New insights into the complex architecture of siliceous copepod teeth

Copepods belong to the dominant marine zooplankton taxa and play an important role in particle and energy fluxes of the marine water column. Their mandibular gnathobases possess tooth-like structures, so-called teeth. In species feeding on large proportions of diatoms these teeth often contain silica, which is very probably the result of a coevolution with the siliceous diatom frustules. Detailed knowledge of the morphology and composition of the siliceous teeth is essential for understanding their functioning and their significance in the context of feeding interactions between copepods and diatoms. Based on analyses of the gnathobases of the Antarctic copepod Rhincalanus gigas, the present study clearly shows, for the first time, that the silica in the siliceous teeth features large proportions of crystalline silica that is consistent with the mineral α-cristobalite and is doped with aluminium. The siliceous structures have internal chitinous fibre networks, which are assumed to serve as scaffolds during the silicification process. The compact siliceous teeth of R. gigas are accompanied by structures with large proportions of the elastic protein resilin, likely reducing the mechanical damage of the teeth when the copepods feed on diatoms with very stable frustules. The results indicate that the coevolution with diatom frustules has resulted in gnathobases exhibiting highly sophisticated composite structures.     

Dissection of the frustules of the diatom Synedra acus under the action of picosecond impulses of submillimeter laser irradiation

Diatom algae realize highly intriguing processes of biosynthesis of siliceous structures in living cells under moderate conditions. Investigation of diatom physiology is complicated by frustule (siliceous exoskeleton). Frustules consist of valves and girdle bands which are adhered to each other by means of organic substances. Removal of the frustule from the lipid membrane of diatom cells would open new possibilities for study of silicon metabolism in diatoms. We found that submillimeter laser irradiation produced by a free-electron laser causes splitting of diatom frustules without destruction of cell content. This finding opens the way to direct study of diatom cell membrane and to isolation of cell organelles, including silica deposition vesicles. We suppose that the dissection action of the submillimeter irradiation results from unusual ultrasonic waves produced by the short (30–100 ps) but high-power (1 MW) terahertz laser impulses at 5.6 MHz frequency.     

The Probable Mechanism for Silicon Capture by Diatom Algae: Assimilation of Polycarbonic Acids with Diatoms—Is Endocytosis a Key Stage in Building of Siliceous Frustules?

Many organisms including unicellular (diatoms, radiolaria, and chrysophytes), higher plants (rice and horsetail) and animals (sponges) use silica as a main part of skeletons. The bioavailable form of silicon is silicic acid and the mechanism of silicic acid penetration into living cells is still an enigma. Macropinocytosis was assumed as a key stage of the silicon capture by diatoms but assimilation of monomeric silicic acid by this way requires enormous amounts of water to be passed through the cell. We hypothesized that silicon can be captured by diatoms via endocytosis in the form of partially condensed silicic acid (oligosilicates) whose formation on the diatom surface was supposed. Oligosilicates are negatively charged nanoparticles and similar to coils of poly(acrylic acid) (PAA). We have synthesized fluorescent tagged PAA as well as several neutral and positively charged polymers. Cultivation of the diatom Ulnaria ferefusiformis in the presence of these polymers showed that only PAA is able to penetrate into siliceous frustules. The presence of PAA in the frustules was confirmed with chromatography and PAA causes various aberrations of the valve morphology. Growth of U. ferefusiformis and two other diatoms in the presence of tri- and tetracarbonic fluorescent tagged acids points to the ability of diatoms to recognize substances that bear four acidic groups and to include them into siliceous frustules. Thus, partial condensation of silicic acid is a plausible first stage of silicon assimilation.     

