecular Chemistry of Fluorinated Criegee Intermediates

Ozonolysis is important for the removal of unsaturated volatile organic compounds emitted into the Earth's atmosphere. The alkene + ozone reaction (alkene ozonolysis) forms a carbonyl oxide – a Criegee intermediate (CI). CIs are interesting from an atmospheric chemistry perspective. They are implicated in enhancing the oxidizing capacity of the troposphere and in secondary organic aerosol formation. CIs may participate in bimolecular reactions with trace atmospheric vapors like water and methanol. Here, the chemistry of the two isomers of CFHOO and of CF 3 CHOO with water, water dimer, and methanol is explored. The present study confirms that the syn-conformer is the minimum energy structure for both CIs and that the reactions of anti-CFHOO display slightly lower activation energies cf. syn-CFHOO, thus promoting faster reaction. For both syn- and anti-CFHOO, the energy barrier in the pathway to adding water, water dimer, or methanol is lower—and the overall reaction exoergicity greater—than for the corresponding reactions involving the nonfluorinated analogue, CH 2 OO. Here, the corresponding bimolecular reaction rates are thus predicted to be faster for CFHOO than CH 2 OO. Similar reactivity trends are found when comparing the same reactions of syn-CF 3 CHOO, cf. syn-CH 3 CHOO, but not when comparing the energetics of the reactions involving anti-CF 3 CHOO cf. anti-CH 3 CHOO.

Guidry, Lily M. [University of Louisiana at Lafaye↗
DOE OSTI2024

A New Triketone Ligand for Extraction of Lithium from Brines**

Recovery of lithium from brines by liquid-liquid solvent extraction (LLE) with diketones and synergistic co-ligands has been investigated for decades, but industrial application has been limited. In pursuit of a ligand with improved properties, a series of ketonamides with beta-carbonyl groups were designed, synthesized, and tested in extraction of lithium from sulfate and carbonate simulants of clay mineral tailing leachates. The best performing ligand, a novel tricarbonyl amide, was characterized for lithium extraction with and without four synergistic co-ligands. Further, the tricarbonyl amide combined with the synergistic co-ligand Cyanex-923 was absorbed on a resin support. The ligand-modified resin was tested for performance in extraction of dilute brine simulants and up to 60 % recovery of lithium was achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Lipids status and copper in a single astrocyte of the rat model for amyotrophic lateral sclerosis: Correlative synchrotron-based X-ray and infrared imaging

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease, causing death of motor neurons controlling voluntary muscles. The pathological mechanisms of the disease are only partially understood. The hSOD1-G93A ALS rat model is characterized by an overexpression of human mutated SOD1, causing increased vulnerability by forming intracellular protein aggregates, inducing excitotoxicity, affecting oxidative balance and disturbing axonal transport. In this study we followed the bio-macromolecular organic composition and compartmentalization together with trace metal distribution in situ in single astrocytes from the ALS rat model and compared them to the control astrocytes from nontransgenic littermates by simultaneous use of two synchrotron radiation-based methods: Fourier transform infrared microspectroscopy (SRFTIR) and hard X-ray fluorescence microscopy (XRF). Here we show that ALS cells contained more Cu, which colocalized with total lipids, increased carbonyl groups and oxidized lipids, thus implying direct involvement of Cu in oxidative stress of lipidic components without direct connection to protein aggregation in situ.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Phaseolus vulgaris SUT1.1 is a high affinity sucrose–proton co–transporter

Plant sucrose transporters are required for phloem loading, and therefore are essential for plant growth and development. In common beans (Phaseolus vulgaris) there are only two sucrose transporters functionally characterized. Through a previous RNA-seq study, we identified a putative sucrose transporter in common bean, which we hypothesize to function in import of sucrose into plant cells. In silico analysis revealed that PvSUT1.1 is a putative sucrose-proton co-transporter distinct from other characterized sucrose transporters in common bean indicating that this is a previously undescribed transporter protein in beans. Further analysis revealed that PvSUT1.1 shares high protein sequence homology to the phloem loader Arabidopsis SUC2; both have 12 transmembrane domains, a typical characteristic of plant sucrose transporters. Heterologous expression in yeast further showed PvSUT1.1 to be functional and it imported sucrose into yeast cells with a K m of 0.7 mM sucrose. Import of sucrose through PvSUT1.1 is also pH-dependent with highest uptake at pH 4.0, and activity is lost in the presence of the uncoupler carbonyl cyanide 3-chlorophenylhydrazone. Consistent with identification of PvSUT1.1 as a Type I transporter, PvSUT1.1 also transports esculin. Finally, PvSUT1.1 showed expression in multiple tissues and the protein was localized to the plasma membrane. The results show that PvSUT1.1 is a sucrose transporter that is probably involved in the uptake of sucrose into source and sink cells. The potential role of PvSUT1.1 in leaf phloem loading of sucrose in common beans and its importance in heat tolerance of reproductive tissues are further discussed.

59 BASIC BIOLOGICAL SCIENCES↗