Teratozoospermia is characterized by the presence of spermatozoa with abnormal morphology over 85 % in sperm. When all the spermatozoa display a unique abnormality, teratozoospermia is said to be monomorphic. Two forms of monomorphic teratozoospermia, representing less than 1 % of male infertility, are recognized: macrozoospermia (also called macrocephalic sperm head syndrome) and globozoospermia (also called round-headed sperm syndrome). Macrozoospermia is defined as the presence of a very high percentage of spermatozoa with enlarged head and multiple flagella. Meiotic segregation studies in 30 males revealed that over 90 % of spermatozoa were aneuploid, mainly diploid. Sperm DNA fragmentation studies performed in a few patients showed an increase in DNA fragmentation index compared to fertile men. Four mutations in the AURKC gene, a key player in meiosis and more particularly in spermatogenesis, have been found to be responsible for macrozoospermia. Globozoospermia is characterized by round-headed spermatozoa with an absent acrosome, an aberrant nuclear membrane and midpiece defects. The rate of aneuploidy of various chromosomes in spermatozoa from 26 globozoospermic men was slightly increased compared to fertile men. However, this increase was of the same order as that commonly found in infertile men with altered sperm parameters. The majority of the studies found that globozoospermic males had a sperm DNA fragmentation index higher than in fertile men. Mutations or deletions in three genes, SPATA16, PICK1 and DPY19L2, have been shown to be responsible for globozoospermia. Identification of the genetic causes of macrozoospermia and globozoospermia should help refine diagnosis and treatment of these patients, avoiding long and painful treatments. Elucidating the molecular causes of these defects is of utmost importance as intracytoplasmic sperm injection (ICSI) is very disappointing in these two pathologies.

Tailoring the surface chemistry of gold nanorods is a key factor for successful applications in biology, catalysis, and sensing. Here, we report on the use of the diazonium salt chemistry for the functionalization of gold nanorods enabling the formation of strongly attached organic layers around the gold cores. The precise nature of the interface between the gold surface and the diazonium-derived aryl layers was probed by XPS, ToF-SIMS, SERS, and DFT. It was shown that the CTAB surfactant was partially exchanged by the diazonium salt which dediazonizes spontaneously to form Au–C covalent bonds with the surface. Interestingly, the silver used during the synthesis of gold nanorods and still present at their surface appears to be also involved in the grafting mechanism with Ag–C covalent bonds detected by ToF-SIMS. From this result, it is clear that the interfacial properties and reactivity of gold nanorods synthesized by the silver(I)-assisted seed mediated growth approach are strongly influenced by the presence of silver.

Infertility is estimated to affect up to 15% of couples of reproductive age. Among the male factors, globozoospermia (also called round-headed sperm syndrome) is a rare type of teratozoospermia accounting for <0.1% of male infertility. Lack of acrosome, whose production is a postmeiotic event in spermatogenesis, and round sperm head are its main characteristics. The acrosomeless spermatozoon is unable to go through the zona pellucida and fuse with the oolemma of the oocyte, and fertilisation failures have been attributed to a deficiency in oocyte activation capacity, even when intracytoplasmic sperm injection (ICSI) is attempted. The pathogenesis of this anomaly is still unclear but genetic factors are likely to be involved. DNA fragmentation rate has been reported for 16 globozoospermic males, usually using the terminal uridine nick-end labelling (TUNEL) assay. Most of the patients had a DNA fragmentation index (DFI) higher than that in fertile men. The rate of aneuploidy for some specific chromosomes was increased in 12 among the 26 globozoospermic males reported in the literature. The same results (high DFI and aneuploidy rates) were observed in infertile males compared to fertile men, notably in those with oligoasthenozoospermia or teratozoospermia, independently of the origins. Mutations or deletions in three genes, SPATA16, PICK1 and DPY19L2, have been shown to be responsible for globozoospermia. Proteins coded by the first two genes localise to the Golgi apparatus and the proacrosomal granules that are transported in the acrosome. It is likely that other proteins involved in the acrosome formation remain to be identified.

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Gold nanoparticles (AuNPs) have been the subject of intensive work recently due to their outstanding optical, catalytic and electronic properties. Although the morphological characteristics (size and shape) of the AuNPs largely determine their properties, their functionalization or association to other materials play a primary role for optimizing their use in various applications such as drug delivery, theranostic, catalysis and (bio)­sensing. Among the many possible options available by chemistry, the coupling of AuNPs with smart polymers is an exciting field offering the possibility to supply stimuli-responsive properties to the resulting nanocomposites. With regard to the photothermal properties of AuNPs, their combination with thermoresponsive polymers, such as poly­(N-isopropylacrylamide) (PNIPAM) is particularly promising, likely to generate new synergies between the polymer component and the metallic nanoparticles. Despite such unique and intriguing advantages of AuNPs–PNIPAM nanocomposites, there is no exclusive review regarding this field at the interface between plasmonics and thermoresponsive polymers. To fill this gap, this review describes the general methods for preparing AuNPs–PNIPAM nanocomposites and their potential applications, highlighting the added-value properties emerging from the combination of AuNPs and PNIPAM in a single composite. New outlook for the near future to merge multiple functions at the nanometer scale and integrate building materials of various chemical nature (such as other stimulable polymers or the combination of AuNPs with other metals) into the same active plasmonic platform is described as well, emphasizing innovative approaches to improve their functionalities.

Site-selective surface functionalization of anisotropic gold nanoparticles represents a major breakthrough for fully exploiting nanoparticle anisotropy. In this paper, we explore an original strategy for the regioselective functionalization of lithographically designed gold nanorods (AuNRs), based a combination of photo-induced plasmon excitation and aryl diazonium salt chemistry.

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Plasmon-mediated multi-functionalization of nanoparticles is presented, in order to achieve the grafting of various chemical groups in distinct nanoscale regions.