Diatom microfossils from cretaceous and eocene sediments contain native silica precipitating long‐chain polyamines

Organic molecules from known biological sources (biomarkers) that are preserved over geological time are critical tools in the study of past conditions and events on earth. Polar molecules are typically recycled rapidly in marine environments and do not survive burial within aquatic sediments in unambiguously recognizable form. As such, geological biomarkers are formed almost exclusively from precursor biomolecules that have been altered, limiting their utility as paleoproxies. Here, we report that nitrogen‐rich aliphatic long‐chain polyamines (LCPAs), biosynthesized by diatoms in species‐specific assemblages for the precipitation of nanopatterned siliceous cell walls (frustules), are preserved unaltered in the oldest available diatom fossils dating to the Lower Cretaceous (early Albian, 115–110 Ma). We further show that the cumulative LCPA pool accounts for 60% of the total C and 80% of the total N preserved in the Cretaceous age sediments. We suggest that silica glass formation by diatoms constitutes an important preservation mechanism for source‐specific, polar biomolecules, protecting them indefinitely by encapsulation within the silicified frustule. LCPAs are a unique, source‐specific carbon and nitrogen archive of diatom biomass, offering a promising tool for reconstruction of global cycles of carbon and nitrogen over geological timescales.     

Silicon nanotechnologies of pigmented heterokonts

Many pigmented heterokonts are able to synthesize elements of their cell walls (the frustules) of dense biogenic silica. These include diatom algae, which occupy a significant place in the biosphere. The siliceous frustules of diatoms have species-specific patterns of surface structures between 10 and a few hundred nanometers. The present review considers possible mechanisms of uptake of silicic acid from the aquatic environment, its transport across the plasmalemma, and intracellular transport and deposition of silica inside the specialized Silica Deposition Vesicle (SDV) where elements of the new frustule are formed. It is proposed that a complex of silicic acid with positively charged proteins silaffins and polypropylamines remains a homogeneous solution during the intracellular transport to SDV, where biogenic silica precipitates. The high density of the deposited biogenic silica may be due to removal of water from the SDV by aquaporins followed by syneresis--a process during which pore water is expelled from the network of the contracting gel. The pattern of aquaporins in the silicalemma, the membrane embracing the SDV, can determine the pattern of species-specific siliceous nanostructures.     

硅藻纳米技术

硅藻是一类微小的单细胞藻类,具有由无定形氧化硅组成的坚硬细胞壁(硅壳).硅壳具有精致的形态和结构,且随硅藻种类和生长条件不同而千变万化.目前估算的硅藻种类超过200 000种,其独特的纳米结构对光子结构、化学生物传感器、新纳米材料和器件的开发具有启发意义.同时硅藻形态形成学和分子生物学的研究,可以推动硅质材料的仿生合成...     

EVIDENCE OF AN ORGANIC MATRIX FROM DIATOM BIOSILICA1

Most biominerals appear to be composites of organic material and mineral. Whether biosilica is such a composite is unresolved because of a lack of evidence for such organic components. We present evidence that organic material exists within diatom biosilica and can be extracted using HF/NH₄F solutions from frustules isolated from Cyclotella meneghiniana Kütz and diatomaceous earth. To eliminate organic casing on the silicified frustules as a source of organic materials, the casing was removed by oxidation of frustules with NaOCl before extraction. The removal of the casing was confirmed in that oxidized frustules no longer displayed the ability to be stained with ruthenium red and fluorescamine. Frustules examined with EDXA showed an emission peak from sulfur before treatment but no peak following treatment, indicating that oxidation removed organic sulfur. The organic material obtained from extracts of fresh frustules contained both soluble and insoluble components. Only soluble material was evident in extracts from diatomaceous earth. The soluble material appears to contain glycoproteins with relatively high levels of serine and glycine. The soluble proteins from fresh frustules also appear to be phosphorylated. Indirect evidence is presented that suggests the soluble proteins may contain regions of primary structure enriched in anionic amino acids. The soluble extracts differ from general cell contents when the two fractions are compared, suggesting that frustules contain specialized organic material. The identification of silica-specific organic material suggests that mineralization in diatoms may be in part matrix-mediated.     

Effect of bacteria from the bottom water layer of lake baikal on degradation of diatoms

Among isolates of the eubacteria Brevundimonas bullata, Sphingomonas rhizogenes, Agrobacterium tumefaciens, Bacillus simplex, Acinetobacter johnsonii, Methylobacterium adhaesivum, and Deinococcus aquaticus isolated from the bottom layer on the medium, where the only source of organic matter was hydrolysate from diatoms, the activity of hydrolytic enzymes, such as proteases, β-xylosidase, β-glucosidase, β-galactosidase, chitobiase, and amylase, is revealed. An algicidal effect and degradation of siliceous diatom frustules are recorded in algal-bacterial cultures. These data show that the bottom water layer of Lake Baikal is inhabited by potential participants of silicon cycle, which degrade siliceous valves of diatoms.     

