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guozhi2009

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Reviewer #2: This paper reports on a simpler method for synthesis of green luminescent silver clusters using bovine serum albumin as a reducing and stabilizing agent. Modifications of pH allowed a variation of the clusters size: higher pH reduced the size. The clusters show relatively low biotoxicity.
A great number of publications concern today synthesis and structural, electronic, optical and toxicological properties of silver nanoparticles. Although, the material synthesis may be of interest, the discussion is of not sufficient quality.
There is confusion of using two terms "clusters" and "nanopartiocles": the difference should be explained. No discrete spectral features were observed in present study. Plasmonic effect related to "hot spots" appearance was not verified. The reported absorption band at 305 nm does not fit the silver plasmon position. The observed green luminescence can belong to oxidised silver and not to metallic silver as proposed by authors. No modification of the spectral bands positions was observed when the size changed. In the same time, the blue shift of the absorption is explained by a small size of the prepared nanoparticles (page 10).
Why spherical particles possess an increased number of 111 planes (page 12)?
The Ag peak is not "obvious" in the presented EDS picture (figure 5b).
Two indicated thiol stretching modes behave differently: one increases and another decreases in intensity (pages 13-14). The explanation is absent.
The peak at 2590 cm-1 intensifies (relative to background) and not weakens as stated in page 13. The same remark concerns discussion of some other peaks.
The toxicity of silver nanoparticles (at least, in major part) depends on released silver ions. The stability of silver clusters in aqueous solutions (stated in Conclusions) is not shown. The dissolution measurements have to be carried out in order to compare toxicities of different silver samples.
Some phrases are misleading, e.g. "within the possible inevitable error" (page 15), "monodisperse Ag clusters exhibit a narrow size distribution" (page 11).
Exclamations "excellent biocompatibility", "unique study" etc. have to be avoided.
English has to be improved.
Summing up, this manuscript cannot be recommended for publication.



Reviewer #4: This manuscript describes the formation of a green-emitting fluorescence Ag Clusters. From the content point of view, this manuscript does not provide any significant new contribution to the existing knowledge. There are several serious concerns that should be addressed, mostly to the obtained results and their interpretation.
First, the title of the manuscript is not adequate. What does it mean the term "relatively" low biotoxiticy? Furthermore, the Abstract section is not concise and informative and should clearly describe obtained results from this study. Obviously, first two sentences from Abstract section should be removed. The manuscript requires improvement in written language.
The use of BSA is well-known and omnipresent approach in preparation methods of many solids, especially in formation of silver nanoparticles and silver nanocomposites. I am confident that the novelty in preparation methods is lacking and that the manuscript does not provide any significant contribution to the existing knowledge.
Serious weakness of this manuscript is inadequate morphological, structural and surface physic-chemical characterization of obtained precipitates. The authors claim that they measured hydrodynamic diameters and zeta potential of obtained particles by Nano-ZS Malvern's instrument (page 5). Surprisingly, the surface charge of obtained precipitates was not presented and discussed in the manuscript.  Furthermore, DLS histograms displayed as inset in Figure 4 are very unusual.  I wonder why authors did not use appropriate Malvern's softer to analyse and present obtained DLS results. The quality of TEM microphotographs displayed in Figure 4 is inadequate. These do not show important size and morphological features of obtained solids. XRD pattern shown in figure 5 does not properly describe structural characteristics of obtained silver nanoparticles. It is not clear which peaks are assigned as (200) (220) and (311) crystal planes. The authors concluded that "high intensity of (111)
peak indicates that their silver solids have large number of (111) planes". All silver compounds have the same number of this crystal planes.  However, these planes were more exposed to X-ray during analyses as a result of oriented samples. It seems that authors ignore some fundamental aspects of crystallography and XRD analyses.


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