Chiral assemblies of nanoparticles (NPs) are typically constructed with helical or tetrahedral geometries. Simple pairs of NPs are not expected to display chirality due to basic symmetry considerations made under the assumption of their spherical geometry. In this study we demonstrate that assemblies consisting of two metallic NPs do possess chirality and strongly rotate polarization of light. Their chiroplasmonic properties are attributed to the prolate geometry of individual colloidal particles. When bridged by biomolecules, the NP pairs acquire scissor-like geometry, with the long axes of NPs forming an angle of ~9°. This small dihedral angle results in chirality of the NP pair, while the consistency of its sign due to the specific conformation of the bridging biomacromolecules breaks the enantiomeric equivalence of the NP pairs. Strong polarization rotation in these nanoassemblies makes possible their utilization in biological analysis. Heterodimers of gold and silver NPs were made using antibody-antigen bridges. Taking advantage of their chiroplasmonic properties, we investigated their bioanalitical potential for detection of an environmental toxin, microcystin-LR, and a cancer biomarker, prostate-specific antigen. The order-of-magnitude improvements in limits of detection compared to all other analytical techniques are attributed to plasmonic enhancement of intrinsic chirality of biological compounds, strong optical coupling of photons with NP assemblies with twisted geometries, and signal amplification due to the bisignate nature of circular dichroism bands.

Polymerase chain reaction (PCR) was realized on the surface of gold nanoparticles (NPs) as a tool for self-organization at nanoscale and as a step toward programmable production of sufficient quantities of functional metallic superstructures. The assembly is controlled by varying the density of the primer on the surface of gold NPs and the number of PCR cycles generating a mixture of dimers, trimers, tetramers, etc., with gradually increasing complexity. This process leads to strong chirality of the assemblies arising from the three-dimensional positioning of NPs in space which had never been observed before. A circular dichroism band of the superstructures coincides with the plasmon oscillations of the multi-NP systems of Au colloids. This new collective optical property of NPs embracing the diversity of shapes and diameters in the starting dispersions opens unique opportunities for the development of negative index materials.

Chiral nanoscale photonic systems typically follow either tetrahedral or helical geometries that require four or more different constituent nanoparticles. Smaller number of particles and different chiral geometries taking advantage of the self-organization capabilities of nanomaterials will advance understanding of chiral plasmonic effects, facilitate development of their theory, and stimulate practical applications of chiroplasmonics. Here we show that gold nanorods self-assemble into side-by-side orientated pairs and “ladders” in which chiral properties originate from the small dihedral angle between them. Spontaneous twisting of one nanorod versus the other one breaks the centrosymmetric nature of the parallel assemblies. Two possible enantiomeric conformations with positive and negative dihedral angles were obtained with different assembly triggers. The chiral nature of the angled nanorod pairs was confirmed by 4π full space simulations and the first example of single-particle CD spectroscopy. Self-assembled nanorod pairs and “ladders” enable the development of chiral metamaterials, (bio)sensors, and new catalytic processes.

Propeller-like nanoscale assemblies with exceptionally intense chiroptical activity and strong luminescence are prepared using gold nanorods and upconversion nanoparticles. The circular dichroism intensity of the tetramer reached 80.9 mdeg, with g-factor value of 2.1 × 10(-2) . The enhancement factor of upconversion luminescence is as high as 21.3 in aqueous phase. Attomolar bioanalysis of a cancer biomarker with two model is also achieved, showing potential for early disease diagnosis and environmental monitoring.

Parallel or angle parked: Gold nanorods (see picture) were selectively modified either on the sides or ends using complementary microcystin (MC‐LR) antibody and antigen (blue). Fast detection of MC‐LR (green) was successfully achieved with these assemblies, and both sensitivity and detection ranges were markedly better for the end‐to‐end motif (right) than the side‐to‐side variant (left).

This is a prospective non-randomized cohort study of 113 consecutive patients to investigate the safety and efficacy of a short-duration intraarterial selective cooling infusion (IA-SCI) targeted into an ischemic territory combined with mechanical thrombectomy (MT) in patients with large vessel occlusion-induced acute ischemic stroke (AIS); 45/113 patients underwent IA-SCI with 350 ml 0.9% saline at 4℃ for 15 min at the discretion of the interventionalist. Key parameters such as vital signs and key laboratory values, symptomatic and any intracranial hemorrhage, coagulation abnormalities, pneumonia, urinary tract infections and mortality were not significantly different between the two groups. Final infarct volume (FIV) was assessed on noncontrast CT performed at three to seven days. After an adjusted regression analysis, the between-group difference in FIV (19.1 ml; 95% confidence interval (CI) 3.2 to 25.2; P = 0.038) significantly favored the IA-SCI group. At 90 days, no differences were found in the proportion of patients who achieved functional independence (mRS 0-2) (51.1% versus. 41.2%, adjusted odd ratio (aOR) 1.9, 95% CI 0.8-2.6, P = 0.192). Combining short-duration IA-SCI with MT was safe. There was a smaller FIV and trend towards clinical benefit that will need to be further evaluated in randomized control trials.

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Safety of water was for a long time and still is one of the most pressing needs for many countries and different communities. Despite the fact that there are potentially many methods to evaluate water safety, finding a simple, rapid, versatile, and inexpensive method for detection of toxins in everyday items is still a great challenge. In this study, we extend the concept of composites obtained impregnation of porous fibrous materials, such as fabrics and papers, by single walled carbonnanotubes (SWNTs) toward very simple but high-performance biosensors. They utilize the strong dependence of electrical conductivity through nanotubes percolation network on the width of nanotubes-nanotube tunneling gap and can potentially satisfy all the requirements outlined above for the routine toxin monitoring. An antibody to the microcystin-LR (MC-LR), one of the common culprits in mass poisonings, was dispersed together with SWNTs. This dispersion was used to dipcoat the paper rendering it conductive. The change in conductivity of the paper was used to sense the MC-LR in the water rapidly and accurately. The method has the linear detection range up to 10 nmol/L and non-linear detection up to 40 nmol/L. The limit of detection was found to be 0.6 nmol/ L (0.6 ng/mL), which satisfies the strictest World Health Organization standard for MC-LR content in drinking water (1 ng/mL), and is comparable to the detection limit of traditional ELISA method of MC-LR detection, while drastically reducing the time of analysis by more than an order of magnitude, which is one of the major hurdles in practical applications. Similar technology of sensor preparation can also be used for a variety of other rapid environmental sensors.