Novel fluorescent dyes based on oligopropylamines for the in vivo staining of eukaryotic unicellular algae

Weakly basic fluorescent dyes are used to visualize organelles within live cells due to their affinity to acidic subcellular organelles. In particular, they are used to stain the silica deposited in the silica deposition vesicles (SDVs) of diatoms during the course of their frustule synthesis. This study involved the synthesis of fluorescent dyes derived from oligopropylamines, compounds similar to those found in diatoms. The dyes were obtained by reacting oligopropylamines with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole. The reaction was realized using methylated oligopropylamines with two or three nitrogen atoms and yielded two novel fluorescent dyes: NBD-N2 and NBD-N3. The dyes appeared to be highly efficient in the in vivo staining of growing siliceous frustules of diatoms at concentrations at least 10 times lower than those required for staining with HCK-123. NBD-N3 also efficiently stained other subcellular vesicles of eukaryotic unicellular algae. NBD-N2 stained only growing diatom frustules, whereas NBD-N3 also stained various subcellular organelles of different eukaryotic unicellular algae. NBD-N2 and NBD-N3 were not removed from stained diatom frustules by drastic treatments with H₂SO₄ and H₂O₂. Fluorescent silica can also be obtained by its chemical precipitation in the presence of NBD-N2 and NBD-N3.     

Associations of diatoms in the surficial sediments of lakes and peat pools in Atlantic Canada

The distribution of diatom frustules in the surficial sediments of lakes and ombrotrophic peat pools in Atlantic Canada are examined especially in relation to pH and bog lake succession. Sedimentary diatom associations for peat pools, strongly acidic lakes, and weakly acidic lakes are characterized. These associations and the derived diatom-pH calibration functions will facilitate improved paleoecological interpretation of natural ontogenetic pathways and assessments of recent anthropogenic impacts.     

The ratio of diatom frustules to chrysophycean statospores: A useful paleolimnological index

Stratigraphic analyses of the postglacial sediments of Little Round Lake and the recent sediments of two additional southern Ontario lakes were used to compare the relative abundance of fossil diatom frustules to chrysophycean statospores. Relatively few statospores were recorded during eutrophic phases in the lakes' histories such as during periods of anthropogenic activity in the lakes' catch me nt, when diatom frustules were abundant. The increased relative abundance of statospores during the early postglacial in Little Round Lake was attributed to both oligotrophy and a short growing season, conditions that currently exist in many high arctic lakes. From these data it is seen that the ratio of fossil diatom frustules to chrysophycean statospores may provide a useful paleolimnological index of trophic status in temperate lakes. The advantages of this index include its simplicity, the fact that frustules and statospores can be enumerated from the same microscope slides, and that the ratio is independent of sedimentation rates.     

Luminescence properties of a nanoporous freshwater diatom

Freshwater diatom frustules show special optical properties. In this paper we observed luminescence properties of the freshwater diatom Cyclotella meneghiniana. To confirm the morphological properties we present scanning electron microscopy (SEM) images. X‐ray diffraction (XRD) studies were carried out to visualize the structural properties of the frustules, confirming that silica present in diatom frustules crystallizes in an α‐quartz structure. Study of the optical properties of the silica frustules of diatoms using ultra‐violet‐visible (UV‐vis) spectroscopy and photoluminescence spectroscopy confirmed that the diatom C. meneghiniana shows luminescence in the blue region of the electromagnetic spectrum when irradiated with UV light. This property of diatoms can be exploited to obtain many applications in day‐to‐day life. Also, using time‐resolved photoluminescence spectroscopy (TRPL) it was confirmed that this species of diatom shows bi‐exponential decay. Copyright © 2011 John Wiley & Sons, Ltd.     

Diatom assemblages in superficial sediments from the Gulf of Riga,eastern Baltic Sea

Twenty one superficial sediment samples from areas of high and moderate eutrophication in the Gulf of Riga were studied with respect to siliceous microfossils, mainly diatoms.The results seem to imply that the number of taxa and the abundance of the frustules are affected by runoff from rivers and the degree of eutrophication in different parts of the Gulf. Areas with high eutrophication, e.g. the river estuaries, have diatom assemblages of varying composition, while in areas with moderate eutrophication the composition is almost constant and the influx of freshwater diatoms and littoral periphyton small. The high abundance and low diversity of brackish-marine and brackish, planktonic diatoms seem to be a result of an influx of nutrients and pollutants in the water and bottom sediments. The sea ice diatoms occurring in the Baltic waters and also in the Gulf of Riga tend to be resistant to eutrophication or are even favoured by it.     

The fascinating diatom frustule—can it play a role for attenuation of UV radiation?

Diatoms are ubiquitous organisms in aquatic environments and are estimated to be responsible for 20–25 % of the total global primary production. A unique feature of diatoms is the silica wall, called the frustule. The frustule is characterized by species-specific intricate nanopatterning in the same size range as wavelengths of visible and ultraviolet (UV) light. This has prompted research into the possible role of the frustule in mediating light for the diatoms’ photosynthesis as well as into possible photonic applications of the diatom frustule. One of the possible biological roles, as well as area of potential application, is UV protection. In this review, we explore the possible adaptive value of the silica frustule with focus on research on the effect of UV radiation on diatoms. We also explore the possible effect of the frustules on UV radiation, from a theoretical, biological, and applied perspective, including recent experimental data on UV transmission of diatom frustules.     

CYTOPLASMIC MASSES PRESERVED IN EARLY HOLOCENE DIATOMS: A POSSIBLE TAPHONOMIC PROCESS AND ITS PALEO‐ECOLOGICAL IMPLICATIONS1

In Lake Suigetsu, central Japan, greenish/light‐brown granules identified as cytoplasmic masses had been preserved in siliceous cell walls of freshwater diatoms in annual layers of lacustrine muds since the early Holocene. The lacustrine muds consisted of alternating dark‐colored (rich in diatom valves, clay, and organic matter) and light‐colored (mainly diatom valves) laminae. The greenish/light‐brown granules were predominately preserved in frustules of the genus Aulacoseira preserved in the dark‐colored laminae. The dark‐colored laminae were inferred to have formed annually under stratified water caused by surface water warming in summer that caused the formation of an organic‐rich anoxic layer on the lake bottom that favored granule preservation. The good preservation of cytoplasmic masses in dark‐colored laminae suggested a cause for diatom assemblage periodicity, a phenomenon that was commonly noted in temperate lakes: the cells containing these masses could be potential seed stocks for subsequent spring blooms. Frustules of the most abundant granule‐containing species, Aulacoseira nipponica (Skvortzow) Tuji, in the dark‐colored laminae of the Early Holocene muds were abundant in the overlying light‐colored laminae, suggesting that these species reproduced abundantly in springtime yielding a massive diatom bloom.     

Diversity of mineral cell coverings and their formation processes: a review focused on the siliceous cell coverings

Mineral cell coverings are found in various protists. Some macroalgae accumulate calcium carbonate in the intercellular space, and some unicellular organisms use calcium carbonate or silica for the construction of loricas, scales, and frustules. Diatoms are representatives of those utilizing silica for the material of the cell covering called a frustule. The development of the frustule is initiated in a silica-deposition vesicle (SDV), which occurs just beneath the plasma membrane and, subsequently, the silicified cell covering expands its area, following the expansion of the SDV from valve face to valve mantle. Sequential valve development with whole valves is reviewed in several diatoms placed in different phylogenetic positions. Every diatom commences its valve formation from its pattern center and then develops by means of individual procedures. The results indicate that the valve development reflects the phylogeny of diatoms. In addition, recent progress in silica biomineralization is briefly reviewed, and the phylogeny of ability concerning siliceous cell covering formation is inferred. Electronic Publication     

SILICON UPTAKE BY ALGAE WITH NO KNOWN Si REQUIREMENT. I. TRUE CELLULAR UPTAKE AND pH-INDUCED PRECIPITATION BY PHAEODACTYLUM TRICORNUTUM (BACILLARIOPHYCEAE) AND PLATYMONAS SP. (PRASINOPHYCEAE)1

Phaeodactylum tricornutum Bohlin, the one diatom known to lack a silicon requirement for growth, and the prasinophyte Platymonas sp. are two representatives of a taxonomically diverse group of planktonic algae that have been reported to take up Si without a demonstrable requirement for the element. For both species, removal of Si from solution during growth in batch culture has at least two components; true biological uptake throughout the growth of the culture, and spontaneous inorganic precipitation of a solid silicate phase–probably Mg₂Si₃O₈ (sepiolite)–under the elevated pH conditions that prevail late in batch growth. It is not clear to what extent previous observations of Si uptake by algae without siliceous frustules may be influenced by inorganic, non-cellular precipitation. The kinetics of true cellular uptake of Si are similar in Phaeodalylum and Platymonas, and different from those reported for the Si-requiring diatoms. Uptake follows hyperbolic saturation kinetics in both species, with half-saturation concentrations of 97.4 μM in Phaeodactylum and 80.9 μM in Platymonas, as compared to ca. 1–6 μM in diatoms that form siliceous frustules. Uptake by Phaeodactylum and Platymonas is not substrate-saturated until the dissolved Si concentration of the medium exceeds 200 μM. Concentrations this high do not occur in the surface layer of the ocean, and the kinetics suggest that both species deposit much less silica in nature than they can be induced to deposit in culture.     

Beyond micromachining: the potential of diatoms.

Diatoms are microscopic, single-celled algae that possess rigid cell walls (frustules) composed of amorphous silica. Depending on the species of diatom and the growth conditions, these frustules can display a wide range of different morphologies. It is possible to design and produce specific frustule morphologies that have potential applications in nanotechnology.     

Application of 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole in analysis: Fluorescent dyes and unexpected reaction with tertiary amines

4-Chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) is widely applied as a fluorescent tagging reagent in biochemistry, as a derivatization agent in analytical chemistry, and as a component for design of fluorescent nanoparticles. Four new 7-nitrobenzo-2-oxa-1,3-diazole (NBD)-tagged polyamines containing two to four amine moieties were synthesized and used as an effective tool for staining of siliceous frustules of the diatom algae and spicules of the siliceous sponges, including fossilized samples. An unexpected reaction between NBD-Cl and tertiary amine groups was found, giving rise to NBD-tagged amines with elimination of an alkyl group. The reaction proceeds through the Meisenheimer complex and quaternary salt, which transform to the product by Hofmann reaction (alkene elimination) or nucleophilic substitution (halogenated compound formation). In the case of polyamines, NBD-Cl causes chain scissoring, giving a set of NBD-tagged amines. The found NBD-Cl reaction with tertiary amines must be taken into account when using NBD-Cl and similar activated aromatic systems for amine derivatization in analytical and biochemistry applications. The reaction with polyamines opens the way to libraries of NBD-tagged compounds.     

Sedimentation of biogenic siliceous particles in Antarctic waters from the Atlantic sector

Sediment traps were deployed in the Drake Passage, Bransfield Strait and west of South Orkney Islands (Powell Basin) during December 1980/ January 1981, December 1983, and between March and December 1983, respectively.Most of the trapped material is biogenic opal except in the lower half of the water column in Bransfield Strait where large amounts of resuspended aluminosilicates and quartz grains were present. Frustules and skeletons of siliceous microorganisms (diatoms, silicoflagellates, radiolarians, chrysophycean cysts), fragments and moults of crustaceans and tests of foraminifera were found. Quantitatively diatoms are the dominant constituent of the trapped biogenic material.Alteration of diatom assemblages in the water column is due to mechanical breakdown by grazing zooplankton. It mainly affects large frustules (e.g. Corethron criophilum Castracane) in the uppermost part of the water column. Dissolution of frustules occurs mostly at the sediment/water interface and leads to the enrichment of strongly silicified valves [e.g. Nitzschia kerguelensis (O'Meara) Hasle, Thalassiosira antarctica Comber (resting spores)].At the Bransfield Strait site a large part of biogenic opal was incorporated into fecal pellets of krill and copepods. The bulk of pellet content consists of fragmented diatom frustules (1–10 μm in size). Most intact valves found in the sediments have settled through the water column by means other than fecal pellet transport: e.g. settling as solitary particles or incorporated into or attached to “Marine Snow” or “Large Amorphous Aggregates